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ENCYCLOPEDIA OF EXPLOSIVES
AND
RELATED ITEMS
PATR 2700
VOLUME 7

BY

BASIL T. FEDOROFF & OLIVER E. SHEFFIELD

ASSISTED BY

SEYMOUR M. KAYE & MANAGEMENT SCIENCE ASSOCIATES

U.S. ARMY RESEARCH AND DEVELOPMENT COMMAND

TACOM, ARDEC
WARHEADS, ENERGETICS AND COMBAT SUPPORT CENTER
PICATINNY ARSENAL
NEW JERSEY, USA
1975
 Copies of the “Encyclopedia of Explosives
And Related Items” can be obtained by requesting CD ROM
from the:

National Technical Information Service

(formerly Clearinghouse)
US Department of Commerce
Springfield, Virginia 22151

1-800-553-6847 USA only

703-605-6000
www.ntis.gov/FCPC

The contents of these volumes are UNCLASSIFIED

The distribution of these volumes is UNLIMITED

Neither the US Government nor any person acting on behalf of

the US Government assumes any liability resulting from the use or
publication of the information contained in this document or warrants
that such use or publication will be free from privately owned rights.

All rights reserved. This document, or parts thereof, may not be

reproduced in any form without written permission of the
Energetics and Warhead Division, WECAC, TACOM, ARDEC, Picatinny Arsenal

Library of Congress Catalogue Card Number: 61-61759

 1

PREFACE

This volume represents a continuing effort to cover comprehensively the unclassified

information on explosives and related subjects in the same manner and format as in
previous volumes. The reader is urged to obtain the previous volumes and to read both
the PREFACE and INTRODUCTION in Volume 1 in order to understand the authors’
way of presenting the subject matter

In preparation for and during the writing of this Encyclopedia, the authors have con-
sulted freely with and have had the cooperation’ of many individuals who contributed
their expert knowledge and advice. This fact is acknowledged throughout the text at the
end of the subject item. A listing of many others who have helped in various ways would
be impractical

Dr Julius Roth, principal scientist at Management Science Associates, Los Altos,

California, contributed significantly in the literature searching and writing of many of
the articles for this volume under Contract DAAA21 -73-C-0725. Mr Henry Herman of
the Explosives Division assisted with proofreading and literature searching. Others who
contributed to the manuscript, by invitation are indicated at the end of the articles

Dr Raymond F. Walker, Explosives Division Chief, provided the financial support

and encouragement to continue this work. Further financial support is expected from
the sale of copies to non-governmental agencies and individuals by the National Technical
Information Service, US Department of Commerce, Springfield, Virginia 22151

Although considerable effort has been made to present this information as accurately
as possible, mistakes and errors in transcription and translation do occur. Therefore, the
authors encourage the readers to consult original sources, when possible, and to feel free
to point out errors and omissions of important works so that corrections and additions
can be listed in the next volume. The interpretations of data and opinions expressed are
often those of the authors and are not necessarily those nor the responsibility of officials
of Picatinny Arsenal or the Department of the Army

This report has been prepared for information purposes or-slyand neither Picatinny
Arsenal nor the Department of the Army shall be responsible for any events or decisions
arising from the use of any information contained herein
 111

ADDENDUM

Heptryl, listed in VOl 7 of Encycl, p H64-L and described in Vol 1, pp A44 I –42 as
N-(2,4,6- Trirritro-N-nitranilino)-trimethylolmethane Trinitrate is claimed now by Dr
Paolo Amat di San Filippo in a letter of June 25, 1975 addressed to the Feltman Re-
search Laboratory Director, to be identical with Eptrile described by him and Dr Michele
Giua (who died in 1966) in Annali di Chimica, Vol 50, 1381 –88 (1960). This claim is
not correct becauseHeptryl has the formula
,C(CH2.0N02)3
N.

while Eptril is N/cH’“CH2 “0N02

\N02

O2N N02
CH2 .CH2 .0N02
N/
\ NO2
N02 (cl 0H9N9O16), and its Chemical
name is 2,4, 6-Trinitrophenyl-1, 3-dinitraminoethanol Dinitrate. It was prepd by Di San
Filippo by nitrating either 4,6-Dinitrophenyl- 1,3-diaminoethanol,

NH.C2H4OH

02N , or 2,4,6 -Trinitro- 1,3-diaminoethanol,

NH.C2H4OH
NO2

NH.C2H4OH
, trysts, mp 127°. In both cases coned
O2N N02 mixed nitric-sulfuric acid was used.
f’l-
 Iv

The procedure is described on pp 1382 & 1386 of Ann di Chimica 50. Eptrile separated
as a greenish-yellow oily-solid which crystallized from ethanol in the form of tiny trysts
melting at 123°. Its mw is 511 .24 and N content 24.55% (calcd 24.66%). Its explosive
properties were not determined

Unfortunately, we did not have the paper of Drs Giua and Di San Filippo at the time
1,3-Di(ethylolamino)-benzene and Derivatives were described in Vol 5, p D1242-R.
This compd NH. C2H4OH

NH.C2H40H
is identical with Phenyl-1,3-diaminethanol which
may be considered as the parent compd of 2,4,6 -Trinitrophenyl- 1,3-dinitroaminoethano1
Dinitrate designated as Eptrile. The compd prepd by K.F. Waldkotter by nitration of
4,6-Dinitro-l ,3-di(ethylolamino)-benzene, described in Recueil de Travaux Chimiques
571307 (1938) and in VOl 5 of Encycl is

; mw 421.27, N 23.285%;a thick sticky mass,

which softened at 30°, decompd violently
at 98° and ignited” at 230°. It is not identi-
cal with Eptrile and was not obtd in crystal-
line form. No attempt was made by Wald-
kotter to further nitrate this compd called
2,4,6-Trinitro- 1,3-bis(N-nitro-B-ethanol-
amino)-benzene
 v

TABLE OF CONTENTS
Page

Preface I

Addendum III

List of Figures and Illustrations VIII

Supplement to Abbreviations for Books and Periodicals x

Supplement to List of Books on Explosives, Propellants, XI

Pyrotechnics and Ordnance Items

Descriptive Text of Encyclopedic Items

H2 to “Hyros” Explosive Hlto H263

IASP to IZZO Il to I184

J (Poudre de chasse) to Jute Jlto J87

K (Prdver) to KZ

L-Alloy to Lysol Llto L63

Tables
Handling Characteristics of Explosives Hll
Thermodynamic Calculations of Compounds and their NFPA H 18
Ratings of Potential Hazard
Comparison of NFPA Reactivity Rating with Reaction Hazard Index H 20
Data Source, Reaction Hazard Index, and National Fire Protection H 21
Association Reactivity Rating
Properties of HBX’S H 24
US Specification Requirements for Grades A and B Compositions of HBX H 25
HBX Composition (Percent by Weight) H 26
Standard Heats of Formation and Heats of Detonation of H 41
Common Explosives
Standard Heats of Formation and Heats of Detonation of H 43
Explosive Mixtures
Melting Points, Heats of Fusion, Heats of Vaporization and H 44
Heats of Sublimation of Common High Explosives
Heat Conductivity Coefficients and Specific Heats of H 45
Common Explosives
Some Examples of the Use of Group Additivity to Check H 47
Experimentally Determined Heats of Formation
Comparison of Estimated Heat of Formation with Some H 49
Measured Since 1969
Group Values Now Available for State and Class of Compound H 51
 VI

Page
Tables (Cent’d)
Measured and Estimated Heats of Formation of Various H 52
Compounds at 298°K in kcal/mole
Heats of Formation of Nitroalkanes H 54.
Group Values for Estimating Heats of Formation H 55
of Nitroalkanes
Heats of Formation of Azo Compounds Measured by H 56
Engel and Wood and Estimated by Group Activity.
Group Values for Calculating Heats of Formation of H 57
Trans Azoalkanes and Azo Radicals
Compositions and Properties of HEX-24 and HEX-48 H 73
Volubility of Hexamethylenetetramine in Solvents H 79
Rf (Relative Movements of Test Sample Thru a Chromatographic H 99
Column) for Various Explosives
Image Dissection Camera Data H 106
Characteristics of Streak Cameras H 108
Specifications for Raw Materials Used in HTA-3 Explosive H 177
Composition of Type I and Type II HT-3 Explosives H 177
Unreacted Hugoniot Data for Condensed Explosives H 180
Critical Relative Humidities for Some Explosives and for H 186
Ingredients of Explosives and Pyrotechnic Compositions
Chemical and Physical Properties of Hydrazine Propellant H 205
Hydrolysis of Plasticizers for NC H 223
Explosive Nature of Peroxides H 225
Peroxy Derivatives of Aldehydes and Ketones H 227
Strength of Sulfuric Acid Required to Give Different H 251
Relative Humidities
Performance Data for Chlorine Trifluoride-Fuel Hyperbolic H 256
Propellant Combination
Performance Data for Bromine Pentafluoride-Fuel Hypergolic H 256
Propellant Combination
., Performance Data for Hydrogen Peroxide-Fuel Hyperbolic H 257
Propellant Combination
Performance Data for Fluorine-Fuel Hyperbolic H 257
Propellant Combination
Performance Data for Nitrogen Tetroxide-Fuel Hyperbolic H 257
Propellant Combination
Performance Data for Red Fuming Nitric Acid-Fuel Hyperbolic H 257
Propellant Combination
Percent Firing of Different Types of Lead Azide versus I 26
. Distance from the Fuse
Ignition Temperature Tests of Initiating Explosives by” Methods a I 27
(Perez Ara) and b (Datta & Chatterje)
Ignition Temperature of Nitroglycerin as Determined by Method I 28
of Snelling & Storm
Ignition Temperature of Various Explosives as Determined by I 28
Method of Micewicz & Majkowski
Ignition Temperature of Various Explosives as Determined by ,128
Method of Taylor & Rinkenbach, .
 VII

Page
Tables (Cent’d)
Comparison of Impact Sensitiveness Tests I 41
Impact Sensitivity Data Obtained with the Rotter I 41
Apparatus at ARDE
Comparison of Impact Sensitivity Tests on the Basis I 42
of Figures of Insensitivity
Qurditative Ranking of the Impact Sensitivity of Common Explosives I 42
Critical Stresses& Thicknesses in Instrument No 2 for 151
Various Explosives
Charge Thickness for Transition from Fracture to Explosion I 52
Critical StressesObtained in Different Pressures I 54
Impact Characteristics of Some Common Explosives I 54
Comparison of Experimental & Theoretical Impulse Constants I 60
Comparison of Measured and Theoretical Impulse Constants (l.) I 61
for Gas Detonations
Characteristics of a Typical IMR Propellant I 64
Materials Used for the Core of an Italian Shell 172
Modified Gap Tests of Various Explosives I 100
Comparison of Approximate and Exact Calculations for Shocked Argon I 131
Shock Temperatures of Noble Gases I 131
Important Data Concerning the Most Used Italian Ammunition I 143
Italian Antitank & Seacoast Guns I 144
Italian Bombs & Grenades I 146
Explosive Charges & Fuzes Used in Italian Bombs of WWI I 147
Italian Mining Explosives with Nitroglycerol I158
Italian Puldverulent Mining Explosives with Nitroglycerol I 159
Italian Pulverulent Mining Explosives without Nitroglycerol I159
Italian Mining Explosives Containing Surplus Propellants I 160
Chemical and Physical Characteristics and Test Methods for Jet Fuels J 72
Thermal Stability Test Conditions for Jet Fuels J 75
Russian Blasting Cap Compositions K2
Isothermal Decomposition of Explosives at CJ Conditions K9
Influence of Kinetics on Adiabatic Explosion Times of PETN K9
Kinetic and Thermochemical Parameters for the Decomposition of K11
Molten and Liquid Explosives
Arrhenius Parameters Based on the Wenograd Test K 12
Old and Krafzahl (KZ) Trauzl Block Expansion Test Values of K 18
Common Explosives
US Military Specification Requirements for Lead Dioxide L9
US Military Specification Requirements for Lead Oxide L 10
Sales (Millions of Pounds) of Industrial Explosives L 20
LDX Compositions and Properties L 21
Detonation Rate of Liquid Methane and Liquid Oxygen Mixtures L 23
Experimental Detonation Properties of Some Liquid Explosives L 29
Common Liquid Bipropellant Systems L 3’7
Properties of “Exotic” Liquid Bipropellant Systems L 38
Current Liquid Bipropellant Applications L 40
Typicrd Performance Characteristics of LP Rockets L 42
Loading Density of Various Explosives L 51
Typical LX Explosive Formulations L 62
 VIII

LIST OF FIGURES AND ILLUSTRATIONS

Page

Hafthohlladung (German Adhering or Stick Hollow Charge) H2

Panzerhandmine 3 (German Magnetic Antitank Charge) H3
Haftmine (German Adhering Mine) H3
Extent of Potential Hazard Rating H 16
Nomograph Linking Decomposition Temperature with Arrhenius H 19
Activation Energy
Example of Use of Reaction Hazard Index with Methane, H 20
Ethylene and Acetylene
Correlation of NFPA Reactivity Rating with . Reaction Hazard Index H 23
Moisture Content Apparatus H 33
Apparatus for 100°C Vacuum Stability Test H 33
Kammerminensprengungen in Balsaltgestein H 64
(Chamber Mine Blasting in Basalt)
Mechanism of Rotating Prism Photec Camera H 105
Diagram of a Simple Drum Camera H 108
Rudimentary Gun Shaped Like a Bottle H 122
Hochdruckpumpe (HDP) Supergun H 163
German Hollow (Shaped) Charges H 165
Hollow. Charge Nose Attachment for AP Bombs H 166
Apparatus for Determining the Temperature of Ignition H 169
Steady Plane Shock Front Propagating into Undisturbed Materials H 179
Alternative Hugoniot Curves H 179
Transmission of a Plane Shock Wave into a Material of Lower Impedance H 182
Transmission of a Plane Shock Wave into a Material of Higher Impedance H 182
Shock Waves Induced in Various Materials by Normally Incident H 183
Plane Detonation Waves
The Rankine-Hugoniot Curve H 183
Pressure-Volume Hugoniot for 1g/cc TNT H 184
Definition of Pressure Values Measured on Film Strips I11
Diagrammatic Representation of Ignition I 11
Apparatus for Determining Minimum Energies for Electric-Spark I11
Ignition by Blanc et al
Lewis & Von Elbe Model of a Minimal Flame in Ignition Process I12
Schematic Illustration of Source Energies and Critical Source - 113
Temperatures versus Critical Heating Period
Relation between Ignition Energy, Mean Firing Current and I 14
Critical Heating Period for Electric Fuseheads
Plot of Energy versus Wire Length for Electric Fuseheads I 14
Relation between Cross-Sectional Area of Wire and Minimum I 14
Critical Energy per Unit Length
Burning Rate for Various Models of Surface Burning Rates 1.15
Anvil Striker Arrangement, ERL Machine I 37
Drop Weight Impact Machine, ERL Model, Type 12 Tools I 37
Rotter Machine Impact Chamber and Anvil-Striker Arrangement I 38
Bureau of Mines Impact Apparatus Showing Anvil-Striking Pin Assembly I 38.
Picatinny Arsenal Impact Test Apparatus 139’
Parts of Picatinny Arsenal Impact-Test Apparatus I 40
 IX

Page
Figures (Cent’d)
Impact on a Layer Density Close to Maximum I 46
Impact on a Layer of Low Density I 46
Design of Apparatus and Connection of the Pick-up to the Oscillograph I 49
Interpretation of Oscilloscope Traces of Pressure Pulses I 49
Average Pressures upon Fracture and upon Explosion vs H 50
Charge Thickness of HMX, RDX, Tetryl and TNT
Average Pressures vs Charge Thickness for PETN and Trinitrophenol I 50
Spread of the Measured Pressures upon Fracture and upon 150’
Explosion for RDX
Explosion Frequency vs Impact Energy for Tetryl and RDX and HMX 151
Explosion Frequency vs charge Thickness in the Case of HMX for I 52
Various Impact Energies
Time Delay Between Impact and Explosion I 53
Impedance, Acoustic and Shock Diagram I 56
Constants for EL 506D as Functions of the Ratio of Foam I160
Neoprene to Target Weights
Laser Interferometer System 1112
Relation between the Light Energy Required for Ignition and 1119
Temperature for Nitrogen Iodide
Italian Cartridge with Igniter Tube I151
Italian Cartridge Bag I 151
Idealized Projectile Types J1
Cross Section of Open Hearth Furnace Tap Hole Showing J 76
Jet Tapper in Position for Firing
Types of Jet Propulsion Engines J 78
Comparison of Turbojet & Turboprop Engines J 79
Schematic of Ramjet Engine J 80
Schematic of Pulse Jet Fitted with Flow-Check Valves J 81
Comparison of Performance Parameters of Jet Engines J 82
Line Wave Generator of the Manifold Type L 17
Line Wave Generator of Sheet Explosive L 17
Line Wave Generator of Warped Sheet of Explosive L 18
Space-Time Representation of Initiation Behavior of Nitromethane L 31
Scoop Loading of Explosive Charges L ,48
Charging Plate Loading of Explosive Charges L 49
Detonator Loading Tool L 49
Tool for Direct Loading of Component L 50
Nomograph of Loading Pressure and Density L 51
Vacuum Pressing Apparatus L 53
Hydrostatic Pressing Principle L 54
Isostatic Pressing Principle L 54
 x

SUPPLEMENT TO THE
LIST OF ABBREVIATIONS FOR BOOKS AND PERIODICALS
GIVEN IN VOL 1, pp Abbr 66 to Abbr 76; VOL 2, pp Xl to XII;
VOL 3, pp XII to XIII, and VOL 4, pp XLVII to L

Blomquist OSRD 4134 (1944) A.T. Blomquist, “Certain Aliphatic Nitra-

rnines and Related Compounds”, OSRD
4134 (Nov 1944)

Bowden & Yoffe (1952) F.B. Bowden & A.D. Yoffe, “Initiation
and Growth of Explosion in Liquids and
Solids”, Cambridge Univ Press, Cambridge,
Gt Britain (1952)

Bowden & Yoffe (1958) F.P. Bowden & A.D. Yoffe, “Fast Reactions
in Solids”, Academic Press, New York (1958)

5th ONR SympDeton (1970) “The Fifth Symposium (International) on

Detonation”, Pasadena, California, 18–21
August 1970, 512 pp

Hackh’s (1 972) J. Grant, “Hackh’s Chemical Dictionary”,

McGraw-Hill, Hightstown, NJ, 4th edn
(1972), 738 pp
 XI

SUPPLEMENT TO THE
LIST OF BOOKS ON EXPLOSIVES AND PROPELLANTS
GIVEN IN VOL 1, p A676; VOL 2, pp C215 to C216; VOL 3, pp XIV to XV
VOL 4, pp LI to LV; VOL 5, pp XIV to XV; and VOL 6, p X

E.J. Hoffschmidt & W.H. Tantum IV, “Second World War – German Combat Weapons”,
WE Inc, Old Greenwich, Corm, Vol 1 (1968)

W.H. Tantum IV & E.J. Hoffschmidt, “Second World War – Japanese Combat Weapons”,
WE Inc, Old Greenwich, Corn, Vol 2 (1968)

Anon, “Principles of Explosive Behavior”, AMCP 706-180, Engineering Design Handbook,

US Army Materiel Command, Washington, DC 20315 (April 1972)

Brodie, Bernard & Fawn, “From Crossbow to H-Bomb”, Indiana University Press,
Bloomington (1973), 320 pp

Collective, “The Problem of Chemical and Biological Warfare”. A study of the Historical,
Technical, Military, Legal and Political Aspects of CBW and Possible Disarmament Measures.
Stockholm International Peace Research Institute, Almqvist & Wiksell, Stockholm and
Humanities Press, NY (1973)
Vol 1. “The Rise of CB Weapons, 396 pp
Vol 2. “CB Weapons Today”, 420 pp
Vol 3. “CB and the Law of War”, 194 pp
Vol 4. “CB Disarmament Negotiations, 1920–1970”, 412 pp
Vol 5. “The Prevention of CBW”, 286 pp

J. Quick, “Dictionary of Weapons and Military Terms”, McGraw-Hill, NY (1973), 515 pp

“Blaster’ Handbook”, Explosives Division, Canadian Industries Limited, 630 Dorchester

Blvd W, Montreal, Quebec (1973), 545 pp

Anon, “Explosives Trains”, AMCP 706-179, Engineering Design Handbook, US Army

Materiel Command, 5001 Eisenhower Ave, Alexandria, Va 22304 (Jan 1974)

Anon, “Design of Ammunition for Pyrotechnic Effects”, Engineering Design Handbook,

US Army Materiel Command, 5001 Eisenhower Ave, Alexandria, Va 22304 (March 1974)

RUSI & Brassey’s “Defence Yearbook 1974”, Praeger, NY (1974), 338 pp

M.A. Cook, “The Science of Industrial Explosives”, Graphic Service & Supply, IRECO
Chemicals, Salt Lake City, Utah (1974), 449 pp

R.W. James, “Propellants and Explosives”, Noyes Data Corp, Park Ridge, NJ (1974),
363pp
 XII

R.T. Pretty & D.H.R. Archer, Edits, “Jane’s Weapon Systems”, Franklin Watts Inc,
New York, NY (1974–75), 852 pp

Major F.W.A. Hobart, Edit, “Jane’s Infantry Weapons”, Franklin Watts Inc, New York,
NY (1975), 860 pp
 H1

ENCYCLOPEDIA of EXPLOSIVES and RELATED ITEMS

Volume 7

H2. Designation of N-Acetylamidomethylhexa- at 1.56; Explosion Temp 610? (rein) in 5 see;

methylenetetraminemononitrate described in Fragmentation Test in 90mm HE, M71 Proj, No
Vol 1, p A54-L of fragments 714 vs 703 for TNT; Friction Sensi-
tivity – unaffected; Gas Volume 733cc/g, vs 730
H2 Kongo or Type 98 Explosive. Japanese WWH for TNT; Heat of Cornbstn 3972cal/g; Heat of
explosive consisting of ‘llinitroanisole 70 & Hex- Expln 923cal/g; Heat Test at 100° – % loss in 1st
anitrodiphenylamine 30%. It was used in bomb 48 hrs 0.78cc, no loss in 2nd 48 hrs and no expln
auxiliary boosters, sea mines & depth chges in 100 hrs; Hygroscopicity S1higher than for TNT;
Ref Dept of the Army Tech Manual TM9-I 300- Impact Sensitivity – same as for TNT; Rifle Bullet
214 and Dept of the Air Force Tech Order TO Sensitivity – more sensitive than TNT; Sensitivity
11A-1 -34, “Military Explosives”, Washington, DC to Initiation – min priming chge less than for TNT;
(1967), p 8-3 Storage – dry
Usage– primarily in HE charges (Refs 1,4 & 6)
H-4. .I’he composition of this solventless Ballistite Preparatwn – same method as described under
in the form of 0.869 x 0.2,62 x 16 inch sticks HBX. US Military Specification requirements and
is as follows: jNC/NG/DNT/Ethyl Centrality/ tests are described under HBX. Its Spec is MIL-E-
potassium sulfate 58.00/30.00/2.50/8 .00/1.50% 22267A (31 May, 1963)
Refs: 1) S.D. Stein, G.J. Horvat & O.E. Sheffield,
This propellant was used in US Ordnance “Some Properties and Characteristics of HBX-1,
rockets HBX-3 and H-6 Explosives”, PATR 2431 (June
Rej Cal Tech Lab Program 209, “Investigation 1957) 2)0.L. Rogers, “Relative Effectiveness
of the Dry Extrusion of Solvent Prepared H4 of TNT, Comp B and H-6 as Mine Fillers”, APG
Propellant”, Status Rept 1-6 (12 Jan 1945 - report on Proj TS 1-200 (Ott 1959) 3) H.
16 June 1945) Herman, PA Feltman Res & Engrg Lab, Instru-
mentation Rept 268-59 (April 1960) 4) Anon,
H-5. An American rocket propellant consisting Navord 2986 (1961) Sect D.2 5) L.A. Potteiger
of NC/NG/Et Cent/DNT/Kz SOq/triacetin/ NWL Rept 1930 “Alternation of Mech Props of
Pb stearate (added) 58/20/8/2.5/1.5/10%/0.5% 16 Metals by Explosively Induced Stress Waves”
NC (13%). Its burning rate is 0.3 to 0.8 inches (July 1964) 6) O.E. Sheffield, AMCP 706-177,
per second for 1000 to 4000 psi at 122”F. The pp 146-149 (Jan 1971)
burning rate of a Russian’ powder examined at
the same time was the same at 1000 psi, but , H-16. Code name for 1,9-Diacetoxy-2,4,6,8 -tetra-
10-15%faster at 4000 psi nitro-2,4,6,8-tetrazanonane or ‘1,9-Diacetoxy-
Refs: 1) OSRD of NDRC Div 3, Sec H, Final Rept 1,3,5 ,7-pentamethylene-2,4,6,8-tetranitramine.
Series P, No 10.2 (1945), p 45 2) W.E. Campbell See Vol 5 of Encycl, p D1 118-R
Jr& L.H. Brown, Aerojet Rept 194 (1946), p 12
H19. A designation for, 4-N-Methyl-2,6-N-dinitro
H-6 Explosive. A grey castable expl compn contg: (Bicycle)-pentamethylenetetramine
RDX 45, TNT 30, Al 20, D-2 Comp 5 and 0.5%
CaC12added; mw ca 93, OB to C02 –66%; density H21 or MSX. Designations for l-Methyl-6-acetoxy-
1.71 to 1.74; Ballistic Mortm Test for Power 135% trimethylene-l ,3,5-trinitramine
TNT; Blast Effects, % TNT: In Air 127% (Shock)
& 138,%(Impulse); Under Water: 118% (Shock) Haber, Fritz (1868-1934). German chemist and
and 154% (Bubble): Brisance by Sand Test 49.5g Nobel prize winner. Discoverer of synthetic
sand crushed vs 48.Og for TNT; Detonation Rate method for catalytically producing ammonia
7191m/sec at d 1.71, vs 6825 for TNT pressed from nitrogen and hydrogen. This discovery
 H2

enabled Germany to manufacture explosives in Hafthohlladung. (Adhering or Sticking Hollow

WWI despite the naval blockade. Did considerable Charge). One of the devices ,consisted of a
work in gas warfare conical metallic container (filled with 3 “lb 5 oz
Refs: 1) Hackh’s Chem Diet, Blackiston, Phila of a HE) to which was attached an elongated
(1944), p 394 2) R. Hanslian, SS 29,59 (1934) apex; serving as a han,d grip and contg the
exploder pellet (PETN/Wax) and a pull (friction)
Hackh & McLeod Explosive. A preliminary delay igniter (4% or ~ seconds). Attached to.
investigation of the effect on the explosion the base of ‘the conical section was a plywood
props of 50/50 Amatol ‘of incorporating with it
Nitronaphthalene & benzaldehyde, in accordance
HAFTHOHLLADUNG
with a process set forth in the patent applica-
tion of Me_ssrsHackh & McLeod, showed con-
clusively that the addn of 10% alpha Nitro-
naphthalene’ (“catalyst;’) & 2% benzaldehyde
(“promoter”) renders the Amatol less sensitive
to friction, less biisant, and undesirably insensi-
tive to initiation to detonation
The results fail to substantiate the claim of
the inventors fid in no way bear out the’ theory FILLING
!.
that the efficiency of nitmexplosives can ‘be
increased by the addn of nonexplosive materials
having specified intra-atomic distances
Ref J.D. Hopper, PATR 731 (April 1936) &
PATR 743 (July 1936)

HADN. See Hexamethylenetetraminedinitrate or

Hexaminedinitrate in this Vol

Haensoson-bakuyaku or Type 88 Explosive.

Japanese WWII expl consisting of Ammonium
Perchlorate 75, ferr,osilicon 16, wood meal 6 &
petroleum 3%. It was’ used in demolition chges,
mines &’ depth chges
Rej Dept of tli~’ Army Tech Manual TM9-I 300-
214 and Dept of the Air Force Tech Order
TO I IA-I-34, “Military Explosives,” Washington, frame-work carrying three powerful horseshoe
DC (1967), p 8-4 m’agnets. A brass chain with a hook was
NOTE:’ Compare with Carlit or Karitto des- attached to the framework. Total weight 3 kg
cribed in Vol 2 of ~ncycl, p C68-L The device could be used either as a hand
grenade “or as a land mine. In the first case the
Haeussermann, Carl ‘(1853-191 8). German cord of the friction igniter was putied off and
scientist specializing in explosives. In 1891 he the grenade thrown against the approaching
developed an industrial method of preparing TNT vehicle. In the second case, the ‘device was
and recommended its use as a military explosive. buried in the ground, close to the surface, with
Refi C. von Hell, SS 13, 325-27 (1918) the magnets up and with the igniter cord at-
.
tached to the ground. At the approach of a” ‘
Hafenegger Powder. A mixture patented in vehicle the magnetic attraction caused the
1868 in England consisting of chlorates, sulfur, grenade to jump towards some iron or steel
charcoal and potassium ferrocyanide part and attach itself to it. Simultaneously the
Refs: 1) Cundill (1889) i: MP 6, 7 (1893) 2) cord was pulled, thus setting off the” explosive
Daniel (1902), p 3,66 3) Cody (1907), p 263 t’rain consisting of delay igniter, exploder and
4) Giua, Trattato 6 (1959), 392 main charge (Ref 2) It was claimed that this
 H3

charge could penetrate as much as 11Omm of HAFTMINE

armor (Ref 1, pp 323-4) !.

Another magnetic antitank charge is described

in Ref 1, pp 262-3 under the name of Panzer-
handmine 3.It consisted of a bottle-shaped
cardboard container with 2 1/3 lb of hollow
charge (TNT or RDX/TNT). Three pairs of mag-
nets were mounted at the bottom of the bottle,
and a 7% “see friction igniter was located in the
neck of the bottle. Total weight of the device
was 8 lb
The device was appWently designed “to be
placed by hired on the tank and the ig@ter
pulled afte~ it has been positioned. If the target ~LOW MELTING PLASTIC
was of non-magnetic material such as wood, the PROTECTIVE CLOTH
charge could be attached by means of 3 spikes
PROTECTIVE COVE R
located at the bottom of t)ie. device ..
J Haftmine (Adhering Mine). An anti~”nk, hollow
Defw ator charge device consisting of a conical container
(filled with HE), provided with a’ flat top and
a handle. The wide portion of the cone was
covered with a layer of a low melting colophony-
oil plastic resin (m p ca. 50°) retained on the”
surface by means of an open mesh cloth. In
back of the flat top, which consisted of sheet
~Churge metal, was placed a thermite-type charge (Mg +
Al + KC103 ) and in back of the latter a time
fuse. The operator hid in a hole and, at the
approach of the tank, ignited the _t7.rse-
which,
in turn, ignited the thermite. Just as soon as
the heat of the thermite melted the resin, the
device was struck (by the operator) to the
bottom armor plate of the tank. At the same
time the heat of the thermite set off the deto-
nator and this in turn initiated the main charge
This device was in an experimental stage
when the war terminated
Refl 1) E.E. Richardson et al, CIOS Rept 25-
18 (1945), pp 23-5 2) PATR 2510 (1958),
p Ger 87-L & R

Hahn’s Explosive. A cheap explosive mixture.

prepared as follows: Burnt lime was dissolved
in raw, odorless nitric” acid so as to produce a
In another type of adhering (sticking) antfi clear transparent fluid resembling petroleum
tank hollow charge there were no magnets but jelly. This fluid was diluted.with 1 to 5 parts of
a sticky pad (located at the wide part of the water according to the desired explosive power, and
conical body) served for attaching the charge then mixed with a powdered celluloiic material
to a tank (Ref 1, p 324) such as peat, sawdust, etc, until a consistent
Kefs: 1) Dept of the Army Manual TM 9-1985 mass was obtained. After giving this mass any
2 (1953), pp 262-3 & 3234 2) H.H. Bullock, suitable form, it was dried and used as a
Pic Arsn, private communication 3)PATR 2510
(1958), pp Ger 85-R to &r 87-R
 .

H4

commercial explosive, eg in rock blasting. It Hake Effect. Some industrial explosives, even
was found to be a powerful explosive insensitive when made of normal consistency, are subject
to shocks, friction, or pressure under certain conditions to a change in storage,
Refi M. Hahn, USP 1751326 (1930) & CA 24, by which they become very insensitive. Quinan
2605 (1930) (Ref) called this the “Hake Effect” in honor of
C. Napier Hake, the late Inspector of Explosives
Hahn’s Powder. One of the chlorate explosives for the State of Victoria, Australia
in which sensitivity of the powder due” to the Mr Hake was the first man of science out:
pressence of KC103 was reduced by the addi- side the ranks of Dynamite makers to make a
tion of spermaceti: KC 103 61/Sb2S3 28/Charcoal study of this curious & interesting observation.
3 & spermaceti 8%. It was patented in England If a small percentage of Blasting Gelatin that
in 1867 and used in primers has become insensitive be reworked & mixed
Refs: 1) Cundill (1889) in MP 6, 8 (1893) with a large percentage of a fresh lot, it will
2) Daniel (1902), 366 3) Cody (1907), 263 infect the mass, and the remade Blasting Gelatin “
4) P4rez Ara (1945), 206 will soon undo the change. Something more
than a mechanical effect is involved; in fact, an
Haid, August (1886-1963). Ger scientist, formerly obscure form of catalytic action seems to be
director of Chemisch-Technischen Reichsanstalt. indicated
Author of numerous papers on explosives, some There are so many unknown factors involved
of them in collaboration with H. Kast, H. Selle, in the “Hake Effect” that it is impossible to
A. Schmidt or H. Koenen take them all into account. One of these is the
Refi H. Koenen & P. Dittmar, Explosivst 1963, coridition of storage, especially the temp. If a
54-6 (Obituary, portrait and list of publications) Gelatin of normal consistency & sensitiveness
has been stored in a comparatively high temp
Haid, Becker and Dittmar Stability. Test (Designed and is subjected for a few months to a low temp,
for high explosives). 42g of powdered explosive, it seems to develop the “Hake Effect” very
previously dried over phosphorous pentoxide, is promptly. On the other hand, a Gelatin which
introduced through a side tube into a glass threatens to develop this effect may show nor-
mal sensitiveness at least for a time if trans-
vessel connected with a manometer which is in
the form of a U-tube and contains mercury ferred to a warmer climate
covered with a layer of paraffin oil. The glass Refi W.R. Quinan, “High Explosives,” Critch-
vessel is rdso fitted with a side tap. The ensemble ley Parker, Melbourne, Australia (1912), pp
27-29. See also Aging of Dynamites in Vol .1,
is heated at 75° for several hours and pressures
are recorded in mm’ of Hg as a function of pp Al 1O-R to Al 12-L)
time. The steeper the pressure-time curve the
Halakite. An explosive submitted during WWI
less stable is the explosive
Ref 2 gives curves for principle explosives as to the Fr & Brit authorities, consisting of
well as for smokeless powders Cordite mixed with Pb nitrate, Ba nitrate &
Pb chromate. It was claimed to be equally
Refs: 1) Reilly (1938), 92, 2) A. Haid, h.
effective as an HE and as a propellant
Becker & P. Dittrnar, SS’30, 66 & 105 (1935)
Refi Marshall, Diet (1920),48
Haishokuyaku. Japanese WWII explosive con-
sisting of Ammonium Perchlorate 77, RDX 17, Hale, G.C. (1891-1948). American scientist
silicon carbide 1.5 & paraffin 4.5Y& It was used who served as Chief of the Chemical Depart-
in demolition blocks ment, Picatinny Arsenal (1929-48). After
Refi Dept of the Army Tech Manual TM9-I 300- military service Dr Hale was assigned in 1920
214 and Dept of the, Air Force Tech order to a task group which was sent to Germany
TOI 1 A-1 -34, “Military Explosives,” Washington, for an exhaustive study of the Ger expl
DC (1967), p 8-3 indush-y of WWI. He made numerous inven-
tions, held many patents, and authored ex-
tensive publications in the field of military
 H5

propellants & explosives. His name has been 2-Chloro-4’,5-dinitrobiphenylhas been prepd
given to an explosive called Haleite because by the mixed acid nitration of 2-chlorobiphenyl,
of the important part he played in its develop- mp 159°, further nitration may yield small
ment as a military expl amts of a tetranitro deriv melting at 127°
See Etliyleneclinitramine in Vol 6, p E238-R & Rejl GIH. Beauveau et al, JChemSoc. (19’61)
Cyclonite ‘or RDXinVol3ofEncycl,pC611 2749 & CA 56, 3377 (1962)

Haleite. See Ethylenedinitramine under Ethy- Haloclastite or Haloklastit. Same as Petroklas-

lenediamine and Derivatives in Vol 6 of Encycl, tite (Ger).’ One of the pre-WWI expls used in
p E238-R potash mines and stone quarries: Na-nitrate
,,Halford-.Kistiakowsky -Wilson Equation of State. 69, K-nitrate 5, sulfur 10, coal tar pitch 15,
See Vol 4, p D608, Eqs 23 & 24 K:dichromate 1%
Refs: 1) Marshall 1 (1917),89 2) Stettbacher
Hail (or Will) Powder. Patented in 1863 in” (1933), 111 3) PATR 2510 (1958), Ger 130L
England, it contained potassium cNorate 47,
potassium ferrocyanide 38 & sulfur 15% Halodinitrophenylnitraminoethyl Nitrates. See
Re@ 1) (lsndill (1889) in MP 6, 8 (1893) under Phenylarninoethanol & its derivatives
2) Daniel (1902), 366 3) Giua, Trattato 6
(1959), 391 Halogenated Acetylenes
Mono and di-halogen-substituted acetylenes and
Hall (John) & Sons. Employed since 1875 their metal salts are very unstable, highly flam-
charges of compressed. Nitroceliulose in mable, and many of them are highly explosive:
blasting of sandstone and clays and found that Acetylene Bromide, Bromoacetylene, Bromo-
such charges were very effective ethyne or Ethynylbromide (called Bromathin
Ref Daniel (1902), p 366 or Bromacetylen in Ger).
BrC;CH; mw 104:93;
Note: Later, compressed Nitrocellulose was colorless gas, bp -4.7°, Qvap 58cal/g, d 4.68g/l
used extensively for bursting charges in shells, at 0° & 1 atm; S1sol in w; sol in eth & dil
bombs & mines. As late as WWI nearly all HN03; tdxic. Prepd from alc KOH & “brorni-
small demolition (called pyroxylinovyive shashki) nated hydrocarbons, also Br2 C: CHBr & HgC12
blocks used in Russia were of compressed & KCN to give the mercuric salt (Ref 1). ‘
pyroxyline. Bursting charges in older models Addnl thermodynamic data (see Acet Chl for ~”
of Whitehead torpedoes also used compressed definitions): (H~-E~)/T 9.702, (Yo-@/T 49 .5’2;
Nitrocellulose, contg ca 18% water c; 13.31 cal/O mole & S0 59.22 eu (entropy
Refi Col M,M. Kostevich, Private Communication, units) (Ref 10)
(1955) It is pyrophoric and w solns give off 03
and phosphoresce. Hg (C!CBr)2 darkens and
HALOBIPHENYL DERIVATIVES explodes above 153°. It also explodes with’
shock .,,
2-Halobiphenyl-Nitro Derivatives. The only
compds of this class that are reported to be Acetylene Chloride, Chloracetylene, Chloroethyne
explosive when they are prepd in quantities or Ethynyl Chloride, @lled Chlor-äthin or
of over 5g are: Chlor-acetylen in Ger), CIC! CH; color-
mw 60.48;
2-Halo-3,5-dinitrobiphenyl, C6H5-C6H2(NOZ)2X less gas, bp-29.6° Qva 89“crd/g (at bp); d. 2.0
mws 278.66,323.11 & 370.11 ;N 10.06. 8.67&’ (Ref 4). Sol in w & aYc (water soln gives off
7.57%; mp 115°, 110°& 132°for X = Cl, Br 03 and glows in dark), nauseating odor and ‘
& I. These comps are prepd by alazouzing probably anesthetic if inhaled. Prepd from
3 ,5-dinit ro-2-aminobiphen yl with nitrosylsulfuric C12C:CHC1 & alc KOH ‘(Ref 6); C12C:CHOOH
acid, followed by treatment with CUX in HX & Ba(0H)2; CHC1:CHC1 & KOH, HgC12 & NaCN
at 0° ,’ to give Hg(C ~CC1)2 which gives acetylene
Refs: 1) Beil 5, {1762, 1766 & 1769} 2) S. chloride on heating with NaCN and” KOH under
Zaheer & I. Kacker, JIndChemSoc, 32, 491 ‘ N and drying with H2SOJP205 (Ref 2).
(,1955) &CA 50; 10688 (1956) Addnl thermodynamic data: H=E~/T 9.442,
 H6

F=E~/T 46.96 Cp” 13.31 (all in cal/deg mol) Iodoacetylene, Acetyiene Iodide, “Ethynylio-
S056.40 eu, HO, FO, c; & S0 are respectively dide, or Iodoethyne (called Iodathin or
standard heat of formation, stand ‘free energy of Iodacetylen in Ger). IC:CH; mw 151.93, bp
form; heat capacity & std entropy., ~~ is heat of 32°, one of the products of the reactri of
formation of a perfect gas,at abs zero (Ref 10) BrMgC;CH with 12 (Ref 6)
Acetylene chloride behaves very unpredictably Refs: 1) Beil 1, 245 (106) &~919? 2) Beil 1,
It is spontaneously flammable in air and it 45, (67), [221] &~917~ 3) Beil 1, 246, [222]
explodes when heated in air or shocked. On &(9191 4) Beil 1, (606), [222] & {918} 5)
pyrolysis it gives off the very toxic phosgene Beil 1, 246, (106), [222] & {919} 6) Beil 1,
(Ref 8). An attempt at defining its explosion [222] 7). Beil 1, 248, [223] & {922}” 8)
limits is made m Ref 2 Sax (1968), 373 9) J. Ziomek & E. Cleve-
The following metal salts of acetylene land, JChemPhys 17, 578 (1949) & CA 43,
chloride are known (Ref 2): 1) Hg (C1CC1)2.,See 8838 (1949)
above for prep; mp 185°, explodes 195° 2) Ag-
C~CCl, prepd by treating acetylene chloride with Bromo-l-rnethylacety lene or Bromopropyne
an ammoniacal Ag soln to obtain a very unstable (called 2-Brom-l-methylacetYlen or Brompro-
white. pptate which darkens in air. It explodes pin (1) in Ger). CH3C~CBr; mw 118.96, bp 65°,
on shocking even under water 3) Cu C~CCl, d 1.35 at 25°, RI 1,4448. Prepd by passing
prepd by treating acetylene chloride with ammo- Me-acetylene into alk KOBr at 0!; from 1,1,2-
niacal. CUCI; shock sensitive tribromopropane heated on a steam bath with
Dibromoacetylene or Dibromoethyne (called alc KOH in an atm of hydrogen. If inhaled it
Dibromäthin or Dibromacetylen Ger) BrCi CBr;
in causes severe headaches. The pure mate~al
mw 183.82; colorless liq, .mp --24°, bp - 76°, self-ignites in air
d -2, ,ins iq w; sol in org solns; toxic: vap Refi Beil 1, [223] & {922} “
inhalation produces violent headaches & dizziness.
Prepd by. action of alc KOH .on Br2 C :CHBr or HALOGENATED AMINES or
,
aq KOBr on acetylene (Ref 3). It is veiy unstable HALOGENATED AMIDES
and yin explode in N2 :or C02 containing traces Organic compounds containing halogen atoms
of 02; also explodes on heating attached to the nitrogen. A large number of
Dichloroacetlene or Dichloroethyne (called such compounds were. prepd by treating amines
Dichloräthin or Dichloracetylen in Ger\, CICi CC]: with’ hypochlorites. Some of these compounds
mw 94.92; colorless Iiq, mp -66 bp 32 to -64°, are explosive:
to 33° (748mm); sol in Etz O & CCIO; ins in ‘ N,N-Dichloroformamide, HCONC12; mw 113.93,
w. Prepd by passing hot Clz C: CHC1 over KOH N 12.3V.; yellowish-red liquid which rnaY be
at’ 130° (Ref 4). Explodes on exposure. to air prepd either by the action of hypochloric
and. on heating to over 130° ,., , acid, or chlorine on formamide dissolved in
Diiodoacetylene or Diiodoethyne (called water and cooled wi~ ice-salt mixture. It is an
Diiodäthin or DiiodacetylenGer). IC;CI; mw
in explosive which already starts to decompose
277.82,; yellowish rhombic ‘trysts (from ligroin), slowly at OO.When brought to room temperature,
mp 8 1°; bp 80 to 100° (decomp); SI sol in it explodes spontaneously within a few seconds
cold ligroin; v toxic~attacks mucous mem- (Refs 1 & 4)
branes. Prepd by action of ~c KOH or NaOEt N,N-Ethyldichloroformamide, N,N-Dichloro-
on C2~, CIC1:CIH or C212Clz; by decomposing propionamid, mw C2H5CONC12, mw 141.99, N 9.87%
C2 ~ ‘in sunlight; from C2 H2+KI+KOC1 or, bp 88-89° ‘at 762mm. It was prepared by
KOBr in w; ,from C2Hz or NaC2H or CaC2+ Rideal (Ref 3) and claimed to ba a powerful
12 iII liq amm (Ref 5). Addd. thermodyn data explosive. suitable as a replacement for NG
(at 373:1 5°K)-see Acetylene Chloride for The following explosive derivatives of
defmitions–,H~-E~ 13.90, FO-E~64.75, cal/ aliphatic diamines were prepd by Chattaway
mole ,c” 1.7.44 cal/deg mole, S0 ,78.65 eu (Ref 2):
(Ref 9~ Explds on, grinding, explodes on Ethylenetetrachloraminodiamine, or. N,N,N’N’-
heating above, 120°, decomp at lower temps Tetrachloroethylenediamine; C1.NCH2CH;NC12;
when heated in light mw 197.88, N 14.16%, yellow fiquid, mp 44.5”
 H’7

bp, 76-78° at IOmm (Ref 5), bp 116” at 50mm at 165-175°. When heated rapidly in flame, it
(Ref 2), d 1.544 at 20° (Ref 5). Explodes wifi explodes (Ref 2)
great violence on heating (Ref 2). Can also be Di-p-toluenesulfonylethylenedibromodiamine, or
prpd in H20/C12 /NaHCO1 SOIII (Ref, 5) N,N’-Dibromo-N,N’-ethylene-bis-toluenesulfonamide
Ethylenetetrabromodiamine, Br2NCH2 CH2 N13r2; H3CC6H4S02NBrCH2CH2 NBrS02C6H4CH3, mw
mw 375.68, N 7.46$ZO; orange-colored trysts, mp 530.28, N 5.28%; pale yellow plates, mp 165°;
about 62° with decomposition, followed almost decomposes beginning at 170° ind explodes at
immediately by a violent explosion (Ref 2) about 180° when heated rapidlv (Ref 2)
s-Diacetylethylenedibromodiamine, CHICONBr- Di-m-nitrobenzenesulfonylethylenedichlorodiamine,
CH2CH2NBrCOCH3; mw 301.98, N 9.28%, pale 02 NC6H4S02NC1CH2CH2NC1S02C6H4N02, mw
yellow prisms; mp 150-155°, giving off bubbles 499.32, N 11 .22%; pale yellow prisms, mp 198°;
of gas and almost immediately exploding decomposes beginning at 220°, explodes when
(Ref :2) heated in a flame ‘(Ref 2)
s-Dipropionylethylenedichlorodiamine, Dibenzoyltrimethylenedichlorodiamine, or.
CH3CH2CONC1CH2CH 2NC1COCH2CH3; mw 241.14, N,N’-Dichloro-N,N’-propylen-bis-benzamide
N 11.62%; yellow liquid, decomposes almost C6H~CONClCH2CH2NClCOC6H5, mw 337.22,
explosively on heating (Ref 2) N 8.31%; colorless plates, mp 85°. Explodes when
s-Dipropionylethylenedibromodiamine or N,N’- heated above 160°
Dipropionyl-N,N’-dichloroethylenediamine, Refs: 1) Beilstein, ,2, (22) 2) F.D. Chattaway,
CH3CH2CONBrCH2CH2NBrCOCH2CH3; mw JCS, 87, 381 (1905) 3) J.D. Rideal, Ger 301.
330.04, N 8.49%; flattened pale yellow needles, 799 & CA 15, 1966 (1921) 4) P.L. Magil,
mp 112°; explodes. at 160° (Ref, 2) - IEC 26, 611 (1934) 5) L.K. Jackson et al, JACS
s-Diphenylacatylethylenedibromodiamine, or 69, 1539 (1947) & CA 41, 5852 (1947)
N,N-Dichloro-N,N’-ethylene-bis-phenylacetamide,
CGHsC~zCONB~HzCHzNB~ OCHzCGHs, mw
454.18, N 6.17%; pale yellow plates; mp 128°. HALOGENATED DERIVATIVES
Explodes it about 150” (Ref 2) OF SULFONAMIDES
s-Di-m-nitrobenzoylethylenedichlorodiamine, or The sulfonamides are distinguished by the great
N,N’-Dichloro-N,N’-ethylene-bis-3-nitrobenzamide readiness with which they form well-crystallized
02 NC~H4CONClCH2CH2NClCOC6HoN02, mw derivatives in which all the amine hydrogen is
427.22, N 13.12%; nearly colorless plates with replaced by halogens, when acted upon by
slight yellowish tint, mp 173°. Stable up to hypochlorous acid at ordinary temperatures. The
about 220°, but explodes when heated in a sulfonchloramides so produced exhibit great
flame (Ref 2) stability when compared with other chloramides.
s-Di-p-nitrobenzoylethylenedichlorodiamine, or Those containing two chlorine atoms attached to
N,N’-Dichloro-N,N’-ethylen-bis-[4-nitroben- nitrogen, melt without decomposition and can fre-
zamide] 02 NCGH4CONC1CH2CH2NC1COC6H4N02, quently be heated considerably above their
mw 427.22, N 13. 12fZO; nearly colorless plates with melting points without undergoing any change, but
slight yellow tint, mp 207°; decomposes at they explode when heated by direct flame. The
about 215°. Explodes when heated in a flame tetrachloroamides derived from disulfonamides
(Ref 2) resemble nitrogen chloride itself in ‘the violence
s-Dibenzenesulfony lethylenedichlorodiamine, or with which they detonate. When similarly heated,
N,N'-Dichloro-N,N'-ethylene-bis-benzenesulfonamide the sulfonalkylchloramides do not detonate, but
CGH~S02NClCHzCH2NClS02 C6H~, mw 413.32, decompose rapidly with evolution of gas. “They’
N 6.78%; colorless prisms, mp 113°; starts to are used as external antiseptics – “sulfa drugs”
decompose at 200°. When heated strongly in a The following explosive sulfonchloramides
flame it decomposes explosively (Ref 2) and their salts’ were prepd by Chattaway (Ref 12):
s-Dibenzenesulfonylethylenedibromodiamine, or I. Sulfondichloramides and
N,N'-Dibromo-N,N'-ethylene-bis-benzenesulfonamide Sulfonalkylchloramides
C6H~S02NBrCH2CH, NIkS02C6H<, mw 502.22, Benzenesulfondichloramide or N,N'-Dichloro-
N 5.58%: ode yellow prisms, mp 134°; decomposes benzenesulfonamide (called N,N'-Dichlorbenzol-
sulfamid in Cer), C6H5S02NC12; mw 226.08, N
 H 8

6.20%; slightly yellowishcrystals, mp 76°. When 6.49% and Sodium, Cl#c(SOzNa:N@2; mw

heated rapidly in a flame, explodes feebly (Ref 399.18, N 7.02%, are in the form of color- .
salts
12). Its anhydrous Potassium salt, C6 H5S02 K:NC1; less hair-like crystals, which decompose ex-
mw 229.7, N 6. 19Z0,’ colorless prisms, explodes plosively at 145-150° and 165-170° respectively
when heated rapidly at 140-145° and the Sodium (Ref l?)
salt, also called Chloramine B, CcH~S02Na :NC1; Il. Arylsulfonalkylamides
mw 213.6, N 6.6%; explodes at 180 to 185° Compounds of this nature are readily produced
(Refs 1 & 12) by the action of an aqueous solution of hypochl-
Toluene-o-sulfondichloramide or N,N-Dichloro-o- orous acid on the sulfonalkylamides. These com-
toluolsulfonamide, (called Dichlor-o-toluolsulfamid pounds, when rapidly heated, decompose with
in Ger), CcHq(CH3)S02N.Clz; ,mw 240.11, N 5.83%; the evolution of gas but without explosion. Two
mp 33”. This compound is not listed as”an examples are:
explosive, but its anhydrous Potassium salt Benzenesulfonmethylchloramide, CCH5S02NC1CH3
explodes feebly at 145”, while its Sodium salt Naphthalenesulfonmethylamide, C10H7SOZNHCH3
explodes with some violence when heated to III. Sulfondibromamides and
17,0-175° (Ref 2 “& 12) Sulfonalkylbromamides
Toluene-p-sulfondichloramide or N,N-Dichloro-p- Toluene-p-sulfondibromamide or N,N-dibromo-
toluolsulfonamide (called N,N-Dichlor-p-toluol- toluene-p-sulfonamide, H3CCGH4S02NBr2; mw
sulfamid in Ger), C fjHq(CHs)SOz NC12; mw 240.11, 329.01, N 4.26%; orange-colored plates, mp 104°,
N 5.83%; mp 83°, is not listed as an explosive, partially sol in chlf (Ref 7). When heated rapidly
but its anhydrous Potassium salt explodes with it decomposes explosively. Its anhydrous Potas-
violence at 160-1650 and” the Sodium salt (also sium and Sodium salts explode mildly at 145-
“called Chloramine T) at 175-180° ~.Large quan 150° (Ref 12)
tities of the Na salt are toxic (Refs 3 & 1,2) Toluene-o-sulfondibromamide, H3CCcH4S02NBr2;
Nitrobenzene-m-sulfonchloramide, Potassium mw 329.01, N 4.26Yo; orange-colored rhombic
and Sodium “02 NC6’HQS02K:NC1; mw
Salts. plates, S1sol in pet eth, mp 80° (Ref 2). When
heated rapidly above its mp it decomposes ex-
274.72, N 10.20%; and ‘02 NC6H4S02Na:NCl;
plosively. Its anhydrous Sodium salt decomposes
mw 258.61, N 10.83%. Both anhydrous salts are
explosively at 135-140° (Ref 12)
explosive. The first explodes at 155°; the
Nitrobenzene-m-sulfondibromamide or N,N-Dibromo-
second at 175° (Ref 12)
3-nitrobenzene-sulfonamide, C6HQ(N02)SOzNBr~
Nitrotoluene-p-sulfondichloramide, H3CCGH3(N02)-
mw 359.98, N 7.78%; orange rhomboids, mp 157,
S02NC12; mw 285.11, N 9.83%;:mp 101°, is not listed
(Ref 8). When heated in flame it decomposes
as an expl, but its anhydrous Potassium salt explodes at
explosively. Its anhydrous Potassium and Sodium
160° No sodium salt is described (Ref 4 & 12)
salti decompose explosively when heated
Benzene-m-disulfontetrachloramide, CGHa:(S02NC12)2; 2-Nitrotoluene-p-sulfondibromamide, H3CCGH3-
mw 374.04, ”N 7.4970; mp 128—3@. Colorless) ~ (N02)S02NBr2; mw 374.01, N 7,49%: transparent
transparent rhombic crystals (from pet eth). prisms, S1sol chlf, mp 142-143° (Ref 9). When
When strorigly heated the melted substance ex- heated, quickly to a high temperature it de-
plodes with’ a violence recalling the explosion of composes explosively (Ref 12) ~
nitrogen chloride itself (Refs 5 & “12)
The rest of the compounds described by
Naphthalene-2-sulfondichloramide, C6HqC4H3S02- Chattaway (Ref 12) do not explode but merely
NCIZ; mw 276.14, N 5.07%; ’is not listedlas an decompose with the evolution of gas
explosive, but its anhydrous Potassium salt ex- IV. N-Halogen Derivatives of
plodes feebly at 17d and the Sodium salt at P-Halogen substituted
180° “(Ref 12)
Benzenesulfonamides
Naptithalene-2,7-disulfontetrachloramide:
C12N02S02CGH3C4H3SOZNC12;mw 456.10, N Baxter and Chattaway (Ref 13) describe several
6.14%; colorless, transparent pyramids, mp 165° compounds of this class, some of which are
(Ref 6). The melted substance explodes with explosive:
great violence when strongly heated. Its anhydrous p-Bromobenzenesulfondichloramide or N,N.
Potassium, C..H, LSO.K:NC1).; mw 431.40, N Dichloro-3-bromobenzene-sulfonamide,
 H9

C6HqBrS02NC12; mw 304.97, N 4.59%; mp 106° (1967) 2) C. Paillard et al, CR AcadSci

(Ref 10). It is not listed as an explosive but Paris, Ser C, 264, 1721 (1967) & CA 68,
its anhydrous Potassium salt explodes, without 6980 (1968)
melting, at 165° and its Sodium salt at 178°
(Ref 13) Halogen-Metal Interconversions with Halo-
p-Bromobenzenesulfondibromamide, CcHaBrS02- genated Anilines. A highly
explosive com-
NBr2; mw 393.87, N 3.56%; rnp 132° dec. It is pound which appears to be p-N, N-Trilithioani-
not listed as an explosive but its anhydrous Iine is formed as a by-product in the reaction
Potassium and Sodium salts explode without of BuL1 and p-Br-anilhe but not o-Br-aniline
melting at 193° and 2110 respectively (Ref 12) (Ref 1). More recently this reaction was re-
p-lodobenzenesulfondichloramide, CGH41S02NC12; peated but no by-product is mentioned (Ref
mw 351.97, N 3.98Y0,mp 147°1dec, is not hsted 2)
as an explosive but its Potassium and Sodium Refs: 1) H. Gilman & C.G. Stuckwisch, JACS
salts explode without melting at 150° and 185° 71,,2933 (1949) & CA 45, 5i27 (1951) 2)
respectively (Ref 12) M.O. Kiwa, NipponKagakuSasshi 84, (3), 272
Refs: 1) Beil 11, 48, (13), [28] & {79} (1963) & CA 59, 14013 (1964)
2) Beil 11, 87 3) Beil 11, 107, (29), [63]
& 301 4) Beil 11’, 112 5) Beil 11, 201 & Halotetrazole Salts. The hazards heretofore
454 6) Beil 11, 217 7) Beil 11, 108 &{302} encountered ‘in the prepn of halotetrazoles have
8) Beil 11, 71 9) Beil 11, 112 10) Beil 11, been eliminated, and a safe method for diazoti-
58 & (17) 11) Beil 11, (19) 12) F.D. zing 5-aminotetrazole has been devised. Several
Chattaway, JCS 87, 145 (1905) 13) R.R. Baxter salts of halotetrazoles were prepd, and aside
& F.D. Chattaway, JCS 107 1814 (1915) from results of practicrd importance such as the
‘production of compds of interest as initiator
Halogenation. Incorporation of one of the halo- materials, this work may give rise to some
gen elements into an organic compound, eg important theoretical consideration as to the
C2H4 + Br2 = C2H4Br2. Review articles and fundamental chemistry of initiators
books on halogenation are listed below Prepns of the following hrdotetrazoles are
Refs: 1) E.T. McBee & O. Pierce, IEC 40, 1611- described by Gaughran & Kaufman (Ref):
1619 (1948), Halogenation, with 207 refs & in Copper Chlorotetrazole in 74% yield,
Sept issues of the succeeding years 2) Groggins Chlorotetrazole in 55% yield,
(1952), 176-265 3) P.B.D. De la Mare & J.H. Silver & Mercury Chlorotetrazole in quanti-
Ridd, “Aromatic Substitution Nitration & Hal- tative yield,
ogenation,” Acad Press, NY (1959) 4) L.R. Copper Bromotetrazole in 7$% yield, :
Belohlaw & E.T. McBee, IEC 50, 1015 (1958) Bromotetrazole in 70% yield,
Silver & Mercury Bromotetrazole,
Halogen Azides are described in Vol’1 under Iodotetrazole in about 10% yield.
Azides: BrNa,, p A525; CIN~, p A529; FNq, It was recommended that some of the salts
p A536; & INS, p A542. A recent review “’ ““’ be thoroughly investigated for possible appli-
(Ref 1) gives the preps, them & phys props ~‘ cation as initiator materials
of halogen azides, and reactions of metal Ref R.J. Gaughran & J.V.R. Kaufman,
halogens to give met~lohalogenazides.. Also ., “Synthesis and Properties of Halotetrazole Salts,”
discussed are reactions of metal carbonyls & PATR 2136 (Feb 1955)
organometallic comps with halogen azides, &
stability relations of azides (Ref l). The heat 1-Halo-2-vinylacetylenes. Chlorine, bromine &
of decomposition and max flame temp of iodiqe vinylacetylenes can be prpd by the
ClN3 have been measured recently (Ref 2). reaction, at 0°, of the halogen in aq KOH with
They are, respectively, -93.2 kcal/mole and monovinylacet ylene (Ref 1). All polymerize. in
3380”K air to form explosive polymers, with the I-compds
Refs: 1) K. Dehnike, AngChem (IntnEdEngl, being the most exdosive of the three. Polymeri-
6, (3), 240 (1967) & CA 66, R 104639 zation is also accelerated by UV, ozonides,
 H 10

benzoyl peroxides, etc. Additional methods of Halsey and Savage Explosives. Several smoke-
preparation and props of the individual comps ~ less powders, containing Ammonium Picrate,
~,..
.,., were patented in the US in 1896. They were
are given below:
1-Chloro-2-vinylacetylene, 4-Chloro-1-buten-3- prepd by adding finely “pulverized Ammonium
yne, C1C:CCH:CH2; mw 86.52; colorl liq (dark Picrate to an aqueous solution of potaisiym
ens on air exposure), bp 55-57°, d 1.003 at 20~ bichromate in such a manner as to form a
RI 1.4663 at 20° (Ref 2); insol in w; sol in plastic mass and then slowly adding a coned
chlf. Can be “prpd by ~eating Me2NCH2CH2 :CHC1 aqueous solution of potassium permanganate.
with MeI followed by treatment with base (Ref No 1 Cannon Powder: Amm Picrate 68,
5). Can be distilled under nitrogen but residue KzCr207 25, KMn04 7%. No 2-Sporting, Pow-
tends to explode, as does polymer formed in der: Amm Picrate 73, KzCr207 .20, KMnOq
air. Hydroquinone appears to act as a preserva- 7%. No. 3 Rifle Powder: Amm Picrate 50,
tive (Refs 2 and 3a) KzCr207 20, KMn04 7, Ba or Sr nitrate 23%
l-Bromo-2-vinylacetylene or 4-Bromo-l-buten-3- Refi Daniel (1902) 367
yne, BrC~CCH:CH2; mw 130.97; colorl liq (darkens
on air exposure), bp 52-53° at 217mm, d 1.480 Halstead Arsenal. An Armament Research
at 20°, RI 1.5182 at 20°; insol in w; sol in chlf. Center, Kent, England
Can be prpd by reacting Br with (CH,:CHC lC), Hg
(Ref 3). The bromopolymer is more explosive Halved Cartridge Gap Method. See under Phys
than chloropolymer. Bromopolymer forg-ied in Tests in Vol 1, p XIV
the absence of air is not explosive
1-lodo-2-vinylacetylene or 4-lodo-1-buten-3-yne, Hamilton patented in England in 1896 the ad-
IC:CCH:CH2; mw 177.97; colorless liq (darkens dition of up to 15% of urea oxalate in order
on @ exposure) bp 71.5° at 102 mm (Refs 2 to lower the temperature of explosion of dy-
& 3), 78° at 125 mm, d, 1.887 at 20°, ~ , namites and smokeless powders
1.5948 at 20° (Ref 2); insol “in” w; sol in chlf, Refi Daniel (1902), 367
& Etz O (Ref 4). Can be prpd by reaction of I
and vinylacetylene in liq ammonia (Ref 4); the Hancock’s Explosive. A blasting composition
reaction of I and vinylacetylene-MgBr in ether; or patented in 1911 consisting of. KC103 16,
I and (CH2:CHCi C)zHg in chlf (Ref 2) KN03 12, brown sugar 3,, K2Cr207 3, S 6;
Refs: 1) Beil 1, {1038} 2) R.A. Jacobsen & W.H charcoal 1, lamp black 1 part
Carothers, JACS 55, 4668 (1933) USP 1,967,864 Ret ‘W.F. Hancock, USP 995134 (1911)&CA 5,2724
3) W.H. Carothers et al, JACS 55,4666 (1933)’, (1911)
3a) Clift & Fedoroff Manual, Vol 2, p FI (1943)
4) TM. Vaughn& J.A. Nieuwland, JCS (1933) 741 Handhabungssichere Sprengstoffe. Cer for Explo-
5) A.T. Babayan et al, DoklAkadNaukArmen, SSR sives Safe to Handle and Transport
26, 153(1958) &CA 5219902 (1958) Refi Davis (1943), 347

Handgrenade. A grenade to be thrown by hand.

Haloxyline. An Austro-Hungarian explosive in-
See Grenades
vented about 1865. It represents a variety of
sulfurless Black Powders such as KN03 75.0,’
charcoal 8.5, wood pulp 15.0 and potassium Handling Bombs. See Bombs in Vol 2, p B238
ferricyanide 1.5%: A similar explosive was
patented, in 1866 in England (Ref 1)
Refs~ 1) Daniel (1902), 367 2) J. Pepin-
Lahalleur, “Poudres, Explosifi et Artifices:’
J.B. Bailli?re, Paris (1935), p 287 3) Thorpe’s
Dictionary 4 (1940), p 463. See also
Fehleisen Powder in Vo16, pF13-L
,.
 H 11

Handling Explosives. The general subject of Refs: 1) NOLR 1111, “Ordn Expl Train
handling explosives is discussed in Ref 2 Designers Hndbk” (1952) p 2-32 2) S.’F.
Specific info on the handling and storing of Vaskovskii, “Guide Book for Handling Explo- ,
common military explosives (taken from Ref 1) sive Materials” (in Russ), Gosudarst Nauch-Tech
is tabulated below Izdatel Lit po Geol i Okhrane Nedr, Moscow (1957),
Graphite-filled PVC provides resilient coatings 159 pp &CA 52, 16746 (1958) 3) J. Donahue &
which can leak off dangerous electrostatic J. Church, NASA Doc N63-i3415 “(1963) & CA
charges from explosives & propellants (Ref 3) 59, 15495 (1963) 4) R. Campbell & E.
Remote control sites for handl~g explosives Whitbread, Ind Chim Beige 32, 543 (1967) &
capable of withstanding detonations of up to CA 70, 59428 (1969)
10 lbs TNT are described (Ref 4)
HANDLING CHARACTERISTICS OF EXPLOSIVES
Explosive Storage Precaution Destroying solution
Mercury Ftiinate Wet Sensitive to flame and sparks Saturated sodium thiosulfate
Lead Azide do Sensitive to flame and sparks. Ammonium acetate
Forms sensitive copper azide
Lead Styphnate do Sensitive to flame and to static Sodium carbonate
electricity
DDNP do Sensitive to flame Cold sodium hydroxide
Tetracene do do
Nltromamite do
PETN do Hydrolyzed slowly by alkalies
RDx do Sensitive mixtures with iron and Hot sodium hydroxide
copper oxides, poison when.
taken orally
Pentolite 50/50 Dry
PTX-2 do
EDNA do Forms compounds with metals
Tetryl do Dust explosion hazard (22); Boiling sodium carbonate
contact with skin may cause
dermatitis.
Torpex-2 do
Composition B do
Composition A-3 do
Ednatol do
Picric Acid do Forms sensitive lead and copper
salts
HBX do
Tritonal 80/20 do
TNT do Slightly tcrxic; reacts with
alkalies and ammonia to
form sensitive compounds
Picratol “ do
Explosive D Dry-wooden When wet reacts slowly with lead
containers and copper to form sensitive
salts
Black Powder w Particularly sensitive to flame
and sparks
 H 12

Handy-Andy Riot-Control Cartridge. ~e E24 Hangfire Test. Due to the fact that delay in
(Cartridge) in Vol 5, p El-L firing of individual shots (hangfire) in auto-
matic weapons (especially in the case of
Hangfire. A brief undesired delay in the func- machine guns firing synchronously with a pro-
tioning of ammunition or blasting charges after pellor of an airplane) would bring disastrous
initiation. It usually refeis to delay .in ignition results, it is necessary to subject the weapons
of a propelling chge. This should not be con- and ammunition to a’ special test. This test
fused with “misfire”, when the shot or round usually consists of firing 600 rounds, in bursts
does not fire at all. Hangfire is ‘of no great of 75 rounds each, through a disc rotating at
importance when blas~ing ‘charges are fired 1800 rpm, the groupings being, measured, in
individually or when weapons such as cannons degrees from the leading edge of the shot
are discharged individually. But it could be nearest the zero mark. For aircraft use, the
disastrous if hangfire were to take place in an groupings must not exceed 15°; for other uses
automatic weapon tiring at high speed, for ex- “27°
ample, in machine guns or anti-aircraft guns (Refs The test may also be conducted in a special
1,2 &4) “electrostatic hangf ire machine”, which should
Twelve reported hangfires since 1932 are stated give the time between the shots of 0.0014
to be explainable if it is assumed that the explo- “seconds for aircraft weapons and 0.0025 sees
sives involved deflagrated at a burning rate not for other weapons
exceeding 300 m/see (Ref 3) Refs: 1) Ordnance Proof Manual 7-16 (1945)
Refs: 1) Marshall 2, (1,917), 589 2) Ohart (1946), 2) Ohart (1946) 6771 3) R.W. Evans, “Design
67 3) H.C; Grimshaw, Minist of Fuel & Power, and Development of Tests for Characterization
Safety in Mines Res Est, Res Rept No 34, 3 of Primers”, Denver Res Inst Final S~mmary
(195 1)& CA 46, 6385 (1952) 4) OrdTechTerm Report (May 1956) [Contract DA1-23-072-501-Ord-(P)- 14]
(1962), 151-L
Hannan Explosives. F. Hannan in 1882 de-
Hangfire A hangfire in small arms
Primers. veloped a chlorate expl consisting of K Chlorate
ammunition (initiated by a blow from a ‘firing 50, K nitrate 24, K ferrocyanide 12, charcoal
10 & paraffin 4% .
pin) can be defined as that condition which
exists when initiation of the usual chain of Refs: 1) F. Hannan, Eng P 5986 (1882) &
events following the release of the trigger irt a JSCI 2, 427-L (1883) 2) Cundill (1889) in NIP
loaded weapon, occurs at a rate slower than 6, 9 (1893) 3) Daniel (1902), 368 4) Giua
normal; the definition of hangfire for electri- Trattato, 6, (1959) 394
cally inhiated ammo is similar Hansen or Hydrogen Ion Concentration Stability
A hangfire may be of very short duration or Test. Hansen (Ref 2) gives the following test
may be several seconds in duration. Hangfire in applicable to proplnts, provided they contain
general can be caused by: weapon defects, slow not more than 0.5% of CaC03: a) Dry” ca
burning of primer compn and/or a slow rate of 50g of ground powder in a v~cuum oven at
ignition or combustion of the propellant chge 40° for 8 hrs b) Put 5g samples into each of
In order to measure hangfire of primers, it 8 tubes 16 mm diam & 360 mm long, graduated
is necessa~ to start a chronograph when the to 50 ml and provided with glass stoppers
primer is initiated and to stop it at the first c) Place the tubes into a constant temp bath
appearance of the primer flash at the flash maintained at 110° d) After one hr of
hole. This time interval can be considered to be heating, remove No 1 tube, cool 1/2 hr in air,
a measure of “primer time”, and any signifi-
and add distilled water of pH 7.0 up to the
cant increase above the average can be con- 50 ml mark. Shake well and determine pH by
sidered, to be a primer hangfue
the quinhydrone method e) Remove the other
Ref R.W. Evans, “D&ign and. Development of “tubes, one at a time, at intervals of one hr
Tests for Characterization of Primers”, @river (ie after 2, 3, 4, 5, 6, 7 & 8 hrs of heating)
Res Inst Final Summary Report (May 1956), and determine pH of, each f) Plot the pH
pp 23-26 [Contract DAl-23-072-501-Ord-(P)- 14] values on graph paper vs time. and dr~.y ?
curve
 H 13

Stability (K) is determined from the Hardingham proposed in 1884 in France, for
formula: mining use, cartridges containing dynamite com-
K= 15- (H) X 104, bined either with liquified NH3 or C02 or with
where (H) is absolute hydrogen ion concentra- flammable liquids such as alcohol, benzene or
tion. For example, if pH is 3.0, then H is 10-3 ether
~d K = 15 - 10-3 x 104 = +5, and the Refi Daniel (1902), 368
powder is satisfactory. If pH is 2, then H is
10-2 and K = 15 - lo-z x 104 = -85 and the Hardy’s Powders. Several powders were known
powder does not pass the test under this name, for example NaN03 60.1,,,
In a modified method, the powder is heated KN03 14.1, sulfur 8.1, charcoal 11.6 ,sugar 4.9,
under water at 100° to induce hydrolytic moisture 1.270
decompn Refi Daniel (1902), 368
Refs: I) I.,. Metz, SS 21, 186-88 (1926) & CA
21, 1013 (1927) 2) N.L. Hansen, F&h III Hargreaves Theory of Aging of Blasting Gelatins.

Nerd Kemistmijtet (Finland) 1926, 227-30 See Ageing of Dynamites in Vol 1 of Encycl,
(1928) &CA 23,4074 (1929) p A11O-R

Harlé (Cordeau dt$tonant de mine ?i la tolite). A

Hansen-Metz Potentiometric Test at 110°. The
French detonating, cord used in’ mining. It con-
following modified Hansen-Metz potentiometric sists of a TNT (core) enclosed in a lead tubing
test at 110° is described by da Rocha (Refs): of 5.9 mm external diam. Its. detonation velocity
Samples of proplnt are cut to pass a 2 mm is 5055 to 5165 m/see
sieve and retained on a 0.5 mm sieve. They are Rejl M. Dutour, M*AF 24, 578 & 583 (1950)
dried for 12 hrs under vacuum at 25-30° and
placed in tubes used in the Bergmann-Junk- Harpax or Harpago. See under Catapult in Vol
Mayerhofer Test (18. ~ 1 mm internal diam & 2, p C91
360 mm long). After heating up to 8, hrs, the pH
is determined. For an absolute hydrogen ion
Harpoon Antiship Missile (US Navy). THE
concentration, H, after 8 hrs of exposure at
NAVY’S HARPOON ANTISHIP MISSILE
110°, the stability is expressed as K = 15 - H
(McDonnell Douglas), has completed six of
x 104. Positive K means good stability, while
twenty scheduled full-scale flight tests following
negative K means poor stability
many launchings to test techniques. and com-
NOTE: Da Rocha proposed the terms static
ponents (CD, October 1972). Harpoon has been
and dynamic stability determinations. The first
fired successfully in its basic form from aircraft;
term refers to a single determination of the
with a 300-pound, 30-inch booster from surface
degree of denigration, while dynamic stability
ships; and from submarine torpedo tubes, with
is a trend expressing the tendency to denigration
folded wings and booster enclosed in a buoyant
of a powder with the time of exposure to 110°
capsule
from O to 8 hrs
THE MISSILE – propelled by a Teledyne
Refs: 1) J.P. da Rocha, Anais Assoc Qu<m
turbojet engine – is 17.5 feet long, weighs
Brasil 8, 141-47 (1949) & CA 45, 353 (1951)
1100 Ipounds, ,and carries a conventional war-
2) J.P.. da Rocha, Engenharia e Qui?n (Rio de
head. It flies at “wave height under midcourse ,
Janeiro) 3, 191-97 (1951); Bol Qufi Peruano
inertial guidance until the radar seeker locks
3, NO 16, 7-12 (195i) & CA 46, 8373 (1952)
onto the target. The missile climbs for a brief
3) J.P. da Rocha, Actas y Trabajos Congr
instant near the target, then dives on it
Sudamer Qufm 5° Congr (Lima, Peru) 1,
An outstanding feature of tlie weapon is its
391-95 (1951) (in Portuguese) & CA 49, 15241
adaptability to many launchers and its compat-
(1955)
ibility with ship and aircraft targeting equip-
ment. These include the Asroc ASW weapon,
late-model Terrier and Tartar launchers, and A-7
attack, S-3 ASW, and P-3 patrol aircraft
 H 14

After the twentieth flight in 1974, a third Hasethrol. A medical name for PETN, which
Defense Council review will make a go-ahead is used as a depressor of blood pressure
decision on pilot production – an extra step
because the Navy, to save costs, was allowed to Hassia – Chlorat or Spreng - Chlorat. Ger WWI
bypass a prototype competition expl consist of K chlorate 65 & combustibles
Ref The Common Defense Bull No 392, 35%. It was claimed to be comparatively
June 15, 1973 insensitive
Refl Marshall, Diet (1920), 48
Harries Method of Ozonization of Organic
Compounds. See under Ozonization of Organic HAST. Abbrev for High-Altitude Supersonic
Compounds Target
Ref’ Maj-Gen J.G. Zierdt, Ordn 58, May-June
Harrisite. See Composition C-4 in Vol 3, p 1973, 480-82
C485
Haswelite. A British permitted explosive which
passed the Buxton Test (See Vol 2, p B 394).
Harrison Powders (1 860), A mining expl con-
It contains Am nitrate 59, Ba nitrate 3.5,’TNT
sisting of potassium chlorate 70, starch 10,
12 ,Na chloride 25.5%
carbon 10 & sulfur 10’ZO.An army incendiary
Refi Marshall 3, (1932), 119
rnixt was composed of KC103 65, starch 6,
carbon 6, sulfur 12, licopodio ,2, tar oil & Haubitze. Ger for Howitzer
charcord dust 3Y0. A patent of 1862 reported an
expl consisting of KC103 or NaC103 56, K Hawk. See under Missiles and Glossary of Ord
ferrocyanide 28, starch 4, sulfur 7 & charcoal (1959), 146-R
5%
Refs: 1) Cundill (1889) in MP 6, 9-10 (1893) Hawkins. Patented in ‘England, in 1894, a liquid
2) Daniel (1902), 369 3) Giua, Trattato, 6, explosive which was used as a fuel in internal
(1959), 391 combustion engines. A mixture of KN03
50.0, sugar syrup 33.4, KC103 9.3, and K2Cr207
Hart Powder (1888). A powder patented in 8.3% was dissolved in 300 parts of water and
1888 in England, made by impregnating the was fed by means of an injector into a combus-
grains of KC103 with a solution of sugar, or tion chamb& of a motor
with a liquid hydrocarbon Refi Daniel (1 902), 369
Refs: Cundill (1889) in MP 6, 10 (1892)
2) Daniel (1902), 369 Hawkins Brothers. Patented in 1896 in England,
a mixture of the following approximate composit-
Harry Diamond Labs. The Army has classified ion KC103 60 to 64,,sugar 30 to 32, wood flour
the Harry Diamond Laboratories at Adelphi, or soot 2 to 4,potassium bichromate 2 to 8%
Maryland, as a permanent US Army installation. Refs: 1) Daniel (1902), 370 2) Giua, Trattato ~
The facility is a corporate laboratory of the 6, (1959), 391
US Army Materi61 Command, specializing in
fuzes, fluidics, special purpose radars, nuclear Hawkite. .A mining explosive of the Favier type:
weapons effects, and other research, develop- NHdN03 59 to 63, Ba(N03)2 4 to 2, TNT 15
ment, and engineering for weapons systems to 17, NaCl 23 to 18%. It has 76-81% of the
Refi The Official Magazine of United States power of standard 60% Gelignite
Army Logistics, Vol “5, No 2 (Mar-April 1973) Refi Marshall 3, 119

Harvey’s Explosive. An initiating composition Hay (Foin in French). Cured grass usually used
which was detonated by the addition of a drop as animal fodder and in:
of coned sulfuric acid. It contains KN03 74.3,
sugar 19.2 ,gallnut 6.5% Nitrohay (Nitrofoin in French) An explosive, :
Refs: 1) Daniel (1902), 369 2) Giua, which may be prpd by the nitration of dried
Trattato 6, (1959), 400 and powdered hay. It was patented in England ‘
 H 15

in 1873 by Trench, Faure and Mackie for use be quite hazardous. Here too, some way is
in composite explosives such as Nitrohay + resin + needed to select the composition of hazard.
ozocerite, coilodion cotton dissolved in a volatile Although there are many sorts of hazard, we are
solvent, glycerin and charcoal or soot concerned here with the risk, danger, o: peril
Rejl Daniel (1902), pp 522 under Nitrofoin resulting horn handling or processing a given
and 773 under Trench chemical or a composition of matter
The manufacture and handling of chemicals
Haylite. British explosive of the carbonite type: has generated a body of experience that is use-
NC 25 to 27, NC 0.5 to 1.5, KN03 19 to 21, ful, as far as it goes. The National Fire Codes
Ba(N03)2 19 to 21, wood meal 12 to 14, gela- segregates hazardous materials into five levels of
tinized silicic acid 6 to 8, ammonium oxalate reactivity ranging from zero, indicating no special
10 to 12% reaction hazard, to four, indicating the most
Refi Naoiim, NC (1928), 402 severe reactivity hazard. This ,code lists a degree
of reactivity for nearly 1000 chemical materials
Hazards of Detonations (and Explosions). See For many years the” explosive industry has
Detonation (and Explosion), Hazards of in Vol used the drop weight test to gauge reactivity by
3, p D5-L activating a material placed on an anvil with
the energy imparted by a falling weight. Drop
Hazardous Materials. See Dangerous Materials weight tests are difficult to interpret since the
in Vol 3, p D6 physicaJ properties and characteristics vary from
one sample to the next, but the comparative
Hazardous Materials Regulations, Index. A order of explosives by this test is known. If a
101 page pamphlet, published as Title 49, Code sample gives a positive drop weight test, it is
of Federal Regulations, Parts 170-180 (1972 hazardous, but a negative test does not necessarily
Revision), Supt of Documents, Govt Printing prove lack of hazard. Some of the less sensitive
Office, Washington, DC, 20402, 501# materials require more activation than the drop
weight gives. For example, tests are often run
Hazards of Detonations (and Explosions). See in which a No 8 blasting cap, or a 50 g
Detonation (and Explosion), Hazards of in charge of Tetryl are used to provide increasing
Vol 3, p D5-L steps of activation energy
Energy Relationships Within a Molecule
The intrinsic energy of a substance determines if
Hazards, Prediction of. D.R. Stun has developed decomposition will be exothermic, and its
methods of linking thermodynamics and kinetics ability to react exothermically with one or more
to the prediction of potentird and real hazards additional substances. Once initiated, a hazar-
arising from exothermic chemical reactions dous compound generates energy. The energy
(including explosions). We quote extensively generated may be derived from (1) the release
from his publications of stored energy in the compound, or (2) a
“Modern technology has been quite successful chemical reaction forming more stable products
in developing tailor-made chemicals to cope with from the atoms in the compound or mixture
specific problems. However, this effort has also An example of (1) above is acetylene that
introduced some additional problems since manu- absorbs 54.2 kcal/mole (stored within the
facturing and handling experience is frequently molecule) when it is made from its elements:
inadequate” to properly answer questions of graphite and hydrogen gas. Once decomposition
hazard. Some way is needed to distinguish of acetylene starts, the 54.2 kcal of heat is
hazardous from nonhazardous chemicals, and to evolved which raises the temperature of the
establish a measure of the extent of hazard products (graphite and hydrogen gas) to 2898‘K
As technology solves the questions it en- with an accompanying pressure increase if’ the
counters, new compositions of matter are “volume is held constant. Self decomposition is
formulated. These formulations are compounded regarded as the primary hazard
of two or more chemicrds, each of which’ may An example of (2) above is ammonium
present no special hazard but, once mixed, may nitrate that evolves 87.27 kcal/mole when syn-
 H 16

thesized from its elements: hydrogen, oxygen, The large numbers (1 ,2,3 & 4) in this Figure
and nitrogen gases. Thus, ammonium nitrate is refer to NFPA Chemical Reactivity Ratings
lower on an absolute energy scale than acetylene. which are described below:
However, once decomposition of ammonium O....Materials which are normally stable even “
nitrate starts, the decomposition products, nitro- under fire exposure conditions and are not
gen, water, and oxygen gases, are lower on the reactive with water
absolute energy scale than ammonium nitrate, 1....Normally stable materials that may become
and -28.2 kcal/mole are released heating the unstable at elevated temperatures and
product gases to 1242 “K with an accompanying pressures, or which may react with water
pressure increase if the volume is held constant with some release of energy, but not
In addition to the energy released by de- violently
composition of a compound, there is the 2 . ...Materials which are normally unstable and
possibility of additional energy release by a readily undergo violent chemical change, but
secondary reaction with one or more other do not detonate. Includes materials which
substances present. In the acetylene example can undergo chemical change with rapid
above, the initial decomposition produced release of energy at normal temperatures and
graphite and hydrogen gases at a decomposition pressures or which can undergo violent
temperature Td of 2898 ‘K. In the presence of chemical change at elevated temperatures and
oxygen gas, an additional reaction to carbon pressures. Also includes materials which may
monoxide and water ‘takes place with further react violently with water or which may
release of energy causing a further increase of form potentially explosive mixtures with
temperature and pressure. We have arbitrarily water
elected to call the latter temperature (with 3 ....Materials which are capable of detonation or
oxygen) the “flame temperature,” To. As we of explosive decomposition or of explosive
shall see, these two conditions, self decomposi- “reaction but which require strong initiating
tion, and oxidation to the most stable natural source or which must be heated under con-
products at the flame temperature, are impor- finement before initiation. Includes materirds
tant conditions. We shall use the symbols d for which are sensitive ~to thermal or mechanical
decomposition and o for oxidation” (Ref 1) shock at elevated temperatures and pressures
After presenting the methods of calculating or which react explosively with water with-
the requisite thermodynamic quantities Dr Stun out requiring heat or confinement
suggests the correlations between them and 4 ....Materials which are readily capable of deto-
potential hazard ratings shown in Figure 1 nation or explosive decomposition or ex-
(taken from Ref 1) plosive reaction ab normal temperatures and
pressures. Includes materials which are
sensitive to mechanical or localized thermal
shock
l NFF’A
O
!
& NI$PA 1 According to Dr Stun examination of Fig 1
1500 - l+ 9
6
t4FPA 2
NPPA 3 reveals the following:
* NFPA 4
l
+ U.clsssifie.d “1. Materials that achieve zero oxygen balance,
1000 -
0 can detonate, and present the greatest hazard
lt are along the base line
1500 -
/’1/ 2. The lower third of the chart (up to To-Td
It ,.
,,
l = 1,000”K) contains hazardous explosives or
1000 - )H ,’ 2 .s materials with an NFPA riiting of 3 or 4 (shock
)1 N! ~--
t #@ ~- sensitive explosive materials). The single excep-
-.” 3
Soo - ,’ ,0
tion is hydrogen cyanide with an NFPA rating
of 2 (unstable, capable of violent chemical
&..—
0 Soo 1000 - “isoo 2000 2500 ““3000 change, but does not detonate)
3. The middle third of the chart (from
Fig, 1 Extent of Potential Hazard Rating Td 1000 to 2000 “K) contains materials that are
explosive and have NFPA ratings that range
 H17

from 4 (shock sensitive’ explosives), such as TNT

at 1,084”K, through ratings of 2 (unstable
m?terials that do not detonate), to a rating of
1 (normally stable materials that become un-
stable at elevated temperatures and pressures),
such as 4-nitroaniline at 2013”K. Nitroethane
with an NFPA rating of 3 is a glaring exception
at 1943°K, only 70” K under 4-nitroaniline,
whose NFPA rating is 1
4. The upper third of the chart (above
2000 “K) contains materials that are, almost
entirely normally stable with an NFPA rating of
O. The two exceptions are 1,3-butadiene and
styrene with NFPA ratings of 2 (normally un-
stable and can undergo violent reaction, but do
not detonate)
Thus, there is a more or less gradual pro-
gression from the most hazardous materials in
the lower right corner to the “safe”, or nor-
mally stable materials, in the upper left corner.
Of the 50 compounds studied; 44 were rated,
and 6 were unrated. The latter, (acetamide,
benzamide, hydroquinone, cellobiose, 1-(p-
nitrophenyl) ethanol, and phenylacetylene) seem
to be fairly placed in the chart. The’ four
exceptions mentioned, (hydrogen cyanide, ,nitro-
ethane, 1,3-butadiene, and styrene) demonstrate
that individual peculiarities will cause certain
materials not to follow the general pattern
exactly. A line was drawn by eye from Td =
3000 “K on the baseline to Td = 500”K at
(To-Td) = 2600”K fits the points fairly well.
This line was divided into five equal segments,
then four lines were drawn from the origin
through boundaries of each segment and each
segmental area was given an “extent of potential
hazard rating” similar to the NFPA Chemicrd
Reactivity Rating”
The results of the thermodynamic calcns and
the compounds for which they were made,
together with the NFPA ratings are shown in
the following Table (taken from Ref 1):
 H 18

TABLE 1
* ** ***
—
~ n kc 100 gram Pressu in o,c.heres
-—
r -Td) AC iii-- [f.H -AH ~ PO-P*)
~~ -T;*
1. GLYCOL D!)L1TRA7E (tj . . . o -97 o 36.4 0.0
2. NITROCELLULOSE 14,14t (8] . . .229 .80(s) 28s4 2213 641 -114 -66 -48 41.4 27.6 1s.8
w% @
3. MANITOL HSiU;TWTE (11) . . 154.00 (s] 286S 286s 0 -89 -89 0 33. s 33. s 0.0
C6H8%C1 e
4. OIPENTAERYTHR:TOL HEXA.. I7RA7E (14; ,220.00 (s]’ 2944 2806 138 -11s -98 .17 44.0 38.8 3.2
c10H16N6019
S. GLYCEROL6P2SOLACTATE TSI:NITPATE (~) C6H9N3011 1S4.8S(1) 2932 2718 214 -12s -94 -51 46.7 17.2 9.s
6. NITROCLYCER1!iE (1S) .< . . -89.00(1) 2ss9 28s9 o -93 -93 0 34,6 34.6 0.0
‘,”,N,”, 6
7. POLyvImL N1T2L4Tz (~) . . (C2H3X03)n -28. s8(s) $011 2S64 447 -14s -91 -s4 55.4 39.0 16.4
8. TETRYL (26) . . . . .8 .00(s) .3097 2673 424 -138 -84 -54 s4.6 37.8 16.8
C7WS%
9. BETA S(MX (s2) . . . . .17 .92(C) 299S 2921 74 .119 -100 -19 47.6 41. s 6.1
CW808
10. CYCLONITE ROx (32) . . . +16.90(s) 3001 2932 69 -120 -1oo -20 47.8 4L.7 6.1
C3N6N606
11. S,3, S- TRIANINO- 2,4,6 -TRIN1TROBEYZ5KE (~] C6H6N606 -36.8$ (s] 3009 1626 1383 -14s -47 -98 S6.4 2s.3 31.1
12. l, S- 01AMINO-2,4,6 -TR1NITS02ENZEKE (4_4) C6H#s06 +8.0 (s] S091 2195 896 -141 -68 -7s S6.2 33.3 22.9
1S. NSTRIOL TRINITRA?E (47) . . CsHgN309 106.00(&) 2962 2688 274 -13s -97 -3a 51.0 39. s 11. s
14. N1TROGUM41OINE (47) . . . af4N402 -21.76(s) 2796 1048 948 -124 -61 -63 49.0 29.7 19.3
1S. ETNYLENEDINITRMINE (48) . . -24.70(s) 2929 2s41 387 -134 -93 -41 S2. S 40.0 12. s
c2H6N404
16. A26S2NIUN PICWTE (@ . . -93.0 [s) 2976 1?43 123s -141 .s2 -89 S3.6 26.1 ?7. s
c6H6N407
17. 2,4,6 .TRINITRoMILINE (g . -17.8 ,(s) 3072 2077 99s -144 -61 -83 S6.4 30. s 2s.9
c6H4N406
18. 1,2,4 -BUTLYETRIO.TRI NITRATE (s.q) -9s.1s(1) ,?916 2889 27 -10s .100 -s 40.0 38. s 1.s
C4W33’J9
19. M040NIUM PERCHLORATE (67) . . NHJCIO, @ -70.69(c) ls7e 1S7B o -11 -32 o 16.7 16.7 0.0
20. PICRIC ACID (8S) . . . - ‘ 4 -51.70 (s] 30s1 2464 507 -110 -72 -s8 SO.2 32. S 17.7
c6H3N307
21. AWONIUN HITRATE (100+) . .
NH4W ‘ 83 .87.27 (C) 1246 1246 0 -3s -3s o 18.2 18.2 0.0
22. DIETNYLENECLYCOL D1N1TP_4TE (100. ) 102.0 (1) 2949 2470 479 -144 -92 -ss S4. O 38.1 1s.8
C4H8N 2°7
23. TRIETNTLENEGLYCOL OINITRATE (100. ] C6H12N208 las. oo(t) 2975 1s93 1S80 -173 - S6 -117 6S.0 28.9 36.1
24. 2,4.6 .TRINITROTOLUENE [loo+) . -14.2 O[S)]31O9IZO2S 1084 -16S -63 -102 64. E 29.0 3s.0
C7%N3’% o
2S. 2,4- DINITROPHEYOL (K) C6H4N20S -ss. s0(s) 306S 1477 1s88 -16S -42 -123 63.7 21.4 42.3
26. ACETYLENE . . . +s4. 19(g) 3341 1898 443 -449 -las -264 190.6 39.6 1s2.0
C2”2 .
27. NITROETHANE . . -34.33(L) 3007 1064 194s -21s -31 -176 81.4 22.4 S9. O
C25WJ2 “
28. HYDROGEN CTANIDE . HCN +31. zo(g) 32s2 2s77 67 S ‘-2s4 -111 -143 107.0 32.1 74.9
29. Ai.LENE . . . .4s.92(3’) 3249 1861 1388 -466 -11s -3s1 190.6 31.2 1s9.4
CSH4
30. 6sZTWLACETYLENE . . .44.3z(g) 3246 lals 1431 -466 -111 -sss 190.2 So. s 1S9.’7
%“4 “
S1. 1,&OICHLOROPROPENE . -12.00(1) 5021 1228 1793 -266 -19 -137 69.0 11.1 S7.9
C3H4C12 .
12. l, S. BO_TADIENE . .
C4H6
l 20.40(gJ 3184 992 2193 -469 -46 -423 186. S 16. B 169.7
33. S2YREHT . . . +24.8 s(1) 3191 923 2268 -423 -34 -309 160.2 10. Z 158.0
C8N8 “
34. 4-NITROANILINE . . -9.92(s) 3116 1103 2013 -249 -35 -z14 97.8 1S.6 82.2
c6H6N20Z “
33. CYCLOPROPMLE -’ . .lz. 74(g) S16S 936 2229 -s0s -47 -461 201.7 19. s 1s2.2
C3H6 .
36. BIPHEhYL . . . .28. so(t) 3194 B98 2S06 -406 -29 -377 161.6 7.9 1s3.7
%2%0 .
37. BENZENE . . . .11 .72(1) 5183 868 231s -421 -29 -392 167.4 8.8 1S8.6
‘6H6
38. BUTENE-1 . . . .O. es(g) 3143 BZS 2318 -502 -3s -467 196.4 14.4 182.0
C4H8
39. ANIL2SE . . . +7.43(t) Jlso 822 2328 -38o .2s -3ss 1s0.1 9.2 141.0
%H7N .
40. 1,S-DZCHLOROPROPA)+E . -48.30(1) 2961 642 2319 -186 -lo -176 74.3 6.0 68. s
Cs%clz .
41. ACETONE . . . -s9.30(1) 103$ 704 2331 -348 -19 -329 2s1.2 9.1 122.1
c3N60 “
42. PROPA!4E . . . -Z4.82(g) S09S 626 2469” -s44 -19 -s2s Zlo. z 10. Z 200.0
w “
4X. OCTAXE . . . -s9.74(1] 31OZ S91 2511 -s14 -1$ -499 199.0 8.1 190.9
C8%8 “
44. CELLOB1OSE (WDOD)” . S29.40[S) 286S 758 2107 -204 -19 .18s 73.2 9.3 63.9
C12NZ?%1 “
4S. ACETIC ACIO . . 11 S.70(1) 2771 302 2469 -zoo -1 -199 69.8 3.3 66.5
c2H402 .
46. PHEHYLACETYLENE . .
‘8H6
l 67.72(1) S243 1468 177s -406 .67 -339 164.8 14.4 1s0.4
47. 1- (P-NITROphiEWL) ETIfMOL -S3.00(1) 3204 1006 2098 -272 -32 -240 97.8 1S.6 82.2
CBH9N03 .
48. HYOROQUINONE . . -87. S1(s) 5067 803 2264 -286 -21 -25s 107.1 7.s 99.6
C6N60Z “
49. BENZM(l DE . . . -48.47 (,) 3098 748 -18 -502 123.9 6.7 117.2
C7H7N’3 .
SO. ACETAN:OE . ., . C2N#0 . 0 -7 S.90(t) 288S 301 l 8 -274 98.4 3.4 9s.0
1 _, g —. -—
[N l tlon.1 Fire Promc:im Association C1. asific. ci< ‘*d by ..6A; “x ~. Unc sified z e.
3SI. SC).]
.———.
lTh8 parent!ie tic number is=~-c~~— req., —”- re=o~a%i.—~lur. t4~ofieI~t m. t. Yhr,so underlined ?rs
converted Pic.timy Arsenal values. ] (K, is . known explosive. )

*TO = flame temp; Td = decomposition temp

**AHO = heat Of combustion; AHd = heat of explosion
***p = combustion pressure; Pd = explosive pressure; both. at const vol
o
 H 19

The foregoing de~t with the prediction of heat generated by the reaction can be con-
potentiul hazards arising from exothermic tinuously transferred to the surroundings with-
chemical reactions. To predict the real hazard of out creating an increase in temperature, the
a reaction one must also consider how fast the reaction will proceed quietly in a well behaved
reaction takes place. Thus it is necessary to link manner
thermodynamics with chemical kinetics because If the heat from the reaction is not all con-
a potentially dangerous reaction may be so slow tinuously transferred to the surroundings, the
under a given set of conditions that it constitutes temperature of the reaction will increase,
no real danger. The classic example of this slowly at first, but will finally reach a temp-
situation is the 2H2 + 02 = 2H20 reaction erature where the reactiop is catastrophic.
which is highly exothermic, and consequently Such thermal run-away reactions are referred to ‘
potentially dangerous, but exceedingly slow at as “thermal explosions”. These thermal ex-
ambient conditions in the absence of external plosion reaction types convert “potential”
stimuli (sparks, flame, etc) hazardous systems into “real” hazardous
Dr. Stun presents the problem very well and systems. Thus, it is necessary to answer both
we quote (Ref 2): of these two main questions to evahrate the
“In the processing and handling of a chemical real hazard of a system”
or a combination of chemicals, there are two The actual linking of chemical (Arrhenius)
main questions to be answered. First, will there kinetics and thermodynamics was done as
be a reaction? Equilibrium chemical thermo- follows (Ref 2):
dynamics can provide an unequivocal answer to “A square with Td increasing upward from O
this question if the thermodynamic data for the to 3000”K was plotted on the left side, while
system is at hand. The previous paper (Ref 1) Ea was plotted on the right side with values
dealt with this aspect of the problem and was from O to 100 kcal/mole increasing in the
able to identify those systems where energy re- opposite direction (downward). The diagonal
leases were possible, and related the degree of line connecting the zeros of the two scales was
“potential hazard” to the magnitude of the named the Reaction Hazard Index, or RHI for
energy release. However, we do not live in a short.’ The end of the RI-H line at O“K would
static, equilibrium world of potential hazards. It unquestionably be at minimum hazard (or zero
is necessary to couple the potential hazard index), while the end of the RI-II line at O
evaluation with the rate of energy release by kcal/mole (zero activation energy) must surely
‘the reaction, to evaluate the real extent of
hazard. The chemical transformation and its E.
associated energy release will range from well Td ‘K KcALIMOLE
behaved to violent depending upon the rate 3000
of the reaction
The second main question that must be con- 2500
sidered is: what is the time rate of energy
2000
release? Once activated, potentially hazardous 40
materials undergo a nonequilibrium chemical I 500 50
reaction forming the most stable products under 60
the prevailing circumstances. The potentially I 000
[
hazardous systems are those capable of generat-
ing heat. They may require different levels of
activation, but the smaller the energy of activa-
tion, the more readily activated. Some materials
(those capable of polymerization for example)
500

0 ,k”
Reodion
MINIMUM HERE

HozorrJ Index
[ 80
90
100

IIHI = — 10 Td
may be thermally activated by the ambient ~d + 30E0
temperature of the system. Catalysis also plays Fig 2 Nomograph Linking the Decomposition
a vital role in promoting low level activations. Temperature Td 0 K with the Arrhenius Activa-
Regardless of the mode of activation, if the tion Energy Ea in kcalimole (Ref 2)
 H 20

correspond to maximum hazard (assigned an Again we quote Dr Stun:

index value of 10). Thus, RHI values from O to “An extended effort was made to find data
10 cover the whole range from minimum to for as many chemical compounds as possible
maximum hazard. The intercept on the RHI where the NFPA Reactivity Rating could be
line is given by the simple relationship RHI = compared directly witti the Reaction Hazard
10 Td/Td + 30 Es). A single value of the Index. Table 3 lists 80 compounds where the
Reaction Hazard Index between O and 10 pro- direct comparison could be made, and includes
vides a numerical index for a given material all of the basic data necessary to calculate the
Figure 3 shows an example of use comparing Reaction Hazard Index. The 80 compounds are
the reaction hazard of three hydrocarbon gases, grouped into the five NFPA Reactivity Ratings
methane, ethylene and acetylene, with the values as follows: 38 compounds with O rating (the
of Td, “Ea, and RI-H given in Table 2. The RHI largest and best established group), 13 compounds
figures correctly place methane as least reactive, in rating 1 and in rating 2, 6 compounds in
acetylene as most reactive, and ethylene roughly rating 3, and 10 compounds in rating 4. A
midway between the two “ cross plot of the NFPA Reactivity Rating versus
the Reaction Hazard Index is presented in Figure
4. The average RI-H for each NFPA rating is
given in Table 3, and is plotted as a + in Figure
EO 4. The best dotted straight line through the
Td “K KCALlh!OLE average indices shows a remarkable accord
between these two methods of reactivity hazard
10
rating
20
The NFPA Reactivity Ratings represent the
7. I
.
30
consensus of a committee of experts, ~nd
/~ - C<lii
“ 40 because of the number of factors taken into
c2y ---- so consideration the values agreed upon might in
------
lL-; -E some instances border on the next higher (or
&- 60

I/[
4.2
lUUU lower) value, and thus be indeterminate by one
70
unit. Hence, acetylene (No 72) rightfully carries
80
500 the maximum. hazardous NFPA Reactivity Rating
- ---- -!’p~4FfE 90
-.---5H4
----
of 4, and based on the evidence in Table 3, it
0 ~“”g --100
is not unreasonable that vinylacetylene (No 68)
Fig 3 Example of Use of Reaction Hazard should also
Index with Methane, Ethylene, and Acetylene The Reaction Hazard Index method presented
(Ref 2) here is based’ on experimentally observed. quan-
tities representing the Arrhenius energy of acti-
vation for the decomposition process and the
energy generated by the decomposition as indi-
cated by the adiabatic decomposition temperature
reached by the decomposition products. The
TABLE 2
method used develops a single numerical vahre
Comparison of NFPA Reactivity Rating
that is characteristic of the reaction hazard for
with the Reaction Hazard Index (Ref 2)
the compound measured and represents the real
hazard. Minimum definite measurements can be
NFPA prescribed for compounds where handling
Td Ea Reactivity experience is lacking. This objective method can
‘K kcal/mole RHI Rating
— —, be used to evaluate the real degree of hazard
for a single compound or for a mixture of
CHq Methane 298 103 2.9 0
chemicals, and can be used to develop a Reaction
CZHO Ethylene 1005 46.5 4.2 2 Hazard Index system that will effectively rate
CZHZ Acetylene 2898 40.5 7.1 4 all chemical reaction hazards with respect to
each other 7’
 H 21

Table 3
Data Sources, Reaction Hazard Index, and National Fire Protection Association Reactivity Rating
Reaction
AH~298 Activation Energy Wrzard NFPA
kcal/mole for E)ecomposit ion index Reactivity
TdOi(
No. Formula
—— Gaseous Compound Ref. (24) kcal/mcde R=** RHi Rating
1 CHC13 Chloroform - 24.2 683 47.0 (1) 3.26 o
2 CH202 Formic Acid - 90.49 800 30.6 (1) 4,66 0
3 CH3C1 Methyl Cidoride - 20.63 744 74.0 (4) 2.55 0
4 CH4 Methane - 17.89 298 103.0 (1) 0.88 0
5 CH5N Mc[hylamine - 5.50 767 58.0 (21) 3.06 0
6 C21i4C12 i, l-Dichloroethane - 31.05 847 53.5 (10) 3.45 0
7 C2H4C12 1, 2-Dichloroethane - 31.00 849 47.0 (21) 3.76 0
8 C2H.jBr Ethylbromide - 15.30 670 53.2 (21) 2.96 0
9 C2H5Ci Ethylchioride - 26.70 701 56.5 (1) 2.93 0
iO C2,ti6 Ethane - 20.24 597 89.5 (1) 1.82 0
il C2H7N Dimethylamine - 4.50 792 43.4 (21) 3.78 0
12 C2ti7N Ethylamine - 11.00’ 740 43.4 (21) 3.62 0
i3 C3H6 Cyciopropane + i2.74 936 65.5 (J) 3.22 0
i4 C3H60 Acetone - 5i.99 774 68. (21) 2.75 0
15 C3H7CI 1-Chloropropane - 31.io 699 55.0 (21) 2.98 0
16 C3Hg Propane - 24.82 626 63.3 (21) 2.48 0.
i7 C4H8 l-Butene - 0.03 825 59.1 (1) 3.18 0
i8 C4H8 Cyclobutane + 6.37 865 62.5 (7), 3.16 0
i9 C4H80 2-Butanone - 56.97 755 67.2 (21) 2.72 0
20 C41i802 Ethylacctate -105.86 735 48.0 (1) 3.38 u
21 C4fii9Br l-Bromobutane - 25.65 668 50.9 (21) 3.04 o
22 C4H9C1 l-Chlorobutane - 35.20 701 57.0 (21) 2.91 0
23 C4H10 Butane - 30.IS 633 86.3 (1) 1.96 0
24 C4hii0 2-Methylpropane - 32.15 61i 53.5 (21) 2.76 0
2S C4H]00 tert-Butyi Alcohol - 77.87 628 61.6 (1) 2.54 0
26 C4H100 Ethyl Ether - 61.88 761 78.0 (1) 2.46 0
27 C5Hi002 iso-propylacetate -115.40 696 45.0 (1) 3.40 0
28 C5ti12 2, 2-Dimethyipropane - 39.67 597 80.4 (1) 1.98 0
29 C5H12 2-Methyibutane - 36.92 626 58.6 (21) 2.62 0
30 C5Hi2 Pentme - 35.00 645 61.2 (21) 2.60 0
31 C5~i120 2, 2-Dimethylpropanol - 70.00 725 60.0 (1) 2.87 0.
32 C6!-i]2 Cyclohexane - 29.43 677 64.1 (19) 2.60 0
33 C6ti1202 Butylacetate -li6.7 715 46.0 (1) 3.41 0
34 C7H8 ‘Toiuene + 11.95 859 85.0 (1) 2.52 0
35 c7Hi4 Mcthylcyclohexane - 36.99 660 57.9 (19) 2.75 0
36 C71i1402 tert-Amyiacet3te -122.7 705 40.3 (1) 3.68 0
37 C8H1(3 Etilyibenzene + 7.12 830 73.0 (1) 2.75 0
38 C8iilr) 4-Xyiene + 4.29 817 79.5 (1) 2.55 0
Averageof 38 compounds 2.89 0
39 CH6N2 Methylhydruine + 20.40 1022 5i.9 (1) 3.96 0
40 C211402 Acetic Acid -104.93 634 67.5 (1) 2.38 0
41 C2ti@2 i, 1-Dimcthylhydrazin? + 20.30 953 49.6 (1) 3.90 0
42 C3H5Br Allylbromidc + ‘1i .80 988 45.5 (21) 4.20 0
 H 22

Table 3 (Continued)
Data Sources, Reaction Hazard Index, and National Fire Protection Association Reactivity Rating
Reaction
Ati; 298 Activation Energy Hazard NFPA
kcal/mole for Decrrmposit~on Index Reactivity
No. Formula Gaseous Compound Ref. (24) “TdOf( kul/nlOle Ref. ** RH1 Rating
w C3HSN Propionitrile 771iii 903 72.7 (1J x 1
44 c3H(j Propylene + 4.88 866 78.0 (1) 2.70 1
45 c3H(jo Propiorddehyde - 45.90 819 50.3 (21) 3.52 1
46 c4H(jo3 Acetic Anhydride -137.60 793 34.5 (1} 4.34 1
47 C5Hlo03 Diethyl Carbonate -151.60 753 46.0 (1) 3.53 1
48 C6H140 Iso-propyl Ether - 76.20 712 63.5 (1) 2.72 1
49 C7H7C1 Benzyl Chloride - 7:30 831 68.0 (1) 2.89 1
50 C10H12 Dicyclopcntadiene-endo + 46.60 990 34.0 (1) 4.93 1
51 CloH12 Dicyclopentadiene-exo + 46.60 990 38.5 (1) 4.61 1
Average of 13 compounds 3.58 1

52 C2H4 Ethylene + 12.50 1005 46.5 (1) 4.19 2

53 C2H4 Ethylene + 12.50 1005 37.7* (21) 4.71 2
54 C2H40 Acetaldehyde - 39.76 866 48.0 (21) 3.76 2
55 c3ti60 Propylene Oxide - 22.17 948 58.0 (26) 3.53 2
56 C3H602 Dioxolane - 70.0 911 53. (9) 3.64 2
57 C4H6 1, 3-Butadiene + 20.40 991 79.4 (22j 2.94 2
58 c4H(j 1, 3-Butadiene + 20.40 991 24.7 (27) 5.72 2
59 C4H80 Crotyl Alcohol - 37.40 863 41.0 (1) 4.12 2
60 c4k180 Vinyl ~thyl Ether - 33.50 880 44.4 (1) 3.98 2
61 c5Hgo Vinyi Ally] Ether - 12.8 959 30.6 (1) 5,11 2
62 cf3Hj3 Styrene + 35.22 993 19.2* (2) 6.33 2
l For the polymerization process
63 c#]2 Vinyl Cyclohexane + 16.8 876 62.2 (1) 3.18 2
64 N2H4 Hydrazine + 22.75 1338 60.5 (20) 4.24 2
Average.
of 13compounds 4.27 2
65 C2H40 Ethylene Oxide - 12.58 1062 57.4 (i) 3.81 3
66 C2H5N02 Nit roethane - 24.20 1161 45.0 (1) 4.62 3
67 C3H7N02 l-Nitropropwre - 29.80’ 1046 47.7 (1) 4.22 3
68 C4H4 Virsykicetylene + 72.80 ~3~7 28. (3) 7.33 3
69 C8H]802 tert-Butyl Peroxide - 81.50 850 37.4 (1) 4.31 3
70 Cl 2H16N401g Cellulose Nitrate .229.80 2213 46.7 (14) 6.12 3
Averageof6 compounds 5.07 3
71 CH3N02 Nitr,~methwre - 17.86 262I 59.0 (1) 5.97 4
72 c21i2 Acetylerle + 54.19 2898 40.5” (21) 7.05 4
73 C2H403 Peracetic Acid - 97.73 976 32.0 (1) 5.04 4
74 C21i5N03 Ethyl Nitrate - 36.8 2094 39.9 (21) 6.36 4
7s C3H5N309 Nitroglycerine - 73.20 2895 40.3 (1) 7.05 4
76 C4H604 Acetyl Peroxide - 1]6.1 983 29.5 (1J 5.26 4
77 c411100~ tert-flulyl }Iydroperrxitle . r5~.9 919 37.8 (1) 4.48 4
78 C4Hj OOz Die[tlyl Peroxide - 46.1 968 37.3 (1) 4.64 4
79 C8!1]@2 Di-tert-bu!yi Peroxide - 81.5 850 37.5 (25) 4.30 4
80 C9111202 Cumene Hydroperoxirte - 21.9 , 989 29.0 (25) 5.32 4
*For the polymerization process. Averageof 10compounds 5.55 4
**See Ref 2.
 H 23

, I HBX (High Blast Explosive). High explosive com-

positions containing RDX, TNT, Al and a wax de-
sensitizer. HBX-I consists of RDX 40, TNT 38, Al
17, D-2 wax 5%& 0.5% added CaC12. It was de-
veloped during WWII as a desensitized modification
, of Torpex (Ref 1). A further modflcation, HBX-3,
consists of RDX 31, TNT 29, Al 35, D-2 wax s~o
& -.5% added CaC12. HBX-1 and HBX-3 are pre-

pared by adding water-wet RDX to molten TNT

(7
I 2345678 and heating until the water is evaporated. The
RCACTION HAZARD INOCX. RH1 D-2 wax (84% paraffin, 14% NC, 2% lecithin) and
CaC12are then added. Both HBX-I and HBX-3 are
Fig 4 Correlation of the N FPA Reactivity
powerful and brisant explosives whose physical and
“Rating with the Reaction Hazard Index (Ref 2)
explosive properties are tabulated here after de-
scription of prepn
HBX expl compns are prepd by melting TNT in
Refs: 1) D.R. Stun, Chem Eng Prog, Loss a steam jacketed kettle equipped with a mechanical
Prevention, 4, 16 (1970) stirrer. Water-wet RDX is added slowly with stirring
2) D.R. Stun, Ibid, 7, 67 (1973) and heating until all the water is evapd. Powdered
Al is added and the mixture is continued to be
stirred until uniform. D-2 wax and Ca chlo’ride are
then added and the mixture is cooled from temp
Hazards–Prevention of Industrial Gas Explosions. 95–1 00° to a temp considered suitable for casting
In the prevention of industrial gas explosion (the lowest practicable pour temp)
“disasters, the most useful terms for evaluating HBX can also be prepd by adding the calcd
the hazards of various fuel/oxidant systems are amt of molten TNT to molten Comp B to obtain
believed to be limits of flammability and min the desired proportion of RDX/TN’T and then the
spontaneous ignition temp (Ref 3) appropriate weights of other ingredients are added
The addition of a flammable diluent is to complete the compn (Ref 6, p 163)
suggested as a method of preventing explosions in IVOTE: The desensitizer wax, also known as Com-
processes involving flammable gas mixts; e.g., position D-2, consists of 84% paraffin wax, 14%
the addition of sufficient methane to a poten- NC and 2% lecithin. Its Military Specification ‘Re-
tially explosive mixt of H + O in” a hydrogen quirements and Tests are in MIL<-I 864
peroxide plant suppresses explosive reactions
without excessive loss of plant throughput capa-
city which would have resulted if an inert
suppressant (diluent) such as nitrogen were
added to the mixture. Butane or pentane are
even more effective than methane (Ref 1)
Spraying with 10-20 psi steam is suggested
before introducing an air stream (carrying wood
preservatives) into an organic vapor atm (Ref 2)
Refs: 1) E. Jones, Chem Eng 59 (6), 185
(1952) & CA 46, 8374 (1952) 2) M. Hudson,
USP 2633429 (1953) & CA 48,5502 (1954)
3) M.G. Zabetakis and G.W. Jones, Chem Eng
Prog 51, 411 (1955) & CA 49, 15241 (1955)
 H 24

TABLE
Properties of HBX’S

Properties HBX-1 HBX-3

Mol Wts 102 64
OB to C02, % –68 –75
OB to CO, % . –35 –49
Ballistic Mortar: 133% TNT I1l%TNT
% TNT in Air 121 (Shock) 116 (Shock)
% TNT in Air 121 (Impulse) 125 (Impulse)
Blast Effects:
% TNT under water 111 (Shock) 101 (Shock)
% TNT under water 145 (Bubble) 191 (Bubble)
Brisance by Sand Test, % TNT 102 (123) 93.5
Density, g/cc 1.69–1 .70 1.81–1.84
Detonation Rate, .m/sec 7224 6927
Expln Temp (5 see) 480° 500”
Fragmentation Test
in 90mm, HE,M71 Shell
No of Fragments 910 476
vs TNT 703
Friction Serisitivity Unaffected
Gas Volume Not given
Heat of Combstn, cal/g 3882 4495
Heat of Expln, cal/g 919 877
Heat of Formation, cal/g 758 491
Heat Test at 100°
% Loss in 1st 48 hrs 0.058 0.70
% Loss in 2nd 48 hrs 0 0
Expln in 100 hrs None None
Hygroscopicity, % Loss 2.98 2.01
(in 7 days at 30°and 95% RH)
Impact Sensitivity “ comparable to TNT
Rifle Bullet Test more sensitive than TNT
Sensitivity to Initiation Require slightly lower
minimum priming chge
Storage Dry Dry
Usage Principally in HE charges,
such as in GP bombs
Note: HBX-1 was recommended for use in booster charges and in depth charges (Refs 4,5 & 6)

Refs: 1) Anon, “Towerful Explosives Developed”, “Some Properties and Characteristics of HBX- 1,
Army Ordn 30, 102 (1949) 2) S.R. Walter, HBX-3 and H-6”, PATR 2431 (1957) ‘5a) N.O.
“Report on the Program to Develop an Improved Holland, Editor, “Explosives – Effects and Pro-
HBX-Type Explosive”, NAVORD Rept 1502 perties”, NOLTR 65-218 (Feb 1967), Sect D-4
(1950) 3) NAVORD Rept 2986 (1953); Ex- 6) Anon, Engineering Design Handbook, “Pro-
plosive Data Sheet, Sectn D-2 4) O.E. Sheffield, perties of Explosives of Military Interest”, Army
“Blast Properties of Explosives Containing Alumi- Materiel Command Pamphlet, AMCP 706-77 (Jan
num or Other Metal Ingredients”, PATR 2353 1971), pp 156–163
(1956) 5) S.D. Stein, G.J. Horvat & O.E. Sheffield,
 H 25

HBX-1, HBX-3 and H-6 Explosive Compositions sition shall comply with the specifications listed
US Military Specification Requirements and Tests, in 2.1 and shall be of the following grade or class
as described in MIL-E-22267A (3 1 May 1963) as applicable 4
Requirements: Composition B Grade A
3.2 Form. Unless otherwise specified the compns TNT Grade 1
HBX-1, HBX-2 & H-6 shall be supplied in the form Al Powder Type III, Grade F, Class 7
of buds or as strips 1.5 inches wide, 1 inch deep& 3.5 Grade A Compositions. The composition of
3 inches long the Grade A HBX composition shall conform to
3.4 Components. The components used in the the nearest tenth percent as required in Table I
preparation of the Grade A HBX and H-6 compo- when tested as specified in 4.4.3.2 or 4.4.3.3

Table 1. Grade A Compositions

HBX-1 HBX-3 H-6
Ingredient Percent by Weight Percent by Weight Percent by Weight
*RDX plus Nitrocellulose 40.4 * 3 .0% 31.3 *3.0% 45.1 *3.0%
plus **Calcium Chloride
plus ***Calcium Silicate
TNT 37.8 * 3.0% 29.0 * 3.WO 29.2 * 3.~o
Aluminum 17.1 *3.0% 34.8 * 3.0% 21.0 *3.0%
**** w~ plus lecithin 4.7 ~ 1.0% 4.9 * 1.()% 4.7 * 1.()%
* Note. All of the RDX component and portions of the TNT and wax are added as Composition B.
** A separate calcium chloride determination need only be 9one if required in the contract or order (See 6.2).
Percentage requirement of Calcium Chloride is 0.5% *O. 1%
*** Calcium Silicate sh~l be determined as specified in 4.4.1.2 when used in the formulation of HBX com-
pounds. The Calcium Silicate content shall be a minimum of 1.25 weight percent of the TNT content of the
mixture and shall only be used in the HBX compositions when specified by the procuring agency (See 6.2).
Calcium Silicate is designated for use only in Army formulations of HBX type explosive compositions.
**** The major pofiion of the wax and all of the Nitrocellulose and lecithin are added as Composition D-2
I
3.6 Grade B Compositions. The composition of
the Grade B HBX & H-6 Composition shall con-
form to the nearest tenth percent as required in
Table 11when determined as specified in 4.4.3.4

I Table Ii. Grade B Compositions

I Ingredient
HBX-1
Percent by Weight
HBX-3
Percent by Weight
H-6
Percent by Weight

I
RDX plus Nitrocellulose 40.4 * 3 .0%0 31.3 *3.0% 45.1 *3.0%
plus Calcium Chloride
plus *Calcium Silicate
/’

II TNT
Aluminum
Wax plus lecithin
37.8 * 3.0%
17.1 *3.0%
4.7 * 1.0%
29.0 * 3.0%
34.8 * 3.0%
4.9 ~ 1.0%
29.2 * 3 .0%
21.0 ~3.o%
4.7 + 1.0%
Hot melt (asphaltic lining material) – maximum allowable 0.75%
A separate Calcium Chloride detn need only be done if required in the contract or order. An additioml
one-half percent of Calcium Chloride shall be added whenever preparing the reclaimed explosive for re-use.
Percentage requirement is 0.7% * 0.3%
* The Calcium Silicate content shall be a minimum of 1.25 weight percent of the TNT content of the
mixture and shall only be used in the HBX compositions when specified by the procuring agency (See 6.2).
Calcium Silicate shall be determined as specified in 4.4.1.2
 H 26

3. 7Moisture Content, when tested as specified in (d) Temperature – The temperature ‘shall be re-
4.4.4 shall be 0.20% max for Grade A and 0.50% corded, prior to, during, and after each phase of
for Grade B batching
3.8 Vacuum Stability. The max volume of gas (e) Agitation – Agitation shall be maintained from
liberated when tested as specified in 4.4.5 shall the time of the addition of the first component
be 2cc/g/48 hrs at 100° for Grade A and B until the kettle has bee~,drained
4.2 Lot Size. For the purpose of sampling a lot (f,) Mixing time – The mixing time following the
shall be limited to 1300 lbs max and to one batch addition of the last component
from a single vessel. Tests shall be conducted on
each lot Table 111. HBX Compositions
4.3.1 Preproduction Samples. After award of (Percent by Weight)
contract but prior to entering quantity production, HBX-1 HBX-3 H-6
a preproduction sample shall be prepd for in-
Composition B 66.08 51.33 74.20
spection and acceptance tests to determine con-
Composition D-2 4.66 4.73 4.69
formance of the sample with the requirements of
Aluminum 17.10 34.75 20.61
the specification (See 6.2)
Additional TNT 11.66 8.69 –
4.3.1.1 Preproductwn Sample for Subsequent
Calcium Chloride 0.50 0.50 0.50
Contracts. The necessity for such a sample will be
Calcium Silicate o.47a 0.36a o.37a
detd by the procuring activity when production
under a new contract by the same contractor at Each component shall be based on the percent
the same location follows the prepn of any HBX by weight limitation listed in Table I or 11 for each
or H-6 compns covered by this spec HBX formulation
4.3.2.1 Sample for Chemical Composition Analysis a) When specified by the procuring activity,
is taken by catching a portion of the molten expl Calcium Silicate used in the formulation of HBX
compn, from the approx center of the batch, and components shall be a minimum of 1.25 weight
pouring into shallow Al dish 4 inches in diam in percent of the TNT content
order to obtn on cooling a wafer approx % inch thick 4.4.1.2 Determination of Calcium Silicate. When
4.3.2.2 Sample for Moisture Analysis consists of specified by the procuring activity (See 6.2), Cal-
approx 50g reserved from 4.3.2.1 cium Silicate used in the HBX & H-6 compositions
4.4.1 Process Verijkation. Unless otherwise speci- shall be determined by visual verification of the
fied, provess verification used as the inspection weight of calcium silicate added to the batch.
shall be subject to Government verification at the Quantities added shall be calculated in terms of
time the first batch is prepared and at random in- weight percent of TNT content
tervals during the production, but not less than 4.4.2 Lot Acceptance Tests. Unless otherwise
once during each week of continuous operation. specified in the contract or order, samples selected
Verification will consist of surveillance of the from each inspection lot shall be subjected to all
process and related equipment to determine that the requirements and tests of this specification.
practices, methods and procedures are being pro- Failure of the HBX compositions to meet any of
perly applied, and that the products are produced the requirements or tests of this specification shall
under the requirements of this specification. A be considered cause for rejection of the lot
record shall be made of each batch of explosive 4.4.3 Composition Analysis
prepared to insure that the following requhements 4.4.3.1 Sample Preparatwn. Reduce sample thru
have been met: a 20 mesh screen (US Standard Sieve Series)
(a) Explosive components – Components shall using a wooden mortar and pestle
meet the requirements of 3.4 4.4.3.2 Method of Analysis. Grade A:
(b) Composition – The quantities of each compo- 4.4.3.2.1 Determination of Aluminum. Weigh
nent required shall be calculated and weighed to accurately a sample calculated to contain 0.4g of
give the correct composition. Component weights TNT into a tared sintered glass filtering crucible,
may be calculated from Table 111 medium porosity, 30-ml capacity. Extract on a
(c) Order of addition – The order of addition shall Fisher fdtrator with ethylene chloride (purified
be recorded. Order of addition shall be mandatory 1,2 dichloroethane) at approx 20”C, 5 equal
as specified in 3.3 portions totaling 45ml, contact time of 1 min each.

#
 H 27

Collect fdtrate in a 50ml volumetric flask. Re- cooling, reweigh the tube with contents to det exact
serve fdtrate for TNT determination amt of tetrachloroethylene lost by volatilization.
‘ The residue remaining on the filtering crucible Replace the exact amt of loss and insert the tube in
is extracted with hot cyclohexanone (highest the water bath. Set the refractometer to read 1.4910
purity grade) at approx 100”C. Five consecutive as the RI of tetrachloroethylene at 50+0.50 and pour
3-second extractions of 3ml each with continuous several drops of the supernatant liquid from the
vacuum fdtration and no stirring are made. This test tube unto the prisms of ’the refractometer.
is followed by four consecutive 30-sec extractions Quickly close the prisms and at the end of 30 sees
of 10ml each with stirring. After the cyclo- det the RI to sodium D light. The wax+ lecithin
hekanone extraction, wash down the sides of the concn is detd by reference to a graph previously
crucible with approx 2ml of reagent grade acetone. prepd from known solns. The prepns of the solns
Repeat for a total of 3 washings. Dry in an oven at and the graph are described in 4.4.3.5.2
90°C *1O’C for 30 reins, cool in a desiccator and Percent Wax + Lecithin= (C x 100)/W
weigh. The residue is aluminum
where: C = Wt of wax+ lecithin from the graph
Percent Al= [(A–B) x 100] / W W = Wt of sample
where: A = Wt of crucible with Al 4.4.3.2.4 Deterrninatwn of Calcium Chloride.
B = Wt of empty crucible Weigh accurately a 2-g sample into a tared sintered
W = Wt of sample glass faltering crucible, medium porosity, 30-n-rl
4.4.3.2.2 TNT Determinatwn. Dilute the TNT capacity. Using a Fisher fdtrator with water
‘filtrate obtd in 4.4.3.2.1 to 50ml with ethylene vacuum, extract sample with 100m1 of distd w,
chloride. Compare its spectral absorbance at 20° 10 extractions, 10ml each, of 30 sec duration.
with that of a soln, 0.400g of TNT in 50ml ethyl- Collect fdtrate in a 250 Erlenmeyer flask. Cool
ene chloride at 367 millimicrons. Det TNT b y to RT and add 2rnl of 0.1 M K chromate indicator
reference to a graph prepd in advance from known to the filtrate. (For the prepn of O.l M K chromate
soln. The prepn of the solns and the graph is see4.4.3.5.3). Titrate to the end point with O.lN
described in 4.4.3.5.1. A Beckman DK-2 or Ag nitrate. (For the prepn of O.lN Ag nitrate
equivalent spectrophotometer may be used to det sok, see4.4.3.5.4). The end point is noted by
the spectral absorbance the fust of a permanent colored red ppt of Ag
When using the Beckman DK-2 recording chromate. The end point should be detd by using
spectrophotometer, one proceeds under the fol- a white background or by transferring fdtrate plus
lowing conditions: a minimum of distd w washings to a white casserole
a) lomm cell with 9mm spacer Percent Ca Chloride= [VXNX(O.0555)] / W
b) Wavelength setting of 367 millimicrons
c) Time constant of 0.6 where: V = ml of Ag nitrate
d) Seaming time”of 1 N = Normality of Ag nitrate
e) Scale expansion –2X 0.0555 = Millequivalent weight of Ca chloride
f) Sensitivity –1 1.5 W = Weight sample
g) Adsorption scale of –0.3 +0.7 4.4.3.2.5 Determinatwn of RDX + Nitrocellulose.
h) Hydrogen lamp The percentages of TNT, Ca chloride, aluminum, and
i) Photomultiplier position – 1X wax + lecithin are added and their sum subtracted
from 100 percent. The remainder is taken to be
Percent TNT = (A x 100) / W the percentage of RDX plus Nitrocelhrlose
where: A = Wt of TNT from graph 4.4.3.3 Alternate Method of Analysis. Grade A
w = Wt of sample 4.4.3.3.1 Determination of RDX + Nitrocellulose.
4.4.3.2.3 Determination of Wax+ Lecithin. Weigh Weigh accurately a sample calculated to contain
a 3-g sample and transfer it to a small, accurately between 0.35 and 0.40g of TNT into a tared 10O-rnl
tared, test tube. Add exactly 3ml of t etrachloro- beaker. Add 20ml of RDX saturated benzene to
ethylene and reweigh the tube with contents. Heat the beaker. The prepn of the RDX saturated ben-
it in a steam bath to 90° while stirring vigorously zene is described in 4.4.3.5.5. Cover beaker with
and transfer to a water bath used to maintain the a watch glass and place on a steam bath for 30
prisms of an Abbg refractometer at 50+0.5 0. After reins, swirl soln frequently. (An oscillating hot
 H 28

plate may be used if available). Do not boil the 4.4.3.3.3 Determinatwn of TNT For method of
benzene! After removal from the steam bath, cool ( PrePn and standardization of sohls needed in the
sample to RT. Allow a minimum of 1 hour cooling TNT detn see4.4.3.5.6 thru 4.4.3.5.13
Make a quantitative transfer of the sample to Dilute the TNT and wax filtrate obtd in
~ the original tared filtering crucible. Filter using a 4.4.3.3.1 to 100ml with benzene satd with RDX.
Fisher filtrator with water suction. Use a small Transfer a 10-ml aliquot of the TNT soln which
polyethylene wash bottle which contains benzene contns 35–40mg of TNT to a 300-ml reduction
saturated with RDX to make the transfer. Make flask (Scientific Glass Apparatus Co JD2776 or
a total of 3 washings of the beaker and residue on equivalent is satisfactory). Evaporate the benzene
the crucible, using between 10 and 15ml of benzene to dryness with a slow stream of dry air (comect a
saturated RDX per rinse. Make a final rinse of the drying tube between wir supply and inlet tube of
crucible contents with 5ml of benzene saturated flask).
with RDX. Collect the fdtrate which contains Dissolve the residue in 25ml of reagent grade
TNT and wax in a 100-ml volumetric flask. Re- glacial acetic acid (measure in a cylinder). Sweep
serve the filtrate to det the TNT content. Aspi- the flask with N2 or C02 gas for 5 reins. Pipette
rate the crucible for 1 min after the final rinse accurately 25ml of 0.2N titanous chloride scdn into
The crucible plus its contents are placed on a the flask. Add 25ml of 6N HC1. A current of C02
Fisher fdtrator, and extracted with hot distd w, 3 or N2 should be passed thru the reaction flask
portions of 5ml each, 30 seescontact time for during the refluxing, cooling and titration periods
each washing. This is necessary to remove any Ca to prevent air oxidation of the titanous ion. Re-
chloride that may be remaining in the residue. Dry flux for 15 reins, using glass beads to reduce bump-
crucible and its contents in an oven at 90”C ~ 10“C ing. (Ground glassjoints on the flask and con-
for 1 hour. Cool the sample in a desiccator and denser are to be preferred. A Glass-Col heating
weigh. The crucible and its contents are placed mantle is the most convenient source of heat,
on a Fisher filtrator, attached to a water aspirator. though a hot plate maybe used). Cool the flask
Extract the sample with four 20-ml portions of to RT without disconnecting the reflux condenser.
hot, reagent grade, acetone. Allow 30 seescon- (Lift the flask and condenser and substitute a pan
tact time between solvent and sample before of cold water for the heater). Titrate the sample
applying suction for each extraction. Wash down in the flask with standard ferric ammonium sul-
the sides of the crucible with two additional por- fate (O.15N) soln, using a magnetic stirrer if
tions of 10ml each of hot acetone. Place crucible available. As the end point is approached [the
and its residue in an oven to dry at 90”C * 10°C Ti(III) color gets light] add 5ml of 20% ammonium
for 30 reins, cool in a desiccator and weigh. RDX thiocyamte and continue the titration to the ap-
and Nitrocellulose are removed in the fdtrate, Alu- pearance of the “red color
minum remains as the residue on the crucible At least4mlof0.15N Fe(III) soln should be
Percent RDX + Nitrocellulose = required in back titration. If less, repeat adding
[(A-B) X 100] / W more Ti(III) soln in excess to the TNT-wax
ffltrate. [If less than 4ml of Fe(III), soln is used
where: A = Wt of sample plus crucible before in the back titration in either standardization of
acetone exhaction Ti(III) soln or in the detn of TNT, low values may
B = Wt of residue plus crucible after be obtd., If the excess Ti(HI) at the end of the
acetone extraction refluxing is too small, reduction of the nitro groups
W = Wt of sample
may be incomplete. On the other hand, if more
4.4.3.3.2 Detem”ination of Aluminum. The than 10ml of Fe(III) soln is used, an unnecessarily
aluminum is the residue, remaining on the crucible large excess of Ti(III) soln is being added] .
after the acetone extraction Run a blank on a volume of RDX satd benzene
Percent aluminum = [(B–D) x 100] / W equal to the volume of the aliquot of sample soln
where: B = Wt of residue plus crucible after used in the preceding titration
acetone extraction Percent TNT =
D = Wt of original crucible [0.1261 x (AN-BF) - (CN-DF) x 100] /w
W = Wt of sample
 H 29

where: A = ml of Ti(III) soln where: A = Wt of hot melt obtd from the graph
N = Normality of Ti(III) soln W = Wt of sample
B = ml of Fe(III) soln 4.4.3.4.3 Determinatwn of TNT – Spectrophoto-
F = Normality of Fe(III) soln meter. Hot melt interferes with the method for
C = ml Ti(III) added to blank the absorbance of TNT as described in 4.4.3.2.2.
D = ml Fe(III) added to blank 0.01261g Corrected TNT values can be obtd by comparing
TNT, = 1 meq of TNT the TNT soln at 430 millimicrons in addition to
W = Wt of sample represented by aliquot 367 millicrons. At 430 mu, the absorption is due
AN–BF = Meq Ti(IH) used by TNT & RDX to the hot melt alone. Correct the weight for
CN–DF = Meq Ti(III) used by RDX TNT obtd from TNT spectral absorbance graph
4.4.3.3.4 Determinatwn of Calcium Chloride. by subtracting from it the vahre obtd from a cor-
Calcium chloride is determined as in 4.4.3.2.4 rection graph prepd in” advance as described in
4.4.3.3.5 Determinatwn of Wax + Lecithin. The 4.4.3.5.15. The TNT + wax+ hot melt fdtrate
percentages of TNT, RDX plus Nitrocellulose, Ca collected in 4.4.3.3.1, dihrted to 50ml with benzene
chloride, and aluminum are added and their sum satd RDX may be substituted for the ethylene
subtracted from 100 percent. The remainder is chloride solrr in 4.4.3.2.2. Al graphs and standard
taken to be the percentage of wax plus lecithin solns needed will substitute RDX satd benzene for
4.4.3.4 Method of Analysis. Grade B ethylene chloride
4.4.3.4.1 Determination of Hot Melt – VisuaUy. Percent TNT = [(A–B) x 100] / W
Weigh accurately a 1 g sample of HBX into a tared
sintered glass filtering crucible, medium porosity, where: A = Wt of TNT from TNT spectral
30-ml capacity. Using approx 5ml of ethylene calibration graph
chloride, divided into 5 equal portions, 1 min con- B = TNT correction value from the TNT
tact time each, extract sample on a Fisher filtrator correction graph
with water vacuum. Collect fdtrate in a 50ml W = Wt of the sample
volumetric flask and dilute to the mark with ethyl- 4.4.3.4.4 Determinatwn of TNT – Titarwus
ene chloride. Compare the color of the fflt rate chloride Method. Hot melt is present in the TNT
visually with previously prepd standards to det the wax filtrate obtd in 4.4.3.3.1. This filtrate is used
weight of hot melt present. The prepn of the hot in the TNT detn by the titanous chloride method.
melt standard solns are described in 4.4.3.5.14 Hot melt does not interfere with the TNT detn
4.4.3.4.5 Determination of Aluminum. The
Percentage of hot melt= (Ax 100)/W method described in 4.4.3.2.1 or 4.4.3.3.2 may
where: A = Wt of hot melt from comparison with be used to detn the aluminum content
standards 4.4.3.4.6 Determination of RDX + Nitrocellulose.
W = Wt of sample The method described in 4.4.3.2.5 or 4.4.3.3.1 may
4.4.3.4.2 Determinatwn of Hot Melt – Spectro- be used to detn the RDX + Nitrocellulose content
photometer. Compare the spectral absorbance at 4.4.3.4.7 Determination of Calcium Chloride. The
20°C of the ethylene chloride fdtrate obtd in method described in 4.4.3.2.4 is used to detn the
4.4.3.2.1 or 4.4.3.4.1 with that of a standard soln Ca chloride content
(0.4g of TNT/50rnl of ethylene chloride) at 430 4.4,3.4.8 Determination of Wax+ Lecithin. The
millimicrons. The weight of hot melt is detd by percentages of TNT, RDX plus Nitrocellulose, Ca
reference to a graph prepd in advance from stan- chloride, aluminum, and hot melt are added and
dard hot melt solns. The prepn of the solns and their sum subtracted from 100%. The remainder is
graph are described in 4.4.3.5.14. The TNT+ taken to be the percentage of wax plus lecithin
wax + hot melt filtrate collected in 4.4.3.3.1, di- Where the method of analysis described in
luted to 50ml with RDX satd benzene maybe 4.4.3.3 is not used in its entirety, the wax plus
substituted for the ethylene chloride–TNT soln lecithin content can be detd as follows: The
obtd in 4.4.3.4.1. All graphs and standard solns crucible plus residue obtd after the RDX satd
needed will substitute RDX satd benzene for benzene extraction as described in 4.4.3.3.1 is
ethylene chloride extracted with an additional 50ml of RDX satd
Percentage of hot melt= (A x 100)/W benzene (5–10ml portions, 30 seeseach). The
sample is dried at 10O°C for 30 reins. The crucible
 H 30

plus residue are cooled in a desiccator and weighed. solns of known wax concentration under the same
The loss in weight of the sample is equal to the conditions described in 4.4.3.2.3. Plot the refrac-
weight of the TNT + wax + hot melt extracted tive index readings from the samples against weight
Percent wax + lecithin= of wax + lecithin
{[A-(BtC)] X 100}/ W 4.4.3.5.3 reparation of O.lM Potassium Chromate
Solutwn. Accurately weigh 1.942g of reagent grade
where: A = Loss in wt of sample after RDX satd K chromate into a 100-ml volumetric flask. Dilute
benzene extraction to mark with distd w. Mix well
W = Wt of sample 4.4.3.5.4 Preparation of O.IN Silver Nitrate Solution
B = Wt of TNT detd in 4.4.3.2.2 or Accurately weigh 16.989g of reagent grade Ag ni-
4.4.3.3.3 trate into a liter volumetric flask. Dilute to mark
C = Wt hot melt detd in 4.4.3.4.1 or with distd w. It is not necessary to standardize
4.4.3.4.2 the Ag nitrate soln if care is taken in the prepn of
The refractive index method for the detn of the soln. Store the Ag nitrate soln in a dark place
wax plus lecithin described in 4.4.3.2.3 camot 4.4.3.5.5 Preparatwn of RDX Saturated Benzene.
be used when hot melt is present To a gallon of reagent grade benzene, add RDX in
4.4.3.5 Preparations of Solutions, Graphs and excess of solubilit y, and stir for several hours. Let
Standardization of Solutions: stand overnight. The soln should be prepd and
4.4.3.5.1 Prepamtion of TNT Starukrd Solutions kept at the same temp as will prevail at the time
and TNT Spectral Grlibration Graph. Prepare a of faltering the extracted sample. Filter soln just
stock TNT soln. Accurately weigh and transfer before use
8g of TNT into a 500-ml volumetric flask. Dilute 4.4.3.5.6 Preparation of 20 Percent Solution of
to mark with ethylene chloride Ammonium Thiocyanate. Dissolve 60g of reagent
tito each of seven 50-ml volumetric flasks, grade ammonium thiocyanate (NH4SCN) in
pipette accurately the following quantities of the 240ml of distd w. Filter until clear and store
TNT stock soln respectively, 22ml, 23ml, 24ml, 4.4.3.5. 7Preparation of 6NHydrochloric Acid
25ml, 26ml, 27ml, 28ml. Dilute with ethylene Add 250ml of reagent grade 38% HC1 to 250ml
chloride to the mark of distd w. Mix well
Weight of TNT in each standard solution= 4.4.3.5.8 Preparation of 0.2N Titanous Chloride
A X 0.016 Solution. Mix 150ml of 20% titanous chloride
where: A = Volume of TNT stock soln added to soln with 100m1 of 38% HC1 soln. (As the concn
50-ml volumetric flask of the 20’%0titanous chloride varies from bottle
0.016 = Weight of TNT (gms)/ml of TNT to bottle, one may use an adjusted volume for
stock SOhl the prepn of additional 0.2N Ti(HI) soln rather than
Prepare the TNT spectral calibration graph by the 150ml of 20% soln). Dilute quantitatively to
detg the absorbance at 367 mu of the standard 1 liter with distd w. Mix by bubbling a stream of
nitrogen or carbon dioxide gas thru the soln, filter
TNT solns at 20”C compared to a soln of 0.400g thru Whatman No 41 (fluted) or equivalent paper,
of TNT/50ml of ethylene chloride using 1 mm store in a system arranged so that only carbon di-
path cells. Plot absorbance against weight of TNT oxide or nitrogen gas will be drawn into the stock
4.4.3.5.2 Preparation of Wax Standard Solutions bottle as the soln is used. (Scientific Glass Ap
and Wax Refractive Index Calibration Graph. paratus Co JB-7670, burette, automatic, for titanous
Prepare 3-g HBX samples with different weights
chloride solution, improved form; or JB-76 15, bu-
of wax and lecithin. The samples must be prepared rette, automatic, or equivalent is satisfactory. Teflon
with the same materials used to prep the HBX stopcocks are to be preferred).
being analyzed. The weight of wax+ lecithin in 4.4.3.5.9 Prepamtwn of O.15N Fern-c Ammonium
the sample is based on the wax from the D-2 and Sulfate Solution. Dissolve 75g of hydrated ferric
Comp B (if used). The standard wax samples are ammonium sulfate (Fe~ (S04)2. 12H2 O), re-
treated as described in 4.4.3.2.3 to obtn the wax agent grade, in 600ml distd w. Add to this 25ml
in soln of 95% reagent grade sulfuric acid. When dissolved,
Prepare the wax refractive index calibration dilute with distd w to 1 liter; filter, mix thoroughly,
graph by detg the refractive index of the various and store
 H 31

4.4.3.5.10 Preparation of 0.200N p-Nitroaniline 20ml of glacial acetic acid for the p-nitroaniline soln
Solution. Use p-nitroaniline with a mp of 147–
Normality of Ti(III) solution =
148”C, and recrystallize once from ethanol. Dry
4.000 / [(A–RB – (C–RD)]
in a desiccator. For a 0.200N soln weigh exactly
1.151g of recrystallized p-nitroaniline, dissolve in where: 4.000 = Millequivalents of p-Nt roaniline
reagent grade glacial acetic acid, transfer to a in 20.00m1 of 0.200N soln
250-rrd volumetric flask and dilute to the mark A = ml of Ti(III) so@
with glacial acetic acid. Mix well B = ml of Fe(III) soln.
4.4.3.5.11 Comparison of Titanous Chloride and C = ml of Ti(III) in blank
Ferric Ammonium Su~ate Solutions (Detennina- D = ml of Fe(III) in blank
twn of R). This value is necessary in the deter- R = ml of Ti(HI) reacting with 1.00m1
mination of the normality of the ‘Ti(III) and the nor- of Fe(III) soln
mality of the Fe(III). R equrds the ml of Ti(III) The term (C–RD) should be zero. If the value
reacting with 1.00m1 of Fe(III) soln. Sweep the lies outside the range +0.1 O and –0.10, either R is
air from a 300-ml reduction flask with a current incorrect, or the acetic acid is contaminanted. Re-
of nitrogen or carbon dioxide gas for 5 reins. peat the detn of R. Continued high or low values
Continue to passthe current of nitrogen or carbon for (C–RD) probably mean impure acetic acid
dioxide gas thru the flask until the titration is com- If normality of Ti(IH) soln falls outside of the
pleted range 0.19–0.22, add 20$Z0 titanous chloride soln
Pipette 50.00m1ofapprox0.15N Fe(III) soln or water as required to bring normality to approx
into the aix free reduction flask. Add 25ml of 6N 0.2N. Then repeat the detn of R and repeat the
HC1 (use a cylinder to measure the HC1). Titrate detn of the normality
with approx 0.2N Ti(III) soln until near the end 4.4.3.S.13 Determinatwn of the Normality of the
point (the Ti(III) color gets light). Add 5ml of Fem”c Ammonium Sulfate Solutwn. Using the
20% ammonium thiocyanate soln (by cylinder), value of R and the value of the normrdity of
and continue the titration until the red color just titanous chloride detd in 4.4.3.5.11 and 4.4.3.5.12,
disappears. Repeat the procedure until two suc- calculate the normality of the ferric ~,onium
cessivevalues for R agree to within 1 part per sulfate soln
thousand of their mean F = Normality of Fe(III) soln = (R) (N)
R= A/B where: R = ml of Ti(III) soln reacting with 1.00m1
where: A = ml of Ti(III) soln of Fe(III) soln
B = ml of Fe.(III) soln N = Normality of Ti(III) soln
4.4.3.5.12 Standardization of 0.2N Titanous 4.4.3.5.14 Preparation of Hot Melt Standard
C?ubride Solution. Sweep the air from a 300-ml Solutions and Hot Melt Spectral Calibration Graph.
reduction flask with a current of riitrogen or carbon Prepare a stock TNT soln by accurately weighing
dioxide gas for 5 reins. Continue to pass the current and transferring 8g of TNT into a SOOml volumetric
of gas thru the flask until the titration is completed flask. Dilute to mark with ethylene chloride. Pre-
Pipette 20.00m1 of the 0.200N p-Nitroaniline pare a stock hot melt soln using material conforming
soln into the reduction flask. Pipette 25ml of to Specification MIL-C-3301. Accurately weigh and
titanous chloride approx 0.2N into the same flask. transfer 0.45g of hot melt into a beaker and dissolve
Add 25ml of 6N HC1 (by cylinder), and a few glass in a 100rrd of ethylene chloride. Filter soln thru
beads. Connect the reduction flask to a reflux a sintered glass faltering crucible, medium porosity,
condenser and boil for 15 reins. Cool the flask to 30-ml capacity until fdtrate shows no sign of sedi-
RT without disconnecting the condenser (lift the mentation
flask and condenser, remove the heater, and let the To det weight of hot melt per ml of fdtrate,
flask down into a pan of cold water) accurately pipette 15ml of ffltrate into a tared
Titrate the excess Ti(III) with Fe(III) soln: evaporating dish with cover. Evaporate to dryness
As the end point is approached, Ti(III) color gets on a stearn bath or hot plate below 75 “C. Re-
light, add 5ml of 20% ammonium thiocyanate (by place cover, cool in a desiccator to RT and weigh
cylinder), as an indicator and titrate to the appear- Weight of hot melt per ml of solution =
ance of the red color. Run a blank, substituting (A-B) /v
 H 32

where: A = Wt of evaporating dish plus cover plus in O.lml). To the top of the trap is attached a
residue cold water condenser. (See Figure 1). (The use
B = Wt of evaporating dish plus cover of Teflon sleeves on the ground glassjoints in
V = Volume of hot melt filtrate pipetted place of a lubricant will facilitate the cleaning of
into evaporating dish the glassware)
Into each of six 50-ml volumetric flasks, pipette Heat the assembly on a magnetic stirrer hot
accurately 25ml of the TNT stock soln, add to each plate, with agitation provided by the magnetic -
of the flasks respectively, by pipetting accurately, stirrer. Heat to boiling. (The toluene-water
0.5ml, l.Oml, 1.5m., 2.Oml, 2.5ml, 3.Oml of the azeotrope condenses and falls back into the trap.
hot melt filtrate. Dilute with ethylene chloride Water being heavier, collects in the trap and the
to the mark excess toluene returns to the boiling flask).
Continue boiling until no change in the water
Weight of hot melt in standard = WD
volume has been observed for 15 reins. Boil a
where: W = Wt of hot melt per ml of soln minimum of 1 hour
D = ml of hot melt added to the standard CAUTION: Keep soln well agitated at all
Prepare the hot melt spectral calibration graph times. When soln begins distilling, position flask
by detg the absorbance at 430mu of the standard so that an air space is between the flask and
hot melt and TNT solns at 20”C compared to a hot palte. This is to prevent a hot spot from
soln of 0.400g of TNT/50ml of ethylene chloride building up in the chunk explosive. Sample
using 1 mm path cells. Plot absorbance against should not be left unattended during the moisture
weight of hot melt detn. Care must be taken that the cold water
4.4.3.5.15 Preparatwn of the TNT Correction condenser is operating properly at all times. If
Graph for the Presence of Hot Melt. Determine the condenser should fail to trap the toluene and
the spectral absorbance of the hot melt and TNT the flash were to boil dry, there could be a pos-
standard solns at 367mu, at 20°C, using 1 mm sibility of overheating the expl
path cells. The prepn of the solns is described in Care should be taken to prevent condensation
4.4.3.5.13. From this data determine the ap- of atmospheric moisture in the condenser. Five
parent weight of the TNT from the TNT spectral minutes before heating is discontinued wash down
calibration graph described in 4.4.3.5.1. Subtract the condenser with toluene to remove any water
the actual weight of TNT (0.4g) in the standard
clinging to the tip of the condenser
hot melt soln from the apparent weight of TNT.
After the moisture has been collected, transfer
This gives the TNT correction vahre
the trap to a constant temp bath at 40°C * 2“C.
Determine the spectral absorbance of the hot
Allow about 30 reins for trap contents to reach
melt standard solns at 430mu as described in
the temp of the bath. By means of a wire loop
4.4.3.4.14
work any droplets of water trapped along the side
For the TNT correction graph for the presence
to the bottom of the trap. Read the volume of
of hot melt plot the absorbance of the standard
the water collected
hot melt solrrs at 430mu against the TNT cor-
Run a blank on the toluene to det water present
rection values obtd at 367mu
in the t oluene. Calculate the percentage of water
4.4.4 Moisture Determination. Remove sample in the sample
of HBX from closed sample container. Sample
size shall be approx 10Og for Grade A material Percentage of water= [(A–B) x C x 100] / W
and 50g for Grade B material. Break up quickly where: A = ml of water
and transfer the sample to a tared liter Erlenmeyer B = ml of water in toluene
flask with a ground glass neck. Stopper flask C = Density of water at temp of the
and record weight of flask plus sample. (When water bath
sample is broken up, it should be exposed to the W = Wt of the sample
air as little as possible as the Ca chloride in the 4.4.5 Vacuum Stability Test, 100°C
HBX quickly takes up moisture) 4.4.5.1 Calibration of Glass Tube. Determine the
To the flask containing the sample add 200ml volume in mls of the 15.5cm heating tube by
of toluene and a magnetic stirring bar. Atach running in mercury from a buret until the tube
flask to a Bidwell-Sterling trap (graduated 5ml is filled to the level at which the ground glass
 H 33

joint of the capillary tube will make contact

with the mercury. Subtract from the indicated
buret reading, the volume of expl used in the
test. The difference shall be represented by the
symbol A. Transfer 7.Oml of mercury to the cup
at the lower end of the capillary tube. Clamp the
tube “in an upright vertical position, and measure
the height in mm of the mercury column in the
capilla~ tube (approx 25mm). Measure the
length in mm of each of the 3 parts of the capil-
lary tube and add these values to obtn total length.
From the total length subtract ke height of the
mercury column in the capillary tube as previously
obtd. Represent this difference by the symbol
BI. From the total length subtract the height of
the column of mercury in the capillary tube mea-
sured at the end of the test described in 4.4.5.1
Represent this difference by the symbol B.
Determine the capacity of the capillary tube per
unit of length as follows: Transfer an accurately
weighed sample of approx 10g of mercury to the
cup at the lower end of the capillary tube. Mani-
pulate the tube so that when it is horizontal,
mercury is contd in a continuous section of the
longest part of the tube and measure the length
of the mercury column. Repeat this twice with
the mercury in 2 other parts of the long section
of the tube.. Calculate the average of the 3 mea-
sured lengths of ,tie mercury column. Represent FIGURE 1 Moisture content apparatus
the unit capacity in ml per mm of the capillary
tubing by the symbol C. This can be obtd from
the formula:
‘2’-’3” 1
C= W/d~
where: C = Unit capacity of capillary tubing in n--F ‘
ml per mm 2.0 - CAP, LIAUY NBINC
@ TO ,., a UTGUIAL DIA.
W = Grams of mercury !.0 m 2,0 w lNTUNAL DIA

d = Density of mercury at temp of

I
determination
Q = Average measured lengths of mercury I
column in mm”
4.4.5.2 Test Bocedure. Transfer a 1 g sample,
dried at, 65“C for 2 hours, to the heating tube of
the apparatus shown in Figure 2. Connect the
capillary tube to the heating tube. Clamp the
apparatus so that the long section of the capillary
tube is in a nearly vert@al ~osition: Transfer – h-’””
S1!;,,}” TO W STA” M”O TAPcN 12/18
7.Oml of mercury to the cup at the lower end of
the capillary tube. Connect a vacuum pump to
the lower end of the capillary tube and evacuate
the system until the pressure is reduced to approx
5mm of mercury. (Evaluation of the capillary FIGURE 2 Apparatus /or 10o”c vacuum stability test
 H 34

tube is facilitated by placing the cup of the tube 6.3.1 All handling and bathing operations should
in a horizontal position so that mercury does not be conducted,in a neat and orderly manner
block the capillary opening). After evacuation, 6.3.2 Safe equipment and methods should be
disconnect the pump. Seal the connection between utilized for transporting and handling explosives
the capillary tube and the heating tube with 1 ml components and mixtures. Where required, remote
of mercury. Measure the totrd vertical height of controlled barricaded handling equipment shall be
the column of mercury in the capillary tube. Mea- used for explosives operations, such as mixing,
sure and subtract the vertical height of the mer- pouring, weighing, charging, sifting, drying,
cury in the cup. The difference shall be repre- casting, etc
sented by the symbol HI. Note the RT (tl ) and 6.3.3 The exposure of explosive materials and
and the barometric pressure. Subtract the vahre related parts should be so controlled as to mini-
HI from the barometric pressure in mm. Re- mize the absorption of moisture from the atmos-
t.hk difference by the sumbol PI. Insert the phere or other sources during handling and batch-
heating tube in a constant temp bath consisting ing operations
of a soln of glycerin and water (sp gr 1.05). 6.3.4 All explosive components and mixtures
Maintain at a temp of 100.OO°C* 0.5°C for 48 should be stored in suitable storage magazines
hours. Remove the heating tube from the bath located in accordance with American Table of
and allow to cool to RT. Measure the total Distances (ATD) or other applicable safety
vertical height of the column of mercury in the standards; and while in process, in safety lockers
capillary tube and subtract the vertical height and chests if in loading rooms, or in adequate
of the mercury in the cup. This difference shall ready or service magazines located in accordance
be represented by the symbol H. Note the RT (t) with Intraplant distances when outside of loading
and the barometric pressure in mm. Represent rooms. For Navy managed explosive loading
this difference by the sympol P plants, the provisions of the Armed Services Ex-
4.4.5.3 Calculatrbn of Liberated Gas Volume. plosives Safety Board covering quantity-distance
Calculate the gas vol in ml (at standard conditions) relations for explosives will apply
liberated in the test described in 4.4.5.2, using the 6.3.5 Proper care must be exercised at all times
values described by the symbols in 4.4.5.2 and to protect personnel from accidents, fires, or ex-
4.4.5.1 in the following formula: plosions, and to limit damage to equipment and
“ . [A+C(B–H)] x 27~P loading areas. In this connection, the precaution-
760(273+t) ary measures in the following paragraphs should
be obse~ed
– [A+C(BI –Hl)] X 273P,
6.3.5.1 Employ properly proportioned and pro-
760(273+t ~)
perly located protective barricades, screens or
6.3 General Safety Precautions. The preparation shields at rdl required points
and handling of the items covered by this speci- 6.3.5.2 Keep only mhum limited quantities
fication, and the subassembliesthereof, involve of explosives components and expl mixtures at
hazardous operations and therefore require ex- each stage of operations
plosives safety precautions. Use of this specifi- 6.3.5.3 Keep explosives and expl components in
cation will not be construed as to relieve the con- approved covered receptacles with covers in place
tractor or manufacturer of responsibility for the when material is not being taken out of or put
safety of his operations. Listed below are certain into the receptacles. Where necessary, receptacles
minimum provisions which a contractor or manu- should be conductive to ground electrostatic
facturer (who prepares the item covered) should charges
observe in order to fulfdl his responsibility for 6.3.5.4 Protect operations from electrostatic
safety. At Bureau of Naval Weapons, Navy De- charges by effectively grounding all machinery,
partment, and other government plants, these equipment and fiitures; and, where necessary,
provisions are mandatory. Such other warnings employ suitable grounded conductive coverings
and precautions, pertinent to the operational for floors, 2 ork benches and tables, and workers’
effectiveness or safety during preparation of the conductive shoes. Workers’ clothing of a type to
specified items, are included in detailed technical minimize the accumulation of static charges
requirements of the specification
 H 35

should be employed. Fabrics such as silk and nylon, HBX-1 Analytical Procedure. Pristera (Ref)
which promote static generation should be avoided. briefly describes its analysis as follows: Extract
Additional precautions should include mechanical TNT wax and lecithin with carbon tetrachloride;
shielding to contain fragments and blast, also elec- then determine TNT by titanous reduction as
trical shielding from induced electric currents described on p 466 of Refi extract with water the
generated by sources such as lightning, static, Ca chloride from carbon tetrachloride insoluble
radiations from communications apparatus, radar, residue and extract RDX, with hot toluene,
or high frequency heat apparatus, etc. Additional from water-insol residue using Wiley extractor.
grounding devices such as grounding bracelets for Extract NC from toluene-insol residue with cyclo-
workers should be employed where operations hexanone, acetone, or tetrahydrofuran; the re-
are conducted with items which are unusually mainder is Al
sensitive to initiation by static electricity. Where Refi Frank Pristera, “Explosives” in Encyclo-
necessary for safety, humidity of work rooms should pedia of Industrial Chemical Analysis, Wiley, NY,
be appropriately increased, as required, to lessen Vol 12 (1972), Pp 448 & 466
electrostatic effects but without inducing ex-
cessive moisture absorption by any of the com- HBX-3 Analytical Procedure. Accdg to Pristera,
ponents the procedure is the same as for HBX-1. The pro-
6.3.5.5 Protect all expl operations from effects cedure was also described by S. Semel et al in
of electric current originating from equipment such PATR 2459 (1957), entitled “A Chemical Me-
as soldering irons, heaters, switches, wiring, motors, thod for the Composition Analysis of Cast HBX-3°
lights, test instruments, etc, by suitable insulation,
grounding, separation or shielding, Such electric H-6 Analytical Procedure. Accdg to Pristera, the
sources may initiate expls by heat, sparks, arcs. procedure is the same as for HBX-1
Circuits may be inadvertently completed, for Note: No description of Analytical Procedures
example: from a defective soldering iron thru a for HBX-1, HBX-3 and H-6 found in Standard
ground contact Methods of Chemical Analysis, Vol 2B (1963)
6.3.5.6 Enforce, where necessary, the wearing
of suitable safety footwear, gloves, goggles, HC Mixture. A German smoke screen mixture
respirators, and impregnated garments to protect which partly replaced the less stable BM
persomel against burns, poisoning, and associated Mixture during WWI. The HC mixture contains
industrial hazards Zn dust and hexachloroethane (solid) along
6.3.5.7 Allow no fires or exposed electrical or with relatively small percentages of NHqCl,
other sparking equipment, and little or no flamm- NaCIOo, and Mg C03. It is stable, safe and
able material to be present in loading, handling easily handled, but its cost is comparatively
and storage spaces. Enforce proper “Match” and “ high. It ,was used in candles, the 4-inch Stokes
“No Smoking” rules where necessary mortar-shell (burning type) and HC grenades
6.3.5.8 Enforce good housekeeping and maintain Refs: 1) H.W. Walker, IEC 17, 1064 (1925)
effective policing, inspection and supervisory 2) Anon, Field Artillery Journal 33, 352 (1943)
methods thruout the loading area and surround-
ings. Employ effective cleaning methods periodi- HDP Supergun. See Hochdruckpumpe or V-3
cally to minimize the accumulation of explosives (Vergeltungswaffe Drei)
and explosives dust and other contaminants upon,
and assure its removal from floors, walls, celings, HE. Abbr for High Explosives
ledges, tables, benches, piping and equipment or.
the item loaded; also, clean up any spilled ma- Headaches Arising from Contact with NG or
terial immediately Dynamites. Test exposure (oral and skin contact)
6.4 Manufacture by Government Activities. to a 20% NC Dynamite produced severe head-
When the HBX type explosive compnS are to be aches, nausea and vomiting. These effects are
prepd in accordance with this specification by ascribed to intracranial vasodilation produced
government activities, the requirements given by the NG vapors or liquid. Headaches were
herein for bidders and contractors shall apply alleviated by intramuscular injection of mffeine-
to such government activities Na-benz,oate followed by oral administration of
 H 36

amphetamine sulfate. Headaches were prevented Refs: 1) W.J. McConnell, Ind Hyg-Foundation
by daily oral administration of amphetamine Am Inc Proc 8th Annual Meeting (1943), 20-2
sulfate, for 2 or 3 days prior to NC exppsure & CA 38, 3040 (1944) 2) S. Krop, Jet Pro-
(Rt!f 1) pulsion 24, 223 & 236 (1954) & CA 48, 13221
Reaction to NC among pharmaceutical (1954) 3) R.W. Van Dolah et al, Miss UNV
workers is described. Included in” the discussion School of Mines & Met Bull Tech Ser No 98,
are physiological actions, susceptibility and 90-100 (1960) & CA 55, 4963 (1961) 4) C.W.
habituation, toxic effects and methods of con- Kraul & R.H. Duguid, Arch Environmental
trol (Ref 2) Health 3, 680 (1961) & “CA 56, 7652 (1961)
NC headaches are ascribed to distention of 5) J.E. Boysen, Ibid 7 (l), 71 (1963) & CA
intracranial veins or reduction of venous tone 60, 1031 (1964)
or insufficient tone resulting from enhanced
arterial blood flow (Ref 3) HEAT. Abbr for High Explosive Antitank
Refs: 1) A.M. Schwartz, New England J Med
235, 541-4 (1946) & CA 41, 285 (1947)
Heat (Definitions and Selected General References)
2) R.N. Bresler, Ind Med 18, 519 (1949) &
A form. of energy. The mean energy transferred
CA 44, 912 (1950) 3) V.P. Zhururkin; Zh
from one system to another system as a result
Nervopatol i Psikhiat 67, 1336 (1967) (Russ) &
of purely thermrd interactions (temperature
CA 6711576 (1967)
gradients) is called heat
Refs: 1) J.A. Randall “Heat”, J. Wiley and
Health Hazards of Explosives and Propellants. Sons, New York (1913) 2) T. Preston. & J.R.
Health hazards may be encountered in the manu- Cotter “Theory of Heat”, Macmillan and Co.,
facture, handling and use of explosives and pro- London (1919) 3) G.N. Lewis & M. Randall
pellants. These hazards vary with materials and “Thermodynamics”, McGraw Hill, New York
degree of exposure and can range from mild der- (1923) 4) J.R. Partington & W.G. Shilling
matitis to severe poisoning “Specific Heats of Gases”, E: Berm Ltd, London
More serious than dermatoses caused by skin (1924) 5) W. Nernst “The New Heat Theorem”,
contact with Tetryl, TNT, DNT, Hg- Fulminate, Dutton and Co, New York (1926) 6) W.H.
solvents etc, during explosives and ammunition McAdams “Heat Transmission”, McGraw Hill,
production, are exposures to toxic dusts, fumes New York (1933) 7) R.R. Wenner “Thermo-
and’ vapors. Among these are TNT, DNT, oxides chemical Calculations’”, McGraw Hill, New York
of N, Pb. dusts and vapors, and solvent vapors. (1941) 8) J.M. Cork “Heat”, J. Wiley, New
Special skin cleansing agents and solns for York (1942) 9) J. Reilly & W.N. Rae f’Physico-
detecting these harmful materials on the skin chemical Methods””, Van Nostrand, New York
are discussed in Ref 1. (1943) 10) H.S. Carslaw & J.C. “Jaeger
In propellant and missile ‘productions health “Conduction of Heat in Solids>’j Clarendon
hazards may arise from contact with: ammonia, Press, Oxford (1947) 11) M. Jacob, “Heat
aniline, MeOH, furfuryl ale, hydrazine, JP-4, Transfer”, J. Wiley & Sons, New York, V. 1
hydrogen peroxide and red fuming nitric acid (1949) ’12) D.Q. Kern “Process Heat Transfer”,
(Ref 2), as well as other propellant ingredien~s McGraw Hill, New York (195 1) 13) F. Reif
such as NC, epoxy comps, polyurethanes, Amm “Fundamentals of Statistical and Thermal
Perchlorate etc (Ref 5) Physics”, McGraw Hill, New York (1965)
In actual field use explosion product fumes
can be hazardous, eg Ammonium Nitrate-fuel oil Heat of Adsorption (see also Adsorption). The
mixtures (ANFO)
.. are not recommended for heat released”when a gas is adsorbed on a
underground blasting because they produce toxic surface. The differential heat of adsorption is
fumes (Ref 3). “Highly toxic NO is often found given by:
in explosion fumes. The oxidation of NO to the Qdiff = A~g - ARads where AR and
less dangerous N02 was found to be less rapid A~ads are heat contents or enthalpies t see below)
under mining conditions than was previously of the gas and adsorbed phases. ‘
believed (Ref 4)
 H 37

Refs: 1) R.A. Beebe et al, JACS 58, 2196 per inch/second/degree F, the above value has
(1936); 591627 (1937); 60, 2912 (1938) & 62 to be multiplied by 0.00560
(1940) 2) S. Glasstone, “Textbook of Physical If two opposite faces, of a cube, made from
Chemistry”, Van Nostrand, New York (1940), the substance to be examined, are maintained
1179 3) S.J. Gregg, JChemSoc (1946), 563: at temperatures (Tl) and (Tz), the heat con-
(Description of an apparatus which is a combined ductivities across the section of the cube (A)
sorption balance and calorimeter for simul. cm2 and (D) cm thick, the specific heat
taneously measuring adsorption isotherms and conductivity:
heats of adsorption) 4) H. Weissberger, K(T2 - T,) At
~.
“Physical Methods of” Organic Chemistry”, D’
Interscience, New York 2nd ed V1 part 1
where (K) is a constant depending on the nature
(1949) pp 815-817 5) D.F. E~ers et al,
of the substance and (t) is the time in seconds.
“Physical Chemistry”, Wiley and Sons (1964),
See Table 4 of this Vol for heat conductivities
p ’731 & 741 of common explosives
Refi H.S. Carlslaw & J.C. Jaeger, “Conduction
Heat Capacity is the ratio of the heat absorbed of Heat in Solids;’ Oxford Press (1947)
to the riw in temperature for an infinitely small
increase in temperature. For a process occurring Heat Content or Enthalpy. A thermodynamic
at constant volume the heat capacity Cv = (d E/ property closely related to energy. It is defined”
8T)V where t3E is the internal energy change of by’ H = E + PV where E is the internal energy
the process over a temperature change 8T. of the system, P is the pressure on’ the system
Similarly for a constant pressure “process Cp = and V is the volume of the system. Often it is
(8 H/8T)p where 8H is the change in heat con- used in differential form as in. AH = AE + PAV
tent (enthalpy) of the process. When dealing for a constant pressure process
with a unit weight of a substance, a small (c)
is employed and this ratio is also known as Heat of Crystallization. The number of calories
specific heat. In cgs units c is given in calories liberated or absorbed per mol, or gram when a
per gram per degree. For many organic explosive substance passes into the crystalline state. in
compounds c s 0.3 cal/g-O at rm temp cases of solidification of crystalline compounds,
Refs: 1) G.N. Lewis & M. Randall, “Thermo- the heat liberated ‘on freezing may be considered
dynarnics~’ McGraw Hill, NY (1923) 2) J.M. as the heat of crystallization
Perry, Chemical Engineers’ Handbook, McGraw-
Hill, NY (1950), pp 219-235 Heat of Decomposition. The heat evolved or
absorbed in a particular decomposition process.
Heat of Combustion. See Vol 4, p D369 Thus the heat of decomposition of A + B + C
(Tables D380-1) of Encycl under DETONATION is usually different from A + B + D. However,
(AND Explosion), DEFLAGRATION (AND A + E + F + B + C has the same net heat effect
COMBUSTION), AND FORMATION, HEATS as A -+ B + C. The heat of decomposition is
OF generally expressed in kg calories per gram
molecule or in calories per gram
Heat of Condensation is the reverse of Heat of
Evaporation or Vaporization (See under Heat, Heat of Deflagration. See Vol 4 of Encycl under
Latent) DETONATION (EXPLOSION, DEFLAGIU4TION,
COMBUSTION AND FORMATION) HEATS
Heat Conductivity, Specific or Coefficient of OF, p 374-R
Thermal Conductivity (h) is the quantity of
heat in gram-calories transmitted per second Heat of Detonation. See Vol 4 of Encycl pp D
through a plate of material one centimeter thick 370 to 375
and one square’ centimeter in area, when the
temperature differential between the two sides Heat of Dilution. Is the quantity of heat con-
is l“C. When it is desired to express it in Btu sumed or liberated when a solution is dihsted
 H 38

Heat of Dissociation is the heat involved in the (shock, impulse and bubble energy) that the
disruption of a chemical bond explosive produces in air and underwater. This
correlation is confirmed in Ref 9, where it is
Heat of Dissolution or of Solution is the also pointed out that explosive power, as
quantity of heat liberated or absorbed when a measured in the ballistic mortar or lead block,
solid is dissolved or two miscible liquids are can be related to the heat of detonation.
mixed Furthermore, heat of detonation can be an
important parameter in establishing the equa-
Heat Effects – Data for Common Explosives. tion of state of detonation products or in
The datarequired for computing various ‘heat thermal explosion calculations. Consequently,
effects involving explosives and explosions are: the heat of detonation is an important property
standard heats (also called enthalpies) of of an explosive and methods of its accurate
formation, heats of detonation (or explosion), evaluation can contribute greatly to explosive
heats of fusion, vaporization and/or sublima- technology
tion, heat conductivity, and specific heat. To obtain the true value of the heat of
Tables of these data for common explosives detonation one must know the composition of
are given below. Examples of the use of these the detonation products at C-J conditions. At
data are shown in the next section. In con- present such compositions can be obtained only
formance with modern usage exothermic by theoretical calculations. These calculations
heat effects have a negative sign depend strongly on the choice of the equation
of state of the detonation products. For
Heat Effects – Examples of the Use of Heat military CHNO explosives the main equilibria
Data for Estimating Heat Effects in Explosives that determine product composition are (Ref 9):
and Explosions.
1) Heat of nitratwn of glycerin. Suppose we COZ+H2=CO+H20 (a)
wish to estimate the heat evolved in nitrating
1 mole of glycerin with mixed acid. To simplify 2c0 = C02 + c(s) (b)
this illustrative example we will assume: initial
mixture – 1 mole glycerin/3 moles 100% nitric co + H2 = H20 + :(s) (c)
acid/6 moles 100%0sulfuric acid; final mixture – and
Nz + 3H2 = 2NH3 (d)
1 mole nitroglycerin completely separated from
the spent acid which is now diluted by 3 moles
of water; the entire heat of dilution is due to c(s) + 2H2 = CH4 (e)

3 moles water dissolving in 6 moles of 100%0 if the equil mixture of (a), (b) and (c) contains
sulfuric acid. Thus appreciable ‘amounts of Hz. Of these equilibria
a) C3H*03 + 3HN03 = NC + 3H20. only (a) is relatively independent of pressure
AHfO -159.8 -3x41 .4 -88.6 -3x68.3 and only moderately dependent on temperature
in the expected TCJ range. For oxygen-balanced
AHa = -9.4 kcal/mole explosives equil (a) is controlling. Thus, the
b) 6H2SOa(100%) = 6H,S04 (aq) (% H,O) composition of detonation products of oxygen-
balanced explosives should be nearly independent
AHfO -6x193.9 -6x197.67 of the choice of eqn of state
AHb = -22.6 kcal/mole For military explosives that are deficient in
The net heat effect is AHa + AHb = -32 oxygen (negative OB), equil (b) and (c) must be
kcal/mole glycerin, most of which comes from considered and the choice of eqn of state
the heat of dihrtion of H2SOQ. The AHfO’s for becomes important. Currently the BKW eqn of
these calculations were taken from Table 1 and state (see Vol 4, p D284) is used for most
Refs 1 & 7 calculations, eg Ref 4. From Mader’s talcs
2) Heat of detonation. Price (Ref 3) has (Ref 4) combined with the AHfO’s of Table 1,
shown that the heat of detonation of an ex- the heats of detonation of NC, PETN, HMX,
plosive correlates well with the blast effects RDX, PBX 9404, LX-04, TNT and NM are
 H 39

respectively: 1.48, 1.51, 1.475, 1.48, 1,41, 1.31 Expl AHdecomP (kcal/g) AHdet (kcal/g)
(Ref 10), 1.24 and 1.30 kcal/g. These values
are to be compared with experimental AHd’s HMx 0.56 at - 540”K 1.48
(for heavily confined samples) (Tables 1 and 2) RDx 0.61 at - 479°K 1.42
of: –, 1.49, 1.48, 1.42, 1.38, 1.31, 1.09 and Tetryl 0.33 at - 445°K 1.17
1.23 kcal/g. This excellent agreement between
4) Heat Balance in Estimating 0-itical
theory and experiment (except for TNT) is
Dimensions for Thermal Explosion. For thermal
really quite amazing. Theory considers H20 as
explosion to occur the rate of heat generation
gaseous, whereas it is liquid in the’ calorimeter.
must exceed the rate of heat loss. The general
Furthermore, the detonation product composi-
equations for this situation can be solved only
tion in the calorimeter is some frozen equili-
by numerical means. Specialized cases are, how-
brium composition (probably corresponding to
ever, amenable to analytical solutions. An
a freeze-out temperature of Z1600”K), while
interesting case is that of a semi-infmite slab of
CJ temperatures are of the order of 2000-
4000”K. What appears to be happening in the explosive for which Friedman (Ref 5) obtained
confined calorimeter samples is a series corn a series of approximate analytical solutions.
pensating heat effects namely: H, O@) + H20 1) These enable one to estimate the critical thick-
and Nz + 3H2 = NH3 exothermic. & the parti & ness of the slab and the time to explosion as
reversal of equil (b) & (c) (decrease of Cs) functions of the initial slab temperature and
endothermic. Also at T - 1600”K equil (a) the kinetic and thermal parameters of the ex-
is shifted towards C02 as compared to TCJ plosive
which tends to counteract to some extent the The approximate equations in dimensionless
reversal of equilibria (b) and (c) form are:
For a quick approximate computation of the
2 =
acr 400 exp(l /OO)ln[0.608(00 - fJ1)/6~ ] (1)
heat of detonation of military CHNO explosives,
the following is suggested (Ref 9) for obtaining
To s 13~exp(l/OO )/a~r (2)
an approximate product composition:
All H -+ H20@; all remaining O is used to and
form C02; any remaining C + C(s); all N + Nz 00 = RTO/E & 0’1 = RT1/E (3)
As an example of the use of this approximate
method, let us estimate AHdet for Haleite d2 = ~r~E/PRQZ (4)
(EDNA):
to = rOcpd2/A (5)
C2H6NqOQ + 3H20(g) + %COZ + 3/2Cs + 2NZ
where TO is the slab temp, TI = ambient temp,
AH? ‘S –24.6 3(–57.8) %(–94.05) O 0 E&Z are the activation energy and frequency
factor of the explosive, and A, p, c and Q are
~Hdet = 3(–57.8) + %(–94.05) + O + O – (–24.6)
= –195 .8kcal/mole its thermal conductivity, density, specific heat
AHfO’s -24.6 -3x57.8 -%x94.05 O 0 and heat of reaction. The quantities d and to
are respectively the critical 1%thickness of the
slab and the time to explosion at TO if the
AHdet = 195.8 kcal/mole = 1.30 kcal/g
process is adiabatic
which compares amazingly well with a reported
‘To illustrate the use of the heat data in the
measurement (Ref 6) of 1.3 kcal/g
preceding section for estimating thermal explo-
3) Heat of decomposition. Since the products
sion parameters, let us determine the critical
of a relatively slow (“low” temp) decomposition
of an explosive will often be quite different thickness of a semi-infinite slab of Tetryl kept
at 445”K. From Ref (2) we take E s 35000
from deton products, it is not surprising that
cal/mole and Z s 1013sec-1.Substituting these
~Hdecomp # AHdet. Hall (Ref 8) measured the values in eqn (3) and then into eqns (1) and
decomposition of solid nitramines in the temp
(2) gives:
range of 365-540”K. In the following tabulations
some of his data are compared with AHdet
2 = 3.24 X 101s & r. s 0.032
acr
taken from Table 1
 H 40

Now taking Q = 330 cal/g (Ref 8) and the

other thermal data from Table 4, solutions of
eqns (4) and (5) lead to:

d = 5.4 cm and to s 132 sec at

TO = 445°K and p = 1.6 g/cc

In qualitative terms this means that quite a

thick slab of Tetryl must be heated to around
170”C for over 2 minutes before explosion
occurs
Written by J. ROTH
Refs: 1) F. Rossini et al, NBS Circ 500 (1952)
2) Cook (1958), 178 3) D. Price, ChemRev
59, 801 (1959) 4) C.L. Mader, LASL, LA
2900, July 1963 5) M.H. Friedman, Combstn
& Flame “11, 239 (1967) 6) See Ref 12 of
Table 1 7) See Ref 14 of Table 1 8) P.G.
Hall, Trans Farad Soc 67, 556 (1971) & CA 74,
103822 (1971) 9) Anon, “Principles of Ex-
plosive Behavior”, AMCP 706-180 (April 1972)
10) UCRL-513 19 “Props of Chem Expls and
Expl Stimulants”, Dec 1972
 H 41

Table 1
Standard Heats of Formation and Heats of Detonation of Common Explosives

EXPLOSIVE AHfO ‘Hdet

———-.—--—-—- —- ———— —-—
Code or
Chemical Name kcal/mole Ref kcallg Ref
Common Name

Bk (trinetroethyl) nitrazine BTNEN -76.9 12 1.50 4

Bis (N, N-trinitroethylurea) BTNEU -32.7 12 — —

1,3 -Diamino-2,4,6-t rinitro-benzene DATB -29.8 15 1.01 9

4,6-Dinitro-2-diazophenol DDNP -27.8 8 =0.8(d) 14
Diethyleneglycoldinitrate DEGDN -102(a) 14 ~0.8(d) 14
Diethanolnitraminedinitrate DINA . -78(a) 12 — —

2,4-l)init rotoluene DNT -17.1 13 — —

Ethylenedinitramine EDNA or Haleite -24.6 13 WI .3(d) 14

Ammonium Picrate ExplD -92.7 13 ==0.8(d) 14
Bis (2,2 -dinitro-2-fluoroethyl) formal — -178.8 11 1.28 11
Cyclotetramethy lenetetramine HMx +17.93 12 1.48 11
Cyclotrimethylenetrinitramine RDX +14.71 12 1.42 3
1.38(c) 9
Hydrazine Nitrate HN -60.5 4 0.88(e) 10
2,2’,4,4’,6,6’-Hexanitroazobenzene HNAB t57.8 17 — —

Hexanitrostilbene HNs +13.8 13 — —

Lead Azide LA +115.8 7 0.40 7

Lead Trinitroresorcinate Lead +204(a) 8 — —.
/
Styphnate (LSt) +107(a) 5 — —

Mercury Fulminate MF +65 14 ~0.4~d) 14

Nitrocellulose NC
dinitro -180(b) 1 — —

trinitro -156(b) 1 =1.l(d) 14

Nitroglycerine (1) NG -88.6 13 1.48(e) 10
Nitrogwinidine NGu -22.1 13 =0.7(d) 14

Nitromethane ( !?,) NM -27.03 13 1.23 11

Marrnitolhexanitrate Nitromannite -154(a) 12 =1 .5(d) 14
Pentaerythritoltetranitrate PETN -128.7 13 1.49 11
Pentaerythritoltrinitrate Petrin -128(a) 13 =1 .2(d) 14
.
-133(a) 6 —
2,4,6-TrinitrophenoI Picric Acid (PA) -51.3 13 1.Oo(c) 4
 H.42

Table 1 (Continued)
Standard Heats of Formation and Heats of Detonation of Common Explosives

EXPLOSIVE AHfO ‘Hdet

—————.——.—— .——-—-———
Code or
Chemical Name kcal/mole Ref kcallg Ref
Common Name

Tetranitro- 1,2,5,6-tetrazadibenzo- TACOT +128 17 0.98(c) 17

cycloctatetrene
1,3,5-Triamino-2,4,6 -trinitrobenzene TATB -36.9 14 — —

Triethyleneglycoldinitrate TEGDN ,151(a) 2 — —

2,4,6-Trinitrophenylmethylnitrarnide Tetryl +6(a) 13 1.14(C) 9

l,3,5-Trinitrobenzene TNB -8.9 15 — —

Tetranitromethane (L) TNM +8.9(a) 13 — —

2,2,2-Trinitroethyl-4,4,4- TNE -118.6 4 1.47 4

trinitrobutyrate
2,4,6 -Trinitrotohrene TNT -16.0 13 1.09 11

(a) Uncertain
(b) Per monomer unit
(c) Unconfined or lightly confined – these are really AHex~ln
. and not AHdeton
(d) Conditions of measurement are unknown
(e) Computed; for these oxygen-balanced materials the computed Hd should be nearly
independent of the eqn of state of the deton products

Rej3: 1) R.S. Jessup & E.J. Prosen NBS J of Res 44, 392 (1950) 2) P. Tavernier, MP 38, 329
(1956) & CA 51, 15952 (1957) 3) A. Ya. Apin & Yu A. Lebedev, Dokl Akad Nauk SSSR 114, 819
(1957) & CA 52, 3345 (1958) 4) NAVORD Rept 2986 Sect D2 (1958 Supplm) 5) Quoted in
Bowden&Yoffe(1958), p 152 6) Priv comm fromABL(1958) 7) B.L. Evans et al, Chem Rev 59, 546
(1959) 8) B. Glowiak, Chem Stosowana (Poland) 5, 575 to 98 (1961) & CA 57, 3687 (1962)
9) LRL, Gen Chem Tech Note Number 128 “Props of Chem Expl”, June, 1963 10) C.L. Mader,
LASL, LA 2900, July, 1963 10a) N.O. Holland, Editor, “Explosives – Effects and Properties”, NOLTR
65-218 (Feb 1967), Sect D 11) D.L. Ornellas, JChernPhys 722390 (1968) & CA 69,53315 (1968)
12) D.R. Stun, E.F. Westrum & G.C. Sinke, “The Chemical Thermodynamics of Organic Compounds”,
Wiley, NY (1 969) 13) J.D. Cox & G. Pilcher, “Thermochemistry of Organic and Organometallic Com-
pounds”, AcadPress, NY (1970) 14) AMCP 706-177, “Props of Expls of Military Interest” (1971)
15) Priv comm quoted by R. Shaw, JPhysChem 75, 4047(1971) 16) N.D. Lebedeva et al, ZhFizKhim
45, (4), 980, (1971) &CA 75, 11145 (1971) 17) UCRL-51319, “Props of Chem Expls and Expl Stim-
ulants”, Dec 1972
 H 43

Tables of Heat-data “are presented below:

Table 2
Standard Heat of Formation and Heats of
Detonation of Explosive Mixtures

AHfO ‘Hdet
calig Ref
—
kcal/g Ref
—

Bardtol -708 1 — —

Comp B-3 +11 2 1.20(a) 1

Comp C-4 +33 — — —

LX-04(b) -215 1 1.3 l(a) 1

Lx-1 l-o(c) -307.3 1 1.23(d) 1

Octol +26 1 — —

PB9404(e) +0.8 1 1.38(a) 1

Pentolite 50/50 -239 2 1.23(d) 1

XTX-8003(f) -444 1 1.16(d) 1

(a) Moderate confinement

(b) 85/ 15 HMX/Viton
(c) 80/20 HMX/Viton,
(d) Heavy confinement
(e) 94/3/3 HMX/NC/binder
(f) 80/20 PETN/Silicone rubber

Refs: 1) UCRL-51319 “Props of Chem Expls

and Expl Stimulants,” Dec 1972 2) Algebraic
addn of AHfO’s of individual explosive composi-/
tions taken from Table 1
 H 44

Table 3
Melting Points, Heats of Fusion, Heats of Vaporization and Heats of Sublimation of Common HE

rep(a) AHfus(a) AHvap(a) AH~ubl(a)

Explosive “c kcal/mole kcal/mole keal/mole

DATB 290(12) — 33.5(10) ,

/3 HMX 286(16) — 41.9(10)

HNS 318(15) — — 43.0(1 o)

NC 12.8(4) 6.0(5) =(8)

18.5(1) —
26(5) .

Nitroform 15 3.6(9) 7.8(9) 11.1(9)

-29 — ~2(11)
NMethane
8.4(8)
PETN 141(12) 23.0(1) 36.3(4)
17.8(6)
Picric Acid 122(12) 4.7(12) 21.0(1)
RDx 205.5(13) 8.5(13) 26.0(1) 31.1(10)
2~8(4)
TATB 330(12) — — 40.2(1 O)
Tetryl 126.5(13) 6.2(13) 26.0(1) —
6.4(12)
TNA(b) 188 — 27.7(10)
TNB(c) 121 4.0(14) W(7) —
18.5(1) —

TNT 81(12) 5 .4(2) 17(1) 28.3(2)

5.1(12) W(8) 24(3)

(a) Numbers in ( ) are Refs; underlined values are preferred

(b) 2, 4, 6-Trinitroaniline ,
(c) Sym-Trinitrobenzene

Refs: 1) A.F. Belyaev, ZhFizKh 22,91 (1 948) 2) G. Edwards, TransFaradSoc 46,423 (1950)&CA 44, ,
9754 (1950) 3) I. Nitta et al, NipponKagakuZasshi 71,378 (1950)&CA 45,6448 (1951) 4) G. Edwards,
TransFaradSoc 49, 152 (1953) 5) M.D. Kemp et al, JPhysChem 61,240 (1957)&CA 51,8524 (1957)
6) N. Lundborg, Arkiv Fysik 20, 499 (1961) & CA 56, 7567 (1962) 7) Yu. Ya. Maksimov “Teoriyd
V V Sb Statei” (1963) & CA 59, 12206 (1963) 8) J. Roth, Final ReDt SRI Contract NOW 65-
0283-d “Evaluation of the Wenograd Test” p 36” (1966) 9) E.A. Miros~nichenko et al, Zh Fiz Khim
41, (6), 1477 (1967) & CA 67, 85584 (1967) 10) J.M. Rosen & C. Dickinson, J Chem Eng DATA
14, 120 (1969) & CA 11) D.R. Stun, E.F. Westrum & G.C. Sinke “The Chemical Thermodynamics
of Organic Compounds”, Wiley & Sons .(1969) 12) AMCP 706-177 (1971) 13) P.G. Hall, Trans
Farad Soc 67, 556 (1971) & CA 74, 103825 (1971) 14) N.D. Lebedeva et al, Zh Fiz Khim 45, 980
(1971) & CA 75, 11145 (1971) 15) Brochure Del Mar Co of Los Angeles, Calif, date unknown
16) UCRL-513 19 “Props of Chem Expls and Expl Stimulants”, Dec 1972

I
 H 45

Table 4
Heat Conductivity Coefficients and Specific Heats of Common Explosives

Coeff of Heat Conduction Specific Heat

Extdosive (cm) x 104 temp (“C) Cp (cal/deg g)

Baratol 11.8 at 2.5 g/cc (3) -75 0.280 (6)

0 0.213 (6)
25 0.201 (6)
100 0.171 (6)
Comp B 6.3 at 1.71 g/cc (6) -75 0.235 (6)
0 0.220 (6)
25 0.254 (6)
50 0.305 (6)
75 0.376 (6)
4
85 0.354 (6)
100 0.312 (6)
1840 0.324 (7)
DNT 6.2 at 1.32 g/cc (5) — —

HMx -75 0.153 (6)

0 0.228’ (6)
25 0.248 (6)
50’ 0.266 (6)
100 0.295 (6)
150 0.315 (6)
~ HMX -70 to 250”C 0.0935 + 5X10-4T (5)

Lead Azide 1.6 (5) -50 to 50 0.110 (6)

4 at 3.62 g/cc (2) 100 0.100 (2)
200 0.117 (2)
250 0.116 (2)

had Styphnate -50 0.141 (6)

0, 0.158 (6)
25 0.164 (6)
50 0.167 (6)
100 0.164 (2)
200 0.191 (2)
Mercury Fulminate 1 (5) 110 to 125 0.120 (2)
2.9 (1)

NMethane liq 0.414 (4)

NC solid 0.315 (6)
liq 0.356 (6)
LX-04 9.3 at 1.86 g/cc (6) 20 s0.28 (7)
PBX9404 10.1 at 1.83 g/cc (6) -55 0.18 (3)
-lo 0.26 (3)
22 0.24 (3)
55 0.25 (3)
85 0.28 (3)
PETN 6 at 1.46 g/cc (2) 115 0.272 (1)
 H 46

Table 4 (Continued)
Heat Conductivity Coefficients and Specific Heats of Common Explosives

Coeff of Heat Conduction Specific Heat

Explosive ~fe~ x 104 tem~ (“C) Cp (cal/deg g)

Picric Acid (PA) 6.2 at 1.41 g/cc (5) o 0.235 (6)

2.4 at 1.7 (1) 30 0.258 (6)
60 0.282 (6)
120 0.337 (6)
? 0.26 (1)

RDx 6.9 at 1.26 g/cc (5) 20 0.298 (6)

7.0 at 1.53 g/cc (5) 60 0.330 (6)
100 0.406 (6)
140 0.446 (6)

Tetryl 5.8 at 1.39 g/cc (5) -1oo 0.182 (6)

6.8 at 1.53 g/cc (5) -50 0.200 (6)
2.3 at ? (1) 0 0.212 (6)
50 0.223 (6)
100 0.236 (6)
9 0.225 (1)

TNT 5.3 at 1.19 g/cc (5) 0 0.309 (6)

7.1 at 1.51 g/cc (5) 20 0.328 (6)
6.2 at 1.6 g/cc (6) 50 0.353 (6)
80 0.374 (6)
.4 ~ at ~.6\(;)~
93 liq 0.376 (4)
?’
3.5 at 0.89 1)
f c< h 0.35 (1)

Refs: 1) A.F. Belyaev & N. Matyushko, Compt Rend URSS 30, 629 (1941) & CA 37, 531 (1943)
2) Quoted in Bowden & Yoffee (1958), pp 153 & 155 3) LRL, Gen Chem Tech Note Number 128, “Props of
Chem Expls”, June 1963 4) W.C. Davis, preprints Proc 4th Symp on Deton p A41 (1965) 5) H.H..
Licht, Sympos on Chemical Problems connected with the Stability of Explosives, Tyringe, Sweden,
1970, p 177 6) AMCP 706-177, (1971) 7) B.M. Dobratz, UCRL-51319, “Props of Chem Expls and
Expl Stimulants,” Dec 1972

k ‘/
d
 H 47

Heat Effects - Methods for Estimating AHfO. important in predicting reaction equilibria and
In the preceding sections we have emphasized yields, in process design, in thermal engineering
the importance of knowing the heats of forma- applications, and in evaluating fire and ex-
tion of explosive materials in order to estimate plosion hazards. So far, the ideal gas state has
AHd, detonation product compositions, fire & received a large portion of thermochemists’
explosion hazards of potentially dangerous efforts. For example, the first page of the
materials, and critical diameters for thermal fding, order for JANAF Thermochemical Data
explosions. This is by no means a complete list (Ref 6) contains 58 gases, 10 “liquids, and 28
of the uses of heats of formation. Thus the solids. This emphasis on gas phase stems partly
AHf” of a compound is indeed one of its most from its more advanced theoretical status and ‘
useful properties. However, how does one pro- partly from its importance in military pro-
ceed if the AHfO for a material of interest has blems. However, in the incoming requests for
not been determined experimentally? The data at Stanford Research Institute from
obvious answer to thk is by estimating AHfO chemical engineers, we have had many more
on “the basis of theoretical or semi-empirical inquiries for condensed phases than for gases
methods. Many such methods exist. The follow- Estimated data have many advantages.
ing article contributed by Dr. Robert Shaw of Measurements are time-consuming and costly,
SRI presents a method that is particularly appli- and in many cases estimates are all that are
cable to estimating the heats of formation of needed for screening purposes. On the other
explosive compounds hand, a minimum of good experimental data
Estimation of Heats of Formation of Organic is required as a basis for estimates. Estimates
Chemical Explosives by Group Additivity. are especially important in explosives thermo-
Introduction. During the past decade there have chemistry, because so many of the experime~tal
been significant developments of empirical measurements are buried in difficult-to-reach
methods for estimating the thermodynamic, technical reports and in the classified literature
properties of organic compounds based on An important use of accurate estimates, such
group additivity methods as those provided by Group Additivity, is that
Advances in scientific and technological they provide a check on experimental measure-
aspects of chemistry are dependent on advances ments. In all cases where discrepancies have
in basic information. Thermochemistry is existed between measured data and those esti-
important in our understanding of molecular mated by Croup Additivity, repeating or check-
structure including stabilities, strain energies, ing the reported experimental data revealed
and interaction with radiation. It is also errors. Som”e examples are given in Table 1

Table 1
Some Examples of the Use of Group Additivity to Check Experimentally
Determined Heats of Formation
(Units are kcal/mole for the ideal gas state.)

Original Estimated A Revised A

Measure- by Group (Mess - Measure- (Meas.-
Compound ment Additivity Est ) ment Est.)

l-Methylcyclopentene -1.5a -o.3a -1.2 -06b 0.2

2.6a 6.6a -4.0 ~3b
Tetralin 0.7
t-Butyl hydroperoxide -52.1a -57.1a 5.0 -58.8b -1.7
Hexanitrostilbene 29.2C 58.6d’ 29.4 57.0e 1.6

aRef 14 ‘Ref 20
bRef 15 ‘Ref 9 ,
cRef 8
 H 48

Estimating techniques point out where experi- and “Inlplementation of Combined Second
mental data are lacking and where sufficient Order Additivity and Group Equations Methods
experimental data already exist. For example, for the Estimation of Chemical Thermodynamic
Table II shows heats of formation that have Data,” by W.H. Seaton and E. Freedman) dealt
been reported since the 1969 paper on Group with applications of Group Additivity
Additivity was published (Ref 14). The agree- A powerful argument in favor of Group
ment between experimental data and that pre- Additivity is that a start has already been made
dicted by Group Additivity is very gratifying, in the application of Group Additivity to con-
but it raises questions of cost/benefit regarding densed phases. In 1969, groups were derived
the selection of these compounds for experi- (Ref 11) for the heat capacities of liquids at
mental study 298°K that improved the precision of estimation
Having discussed the need for estimated data, from f 4 to better than ~ 1.5 cal/(mole-K).
we turn now to the “question, “why Croup Since then, groups have been derived for heats
Additivity?” The most cogent answer is, user of formation of solid nitroaromatics (Ref 20)
acceptance. In the present state of the art, there and for solid and liquid nitroalkanes (Ref 22)
is a bewildering variety of methods of estima- Group Additivity. The basic idea behind Group
tion, most of which are complicated, time- Additivity is that chemical thermodynamic
consuming, and of limited usefulness. The properties of molecules consist of contributions
Group Additivity method is ‘simple, fast, and from, the individual groups that make up the
accurate, and is quickly gaining wide acceptance molecule. Group Additivity is therefore an ex-
as the best and most general method for esti- tension of the series atom additivity, bond
mation of gas-phase data. For example, ASTIM additivity, . . . , and turns out to be an ex-
Cbmmittee E-27 on the Hazard Potential of cellent compromise between simplicity and
Chemicals has adopted Group Additivity as the accuracy
method of chcice for estimating thermo- A useful way to look at it is to consider an
chemical data. CIBA-GEIGY Inc has recently example of Group Additivity applied to the
sent its Director of Explosion Hazard Research AHfO of gases at 25°C :“ The n-hexane molecule
to SRI for a year to study estimating techniques is made up of two methyls bonded to carbon
with Dr. Benson. E.S. Domalski of the National atoms, indicated by 2 [C-(C) (H)3] , and four
Bureau of Standards has used Group Additivity met,hylenes’ ‘bonded to two carbon atoms, indi-
methods to estimate the thermochemical pro- cated by 4 [C-(C) 2(H)2 ] Similarly, n-octane is
perties of the air pollutants PAN (peroxyo- composed of 2 [C-(C)(H)3] + 6 [C-(C) Z(H)Z] ;
cetylnitrate) and PBN (peroxybenzoylnitrate) thus
AHfO(kcal/mole)
—
(Ref 17). Dr. Benson has been invited by the
new ACS journal, Chemical Technology, to 2 [C-(C)(H)3] + 4 [C-(C)2(H)2], = -40.0
write a paper entitled, “The Use of Empirical
Methods for the Prediction of Thermochemical 2 [C-(C)(H)3] + 6 [C-(C), (H),] = -49.8
and Kinetic Rate Data and the Uses of Limitat-
ions of Such Data in Laboratory Practice and and [C-(C) Z(H)Z] = -4.9 and [C-(C)(H)3] = -10.2
in Plant Design.” The Environmental R-oteclion
Agency has recently sponsored a project at SRI The AHfO of n-decane may then be estimated
to apply computer techniques to the estimation as 2 [C-(C)(H)3] + 8 [C-(C) 2(H)Q] = -59.6 (cf
of thermochemical and kinetic data using Group -59.7 observed). The other groups were obtained
Additivit y. The McDonnell-Douglas Laboratories, similarly. In practice, when there is a large
sponsored by a contract with the Ballistic amount of measured data, the groups are derived
Research Laboratory, is developing a computer by computer, using a least squares regression
program to use Croup Additivity for gases. Two program, giving [C-(C)(H),] = -10.1 and [C-(C),
papers at the 65th Annual Meeting of the (H)z] = -5.0 kcal/mole
American Institute of Chemical Engineers “
(“Thermophysical Properties of Pure Chemical
Compounds,” by P.L. Chueh and C.H. Deal,
 H 49

Table II
Comparison of Estimated Heats of Formation with Some Measured Since 1969a
(The units are kcal/mole for the ideal gas state.)
Estimated
Measured Using Group A’
Compound Since 1969 Values (Mess.-Est. )

n-Pen tane -35.08 -35.10 0.02

2-klethylbutane -36.73 -36.29 -0.44

2, 2-Dimethylpropane -40.14 -39.82 -0.32
n-Propylcycl ohexane -46.0 -45.3 -0.7
l-hlethyl-l-ethylcyclohexane -46.6 -45.8 -0.8
l-Methyl-cis-2-e thylcyclohexane -45.7 -44.9 -0.8
l-hlethyl-trans-2-ethyl- -46 6 -46.5 -0.1
cyclohexane
l-hlethyl-cis-3-ethylcyclo- -48 2 -48.1 -0.1
hexane
l-hIethyl-cis-4-ethylcyclo- -46. 3 -46.5 0.2
hexane
l-Methyl-trans-4-e thyl- -49.1 -49.1 0.0
cyclohexane
n-Propylcyclopen tanc -35.3 -34.6 -0.7
3-hlethylcvcl opentene 2.0 1.s7 0.2
Acenaphthcnc 37.4 36.8 0.6
Accnaphthalcnc 61.6 60.8 0.8
Cyclopropylamine 18.4 17.3 1.1
2-!Jethyl-l-lx] tanethiol -27.42 -27.24 -0.18
3-Methyl-l-butanethiol -27.40 -27.24 -0.16
3-i!ethyl-2-bl]tanethiol -28.91 -29.36 0.45
2, 2-Dimethyl-l-propnnethiol -30.76 -30.77 0.01
2,3-Dimethyl-2-butane thiol -35.22 -36.55 1.33
2-h!ethyl-2-pcntanethiol -35.37 -35.17 -(-).~~

&’I’OIUcncthiol 21.90 21.90 0.00

Diethyl ketone -61.7 -62.0 0.3
Methyl-n-propyl ketone -61.9 -61.7 -0.2
Methyl-isopropyl ketone -62.8 -63.3 0.5
Methyl-n-butyl ketone -66.9 -66.7 -0.2
Methyl-t-butyl ketone -69.5 -70.3 0.8
Ethyl-n-propyl ketone -66.5 -66.9 0.4
 H 50

Table II (Continued)
Comparison of Estimated Heats of Formation with Some Measured Since 1969a
(The units are kcal/mole for the ideal gas state.)
ES t i ma tcd
h!easurcd Using Gr(,[lp A
Compound Since 1969 Va lltes (Mess .- Est.)

Ethyl-isopropyl ketone -68.4 -68.5 0.1

Ethyl -t- butyl ketone -75.0 -75.5 0.5

Diisoprop,yl ketone -74.4 -75.1 0.7
Isopropyl-t-butyl ketone -80.8 -82.1 1.3
Di-n-butyl ketone -82.4 -81.8 -0.6
Di-t-butyl ketone -82.6 -89.1 6.5

Methyl-hexyl ketone -82.5 -76.6 -5.9

Ethyl-pentyl ketone -80.9 -76.8 -4.1
Propylbutyl ketone -83.5 -76.8 -6.7
Di-isobutyl ketone -85.5 -84.3 -1.2
t-Butyl-neopentyl ketone -94.2 -94.0 -0.2
I)i-n-pentyl ketone -92.6 -91.7 -0.9
Acrolein -17.8 -17.8 0.0
8ut-2-ennl -25.5 -25.6 0.1
8enzaldehyde -8.9 -8.9 0.0
3,5-Dioxaheptane -9’3.1 -9.9.8 -0.3
1,1-Diethoxye thane -108.4 -109.2 0.8
3,6-Dioxaoctane -97.6 -99.0 1.4
2,4, 6-Trimethyl-3,5-
dioxaheptane -125.7 -126.4 0.7
.
6-Ethyl-5, 7-dioxaundecane -132.1 -133.9 1.8

3,5, 7-Trioxanonane -138.9 -138.2 -0.7

3,5, 7,9-Tetraoxaundecane -177.1 -177.5 0.4

3,5, 7,9, 11-Pentaoxatridecane -216.5 -216.8 0.3 -

Propionaldehyde -44.5 -44.4 -0.1

Dimethoxyme thane -83.2 -82.7 -0.5

l, l-Dimethoxyethane -93.1 -92.9 -0.2

a The hydrocarbon and amine data are from Ref 19, the sulfur data are from Ref 25, and the data
for oxygenated compounds are from Ref21
 H 51

For a second example, from Stun, Westrum, If the heat of sublimation is known, then the
and Sinke; (Ref4 12) for n-pentane AH~liqirid) = heat of formation of the solid follows. The
-41.4 kcal/mole, and for n-hexane, AHf(liquid) = second method is to develop group values for
-47.5 kcal/mole. n-Hexane has one more solids and to use these directly to calculate the
[C-(C), (H)2 ] group than n-pentane, therefore, required heat of formation. The heats of for-
[C-(C), (H),] ~ = -47.5- (-41 .4) = -6.1 (where mation of some solid nitroaromatic compounds
the subscript !2 denotes liquid phase). Sub- present an interesting example of the two
stituting the above value of -6.1 we obtain the approaches, The results suggest that the direct
methyl group [C-(C)(H)3 ]L = [-47.5 - 4(-6.1)] /2 approach of using group values for solids is the
= [-47.5 + 24.4] /2 = -23.1/2 = -11.6 better method at present
Check: AHf(n-heptane)8 = 2 [C-(C)(H)31 ~ + The Ideal Gas Method. The heat of formation
5[C-(C),(H),] ~ = “2(-1 1.6)”+ 5(-6.1) = -23.2- of a nitroaromatic compound in the ideal gas
30.5 = ~53.’7 ~cal/mole, cf -53.6 measured (Ref state requires that the C~-N02 group be known
12). As an added bonus, we obtain groups for (where CB represents an aromatic, i.e., benzene
estimating heats of vaporization. From previous carbon atom). This group was not given in the
work (Ref 14) we know that for the ideal gas recent ideal gas group additivity review (Ref 14).
the value for the group [C-(C)(H)3] g is -10.1 The group may be obtained from the heat of
kcal/mole (where the subscript g denotes ideal formation of any nitroaromatic compound in the
gas). Therefore, [C-(C)(H)3] “ap = [C-(C)(H)3] g - ideal gas state if the other groups are known.
[C-(C)(H)3] ~ = -10.1 - (-1 1.6) = 1.5 kcal/mole For example, for nitrobenzene AH; = 5(CB-H)
(where the subscript vap denotes heat of vapori- + 1(CB-NOZ) = 16.9 kcal/mole (Table IV).
zation. Similarly, [C-(C)2(H)2] vap = [C-(C)Z(H)2] g From the known value of (CB-H) = 3.3 kcal/
- [C-(C), (H),] ~ = -5.0- (-6.1) = 1.1 kcal/mole. mole, (C B-NOZ) = 16.9 - 16.5 = 0.4 kcal/mole.
Then the heat of vaporization of n-heptane at In Table IV the heats of formation of several
298 K = 2 [C-(C)(H)3] Vap + 5 [C-(C)Z(H)2] vap nitroaromatic compounds in the ideal gas state
= 2(1 .5) + 5(1.1) = 3.0 + 5.5 = 8.5 kcal/mole are calculated from the measured heats of
cf, 8.7 measured (Ref 12) formation of the solid and the measured heats
To date, group values have been derived for of sublimation. In cases where the heat of sub-
heats of formation of the states and classes of limation is not measured at 298°K there should
compounds shown in Table III. be a correction for the differences in heat
capacities of the solid and ideal gas. The data
Table III required to make these corrections are not
Group Values Now Available
available but in general it is expected that the
State Class of Compound Reference corrections will be small and can be neglected.
From the heats of formation of each compound
Ideal gas Organics in general 14 in the ideal gas state, a value for the group
Solids Nitroaromatics 20 CB-NO, (ideal gas) has been derived (Table IV).
A weighted-average value (CB-N02(ideal gas)) =
Solids, liquids, Nit roalkanes 22
3.0 kcal/mole was used, and a heat of forma-
ideal gases tion was estimated for each compound. In
Ideal gas Oxygen-containing Table lV the difference between observed and
organics 21 estimated heat of formation in the ideal gas
Ideal gas Am compounds 26 state is less than ~ 3.2 kcal/mole in all cases

Heats of Formation of Solid Nitroaromatics. h

principle, there are two methods of using group
additivity to determine heats of formation of
solids. If the groups are available, then the heat
of formation of the ideal gas can be calculated.
 Table IV
Measured and Estimated Heats of Formation of Various Compounds at 298° K in kcal/mole

AHf A AHf A
AHf AHf AH AH AHf CBN02 gfOUp Ideal Gat Ideal Gas Crystal Cry$tal
Crystal Ref
— Liquid - —
Raf Sublimaticm Ref Vaporization Ref
— Ideal Gai Ideal GaI est. obs-est est. Obs..est.

Nil rohcnzcne 3.8 2s 13.1 a 16.9 0.4 19.5 -2.6

2.2”,.i.’l”.6,ti. 13.9 9 43.0 al 457°K 17 56.9 2.7 58.5 .1.7
Ik.ani[rost ilbene (I INS)

lr~ns-Stilbene (TS) 32.7 9 20.7 18 53.4

2.4.6- Trit!il mtulume -15.4 9 28.3 7 12.9 3,2 12,2 0.7 .1s.0 4.4
(TNT) 24.4 19 9.0 1.9 12.2 -3.2
2.-l .fi.Tri!, iti ma,,iline .17.8 ,? 27.7 at 350°K 17 9.9 12.9 -3.0 -16.0 +0.2
(TN,\)

I ,3. Dmmill* 2.4,0. -29.2 16 33.5 at 358”K 17 4.3 6.9 .2.6 .27.0 -2.2
trinit rohenzene (DATB) x
m
N
1.3.5-Triaminv.2.4,b. -36.9 16 40.2 at 426°K 17 3.3 0.9 2.4 .36.0 J3,Y
t[initmbenzene (TATtl)

rnflnitmhenzme .6.2 12 .6.0 4.2

(m-DNB)

1.3,5-Trinitrobenzcne .9.6 17 ‘9.0 43.6

(TNB)

pNitrmmiline !(P-NA) .10.0 12 -12.0 +2.0

2,4.DinitrOanifine .15.7 12 -15.0 J3.7

(DNA)

2,6-Din itrotoluene -10.5 lj .12,0 +1.5

(DNT)
m-w minus Ts -18.8 3.5 3.5 0.6 2.9 .18.0 0.8

aFrom the data given by Timmermans (Ref 7), AHva~ = 11.34 kcal/mole at 450”K, For liquids like nitrobenzenell, Cp (liquid) minus Cp (gas)
= 12 cal/(mole deg), so AHvap at 298°K = 11.3 + i2(450-298) = 13.1 kcal/mole
 H 53

The Group Adclitivity for Solids Method. The Another anomaly is found for the 1,1,1-
large number of compounds for which the fluorodinitroalkanes. The experimental AHf for
heat C)f formation of the solid has been 1,1,1-DNE and 1,1,1-DNP both give values for
measured makes the group additivity for the group C-(C)(NOZ)2 (F) which differ by 9
solids an attractive method. From the measured kcal/mole. For lack of definite information, the
data (Table IV), groups were derived by inspec- difference is split equally in setting the group
tion. The values for the groups are (CB-H) = O, value. However, the following comparison
~ (CB-NO,) = -3, (CB-NH,) = -9, and (CB-CH,) = suggests that the experimental AHf for 1,1,1-
-6 kcal/mole. If the groups hdd been derived DNE is suspect:
statistically, there would probably be a slight
improvement, but the convenience of having EtH+ F +EtF + H +9.1 kcal/mole
(CB-H) = O and integral values for the other n-PrH + F + n-PrF + H + 9.2 kcal/mole
groups would be lost in the process. Using
these groups, the heats of formation in the 1,1-DNE+ F ~ 1,1,1-FDNE+ H -1.3 kcal/mole
solid state for a number of compounds have l,l-DNP +F~l~l,l-FDNP +H+7.3kcal/mole
been calculated. The differences between ob-
served and estimated values are small and in More work is needed on the experimental values of
the range expected for group additivity AHf for the 1,1,1 -fluorodinitroalkanes
Cbrrclusion. In general, the fit between ob-
served and estimated values suggests that the
principle of group additivity can be successfully
applied to the heats of’ formation of solids.
At present this approach is more convenient
than using ideal gas groups together with heats
I of sublimation

Heats of Formation of Nitroalkanes. The heats

of formation of several liquid and solid poly -
nitroalkanes have recently been measured by
Lebedeva and Ryadnenko (Ref 10). Their results
support and extend some earlier work by
Holcomb and Dorsey (Ref 2) and by M4dard
and Thomas (Ref 5). Data for the liquid and
gaseous mononitroalkanes have been evaluated by
Stun, Westrum, and Sinke (Ref 12). JANAF
(Ref 6) have reported some unpublished results
by Shomate. All the above results are listed in
Table V with estimates based on group addi-’
tivity using the group values derived by us and
listed in Table VI. The agreement between ob-
served and estimated values is very good with a
few exceptions. The most spectacular exception
is 1,1 ,1,3,5,5,5 -Heptanitropentanc where, even
allowing for 6 alkyl gauche interactions, the
compound is. made unstable by about 14 kcal/
mole, perhaps because of NOZ crowding
 H 54

Table V
Heats of Formation of Nitroalkanes

S~D L~D IOEAL GAS

gauche cliff cliff dif f
rnrrections obs
.— tef eat
—— (ohs.est) obs
—. rnf mt
_— (ohs-est) Obs
—— ref efi (ob$-est)

1-NITROALKANES
Nitroethane .33.9 12 -33.I 4.8 -?4.2 12 -24,5 0.3
l-Nitropropane 40,2 12 -39,2 .1.0 -29.8 12 .2.9.5 J3.3
l. Nitrobutane 46.0 12 45.3 4.7 -34.4 12 -345 0.1

2-NITROALKANES 12 12
2-Nitropropane 43.3 12 44,4 1.1 .33.5 12 .33.8 0.3
2-Nkrobutane l-alk-N02 49.6 12 48.5 1.1 -39.1 12 -38.8 4.3 .
1,1-DINITROALKANES
1,1-Dinimethtme .35.4 10 -35.6 0.2 -20.0
1;1-Dinitropropane 1.alk-N02 -39.9 10 .39.7 ~.~ .2s.0 .22: [O]b
1,1-Ditit ropentme I alk.N02 .51.9 10 .51.9 0.0
1,1,1-FLUORODINITROALKANES
1,1,1-flurodinitroetlmne 473 6 -71.8 4.5 -57.024 -5;.0 [0]
1,1,1.Fluomdinitropropmle 1 alk-N02 430.4 6 -75.9 4.5 -62.0
ALPHA-OMEGA DINITROALKANES
1,2-Dinitroe[hane 42.7 10 44.4 1.7 .39.7 10 43.0 3.3 -28.8
1,3-DinitrOpropane “ -51.3 49.5 10 49.1 0.4 -33.8
1,4-Dinitrubutane -59.6 10 -58.1 I .5 -56.8 10 -55.2 .1.6 .38.8

PRIMARY-SECOXDARY’ 131NITROALKANES
1,2-DinitrOprfipane I alk-N02 -S2.3 -38.1

2,2-DINITROALKANES
2,2-Dmit ropropnne 46.0 10 47.5 1.5 43.3 10 44.2 1.1 .30.4 2 -30.4 [0]
2,23,3-Tet ranitmbu!ane 4 armoz 43.6 10 42.7 CL9 40.1 10 .39.2 4.9
2 N02-NOY

1,1,1-TRINITROALK.ANES
1,1, l-Trinitrocthanc .26.9 10 -26.8 Q.1 -23.2 10 -24.6 I .4
Hexanitroethane 6 N02 -NO, 26.6 6 26,8 1.8
1,1, I -Trinit ropropane 2 alk-N02 -28.1 6 -20.7 .1.4
1,1,1,3.Tetrani[roprupane 2 alk.N02 .38.6 6 -38.7 0.1
1,1,1,4.Tetranitrobutane 2 dk.No2 45.4 10 45.5 0.1 42.8 10 42.7 ill
1,1,1,3,5,5,5 .heptanitrupentme 6 alk-N02 .36.7 10 49.9 13.2 .33.7 10 47.4 13.7

TERTIARY NITROALKASES
2,3-Dimethyl.2,3 .dini[robuUme 6 &k-NO, .74.5 10 .74.5 [0.0] .71,0 10 -71,0 [0]

NITROALKENES
Nit roethylene 13.4
l-Nit ropropylene 5.6
2.Nitropropylene 0.6

aCalculated from datain reference 2

bSquare brackets indicate that the compound was the sole source of this group, so that there is necessarily a
fit between observed and estimated data

.
 H 55

Table VI
Group Values for Estimating Heats of
Formation of Nitroalkanes
Ideal
GrouP Solid Liquid Gas
C-( C)(H) Z(N02) -22.2 -21.5 -14.4
C-( C)2(H)(N02) (-21)a -21.2 ‘ -13.6
C-( C)a(N02) -17 -18.3
C-( C)(H) (NOZ)2 -24.0 -9.9
C-(C)(F)(N02)Z -60.2 -46.9
C-(C)2(N02)Z -21.2 -21.0 -10.2
C-(C)(NOZ)3 -13.6 -13.0
alk-NOz gauche 2 2 0
NO=-N02 gaucho 9 9
c1
C-(C)(H)~ -13.5b -11.6= -10.1
C-(C)2(H)2 -6.85b -6.1C -5.0d
cd-(H)(No2)a 7. 1=
a
Cd-(C)(No2) 4.4e

aBa~ed on liquid phase group

bBasedonnC18H3, aqdnC,,H66 (Ref12)

cBased on nC5H12 and nC6H1a (Ref 12)
‘Ref 14
‘Estimated from kinetics (Ref22)
 H 56

Table Vll
Heats of Formation (in kcal/mole) of Azo Compounds Measured by
Engel and Wood (Ref 23) and Estimated by Group Additivity

Compound AHf liquid AH AH; ~aS AIIj gas Difference

vap
Obs est obs - e~t

[CH,CH,C112N], trans 4.0 8.0 12.0 12.0 [0]

[( CFI,) ,CHN], trans O.i 8.0 8.4 S.4 [0]

Cis 0.4 10.0 10.4 9.4 1.0

[( CH3)3CN], trans -18.4 8.8 -9.6 -9.6 [01

35.5 11 46.5 48.6 -2.1

5.6 13 18.6 21.7 -3.1

1.1 9.7 10.8 6.0 2.8

 H 57

A small but mathematically significant devia-

tion from group additivity is shown by 1,2- Table VI Il.
dinitroethane in the liquid phase. The difference Group Values for Calculating Heats
of 3.3 kcal/mole between the observed and of Formation of Trans Azoal kanes
estimated values is too large and cannot and Azo Radicalsa
reasonably be reduced by altering the group
value. An experimental value of the heat of AHfO
vaporization of l,2-dinitroethane is needed Group (kcal/rnole)
Azo Compounds in Ideal Gas State. As Benson
and Walsh have commented (Ref 14), “(Thermo- NA-(NA”)(C) 56.4
chemical) information on azo compounds is NA-(C) 27.0
particularly lacking.” The only azo compounds -10.1
C-(NA)(H)3
for which experimentally determined heats of
formation have been published are difluoro- C-(NA)(c)(H), -6.0
diazine FNNF, diimide I-INNH, and azoiospropane C-(NA)(C),(H) -3.4
(CH,),CHNNCH(CH, ),. However, Engel and Wood -3.0
C-(NA)(C)3
(Ref 23) recently measured the heats of com-
bustion and vaporization of a large group of
azo compounds. Their results are summarized in aThis table was compiled from data in references
Table VII 23 and 18 and after considerable discussion with
Engel and Wood’s value for the heat of for- S.W. Benson. There are some typographical errors
mation of azoisopropane is 11 kcal/mole less on p 32 of O’Neal and Benson’s monograph
stable than Coates and Sutton’s 1948 value (Ref 15). The groups [C-(N)(H),], [C-(N)(H)(C)],
(Ref 1) of 19.4 kcal/mole. A consequence of and [C-( N)(C)2] in the third column of Table
this change is that AHfO of azomethane cal- V-8 are all missing a carbon atom. They should
culated from graph values (Table VI 11) becomes read [C-(C)(N)(H) Z], [C-(N) (H)(C) Z], and
34.0 kcal/mole instead of the previous value [C-(N)(C)3]. Also in the text DH,O - DH20
(Ref 6) of 44.7 kcal/mole. A further con- should read DHI 0 + DHZ”.
sequence is that the heat of hydrogenation of
azomethane then becomes 12.4 kcal/mole, Conclusions. Group additivity, an established tech-
which is very different from the heat of hydro- nique for estimating the heats of formation, has
genation of diimide (27.4 kcal/mole). However, been well developed for application to organic
Engel and Wood’s data are very self-consistent chemicals, in general, in the ideal gas state.
as shown by the reasonable agreement be- However, very little has been done in deriving
the group values for the many classes of or-
tween their experimental results and those cal-
ganic explosives in condensed phases, especially
culated by group additivity for the cyclic com-
pounds (Table VIII). Therefore the more recent the solid state. The principles are there; it is
work by Engel and Wood is favored only a case of doing the work
Written by R. SHAW
 H 58

Refs: 1) G.E. Coates & L.E. Sutton, J Chem - Heat of Evaporation. See under Heat, Latent
SOC 1948, 1187 & CA 43, 931 (1949) 2) D.E.
Holcomb & C.L. Dorsey, Jr , Ind Eng Chem Heat Evolution (or Liberation) in Explosives.
41, 2788 (1949) & CA 44, 2812 (1950) For a detonation to be self-sustaining the
3) 1. Nitta et al, Nippon Kagaku Zasshi, 71, detonating explosive must liberate a considerable
378 (1950) & CA 45, 6448 (1951). 4) J.J. amount of heat. If energy is lost to the
Engiesman, Ph D Thesis, Vrije Univ, Amsterdam, surroundings the detonation characteristics are
1955 5) L. M6dard & M. ~homas, MP 36, 97 altered, and if sufficient energy is lost the
(1954) & CA 50, 3763 (1956) 6) JANAF detonation fails. For a steady detonation, the
Thermochemical Tables, Dow Chemical Co, energy evolved in the detonation reactions
Midland, Mich, 1960 7) J. Timmermans, must obviously be greater than the energy
“Physico-Chemical Constants for Pure Organic lost to the surroundings
Compounds” Vol I & II, Elsevier, NY, 1960 [See Vol 4 of Encycl, under Detonation (and
& 1965 8) S. Marantz & G. Armstrong, J- Explosion), Heat of]
Chem Eng Data, 13, 118 (1968) & CA 68,
77594 (1968) 9) S. Marantz & G.T. Armstrong, Heat of Formation. See Vol 4 of Encycl under
J Chem Eng Data, 13, 455 (1968) 10) N.D. DETONATION (AND EXPLOSION), DEFLAG-
Lebedeva & V. I,. Ryadnenko, Russ J Phys- RATION (AND COMBUSTION), AND FOR-
Chem, 42 (9), 1225 (1968) & CA 69, 1“10602 MATION, HEATS OF & Tables 1 & 2 this
(1968) 11) R. Shaw, J Chem Eng Data 14, Vol
461, (1969) & CA 71, 129476 (1969)
12) D.R. Stun et al, “The Chemical Thermo- Heat of Fusion. See under Heat, Latent and
dynamics of Organic Compounds”, John Wiley Table 3 of this Vol
& Sons, NY, 1969 13) J.M. Rosen & C.
Dickenson, J Chem Eng Data, 14, 120 (1969) Heat of Hydration is the amount of heat
& CA 70, 94800 (1969) 14) S.W. Benson et absorbed or liberated when a substance combines
al, Chem Rev 69, 279 (1969) & CA 71, 33973 with water
‘(1969) 15) J.D. Cox & G. Pilcher, “Thermo-
dynamics of Organic and Organometallic Com- Heat, Latent (“Latent” means “lying hidden”
pounds” Academic Press, NY, 1970 16) C.H. or “not manifest”). It is the heat absorbed by
Shomate, NOTS, China Lake, Calif, private a substance without causing a rise in temp-
communication, 1970 17) E.S. Domalskl, Nat- erature
Bur Stds, Wash, DC, private communication, There are two kinds of latent heat:
1970 18) S.W. Benson & H.E. O’Neal, a) Latent heat of fusion is the amount of heat
“Kinetic Data on Gas-Phase Unimolecular necessary to transform (melt, fuse) a unit
Reactions”, NSRDS-NBS 21, Gov Printing quantity of solid into a liquid at the same
Office, Wash, DC, 1970 19) W.D. Good & temperature and standard pressure. Tables
R.T. Moore, J Chem Thermodynamics, 3, 701 usually express it in calories per gram
(1971) & 4, 709 (1972) & CA 76, 18689 b) Lutent heat of vaporization (or evaporation)
(1972) 20) R. Shaw, J Phys Chem 75, 4047 (L) is the quantity of heat required to convert
(1971) & CA 76, 18701 (1972) 21) H.K. a unit quantity of liquid to vapor at the same
Eigenmann et al, J Phys Chem 77, 1687 (1973) temperature. Tables usually express it in calories
22) R. Shaw, int J Chem Kinetics 5, 261 per gram. (L) can also be calculated, approxi-
(1973) 23) P.S. Engel & J.L. Wood, mately, by the Trouton’s rule: L = CT/M,
unpublished work, 1973 24) R.W. Woolfolk, where (C) is a constant equal to 21 for most
unpublished work 25) R. Shaw, Thermochem- liquids, (T) boiling point in absolute degrees
istry of Thiols, “Chemistry of the Thiol and (M) molecular ‘weight. Example: L for
Group”, S. Patai, ed, John Wdey, NY, 1973 acetone = 21 x (56 + 273)/58 = 120 cal/g
26) R. Shaw, Thermochemistry of Azo Com- against 124 actually measured
pounds, “Chemistry of Hydrazo, Azo, and Refs: 1) Marshall, 3 (1932), p 250 2) S.
AZOXY Groups”, S. Patai, ed, John Wiley, NY, Glasstone, Physical Chemistry, Van Nostrand
1974 NY (1940), pp 449 & 453 3) R.R. Wenner,
“Thermochemical Calculations”, McGraw-Hill,
NY (1943), pp 20-5
 Heat, Molecular is the amount of heat required Heat of Transition is the quantity of heat
to raise the temperature of one mol of a sub- liberated or absorbed when a substance changes
stance, 1‘C, ie, the specific heat of the sub- from one allotropic crystal form to another
stance multiplied by its molecular weight
Heat Tests. Under this term may be placed all
Heat Pulse. (Also Flash-Across,
see Detonation, the stability tests which involve heating an
Heat Pulse and Hypervelocity Phenomena in explosive, eg Abel Heat Test, Acidity Measure-
Vol 4, p D348-49). A concept advanced by ments (pH measurements), American Test at
M.A. Cook (Refs 1 & 2) to provide a theoretical 65.5° or 80°, Bergmann-Junk Test, Brame’s
mechanism for the shock initiation of explo- Test, Brunswig’s Test, Chiaraviglio & Corbino
sives. Cook also used the heat pulse concept in Test, Conductivity Method (De Bruin & de Pauw),
his explanation of certain unusual luminosity Continuous Test, Deflagration Test, Desmaroux
effects observed primarily in the detonation of Test, Dupr6’s Vacuum Test, Dutch Test,
liquid explosives. Briefly stated, Cook believes German 132° Test, Crottanelli’s Test, Guttmann
that detonation is initidted when as a result of Test, Haid, Becker & Dittmar Test, Hansen’s
rising temperature, produced by reaction in the Test, Hess Test, Hoitsema Test, Horn-Seifert
already shocked region of an explosive, a Test, International 75° Test, Jensen’s Test,
portion of the explosive becomes thermally Loss of Weight Test, Marqueyrol’s Test,
“super-conductive” and a “heat-pulse” flashes Meerscheidt-Hfi~ essem Test, Mittasch’s Test,
thru it and catches up with the shock front. Obermtiller’s Test, Pavlik’s Test, Methyi Violet
. Studies conducted by Kendrew & Whitbread Test, Silvered Vessel Test, Simon Thomas Test,
(Ref 3) tend to discount the necessity for Spica Test, Sy Test, Taliani Test, Taylor’s Test,
postulating ‘a “heat-pulse” in a theoretical Tomanari’s Test, Vacuum Stability Test, Vieille
explanation of shock initiation or the above Test, Warrnlagermethode 75° (German Storage
unusual luminosity effects. More recent studies Test), Will Test
of shock initiation have also failed to produce These tests are described separately in
any conclusive evidence of a “heat-pulse” alphabetical order
(Ref 4)
Refs: 1) Cook (1958) pp 83-89 & 164-166 Heat Value is the number of calories obtained
2) M.A. Cook et al, Proc Third Symposium on by the complete combustion of a unit weight
Deton (1960), pp 150-183 3) E.L. Kendrew of substance
and E.G. Whitbread, Ibid, pp 202-204 &
pp 574-583 4) Several papers on shock Heat of Vaporization. See under Heat, Latent
initiation in the Fifth Symp on Deton (1970)
Heath and Frost patented in 1877 the use of a
Heat Sensitization of Explosives and Memory water-retaining paste such as soap 5, starch 0.5,
Effect. See under Detonation, Heat Sensitiza- ghre 0.5 & water 94% for tamping bore-holes,
tion and Memory Effect in Vol 4, p D367-R loaded with dynamite, in order to prevent the
ignition of firedamp
Heat of Solidification. See Heat of Fusion Refi Daniel (1902), 371
under Heat, Latent
Hebler Powder or Wellite. Smokeless powder
Heat of Solution. Same as Heat of Dissolution used in Switzerland before the introduction of
NC smokeless powders. It contains KN03 62.3,
Heat of Sublimation is the number of calories NHq N03 15.8, charcoal 11“.5, sulfur 9.5,
required, in a constant temperature process, to moisture 0.9YL Use of this powder was aban-
convert a unit weight of solid directly into a doned because it is too hydroscopic
vapor Refs: 1) Daniel (1902), 371 2) Van Gelder
& Schlatter (1927) 782
Heat of Swelling is the heat evolved when a
colloid (eg gelatin, NC) absorbs a liquid (such
as HZO, acetone etc)
 H 60

Hecla Powder. American Dynamite con-

An nitrobenzene 25.81 carbon disulfide 6.45 and
taining 20 to 75% NG absorbed by wood pulp, aluminum bronze 3.Z3?0 was found to be one
sodium nitrate etc of the most effective. A mixture prepd by
Refi Daniel (1902), 371 dissolving 66.7 parts of Dinitrobenzene in 100
parts of fuming nitric acid was also claimed to
Hedgehog. A British antisubmarine device for be effective
projecting 24 spigot type projectiles equipped Refs: 1) Davis (1943), p 354 2) Thorpe’s
with contact fuzes. They contain approx 30 lbs Dictionary, v 4 (1940), p 545 3) A. Stettbacher
of HE each SS 38, 158 (1943) 4) A. Stettbacher, Spreng-
Refs: 1) B. Rowland & W. Boyd, US Navy und Schiesstoffe, Ziirich (1948),. p 71
Bureau of Ordnance in WWII, Bur of Oral, 5) PATR 2510, (1958), p Ger 87-R (See also
Dept “of the Navy (1953) 136 2) P. Eleson, Vol 6, under “Explosifs de Sprengel”)
Ordn 47, 610 (1963)
Hemellitene and Its Nitrated Compounds. See
under 1,2,3-Trimethylbenzene
HEI. Abbreviation for High Explosive Incendiary
Hemicelluloses (or Semi celluloses). A group of
Height of Burst of Ground Type Pyrotechnic gummy substances intermediate in composition
Signals, Determination. See under Position between cellulose and sugars. They are in-
Finders soluble in hot water but readily soluble in
dilute (4-5%) aqueous NaOH solutions. They
HEIT. Abbreviation for High Explosive are converted by warming with dilute acids
hcendiary Tracer (hydrolysis) at normal pressures into pentoses
and hexoses (with galactose and glucose pre-
Heliophanite. See under Panclastites dominating), whereas cellulose itself yields only
glucose (Ref 2)
Hellhoff Explosive. According to GerP12122 of According to Karrer (Ref 4) hernicelluloses
1880, it was prepared by the nitration of. comprise a series of c~mplex polysaccharides,
purified. tar oil, followed by washing, drying which like lichenin, occur as constituents of
and mixing of the nitrotar with oxygen carriers, the cell walls, as well as reserve substances,
such as K (or Na) nitrate (or chlorate), etc. lt occasionally becoming reconverted into sugar by
was claimed that this explosive mixture was the plant. On hydrolysis, many of them give
very powerful galact ose and mannose “in addition to glucose;
Ref See under Hellhoffit they are therefore known as galactans, mannans
etc. Whether these substances are true com-
Hellhoffit (Hellhoffite). One of the Sprengel pounds is very doubtful. Certain enzymes found
type explosives, invented about 1870 by Hell- in plants and in the intestinal tract convert
hoff and G&on. It consisted of 28 parts of them into sugars
nitrobenzene and 72 parts of fuming nitric acid. Dor6e (Ref 3) describes them as a poly -
This liquid was sometimes used absorbed on saccharides, which in their natural state are in-
kieselguhr (See Cuhrhellhoffit). The disadvantage soluble in boiling’ water, but readily soluble in
of these Sprengel type explosives was their dilute caustic and easily hydrolyzable on
extreme corrosiveness (Ref 1) warming with dilute acids
According to Thorpe (Ref 2), Hellhoffit was Hemicellulose may be divided into pentosans-
tried in shells, the two ingredients being mixed those yielding pentoses on hydrolysis, hexosans-
during flight & exploded on impact (see also those yielding hexoses and xylans- those
Anilithe under French explosives) yielding xyloses
Stettbacher (Refs 3 and 4) investigated The hernicelluloses give explosive compounds
Hellhoffit and its modifications and found that on nitration, but the yields are small and
the glass-lined depth charges (Tiefenbomben) stabilization difficult (Ref 1)
containing Hellhoffit, were much more effective Ref$: 1) N. Solechnik, J Applied Chem (USSR)
than those loaded with Picric Acid. The mixture 6, 93-8 (1933) & CA 27, 5964 (1933)
consisting of fuming nitric acid (d 1.52) 64.51, 2) Marsh & Wood, Cellulose (1945), 2 & 75
3) Dor6e (1947) 31 4) Karrer (1950), 357
 H 61

HEMP. A hydrodynamic code used for detona- Henrite. Brit 33 grain NC rifle powder manu-
tion product flow calculations. See Vol 4, p factured since 1900
D152 Refs: 1) Daniel (1902) 373 2) Marshall I, 326

Hemp Fiber (Chanvre in French). The bast-

HEO. Di(-hydroxyethyl) oxamide used in prepn
fiber obtained from the plant Cannabis indica
of Dinitrodi(-nitroxy ethyl) oxamide; see Diethylol-
or C sativa, which is a perennial herb (Ref 1).
oxanide in Vol 5, p D1243-R
The plant is native of western and central Asia,
but has long been cultivated in Brazil and
HEP. High Explosive, Plastic (HEP) is defined as
tropical Africa, and is now extensively culti-
vated in many countries. Its fiber is used for ammunition designed to defeat armor by
preparation of ropes and paper, but was also spalling or scabbing. Conventional HEP shells
proposed by Trench (Ref 2), in 1877 to be have thin walls, ogival noses, base fuzes, and
nitrated to an explosive large filler capacities
Refs: 1) Daniel (1902), 773 2) Webster’s The expl chge is base detonated upon
7th New Collegiate Diet (1969), 388 impinging on the target producing a high energy
impulsive load. The incident shock wave is re-
flected from the rear surface of the target as a
Hemp Nitrate (Nitrohemp) (In French Nitro-
tension wave. When the stress exceeds the
chanvre). Nitrohemp resembles cotton nitro-
critical fracture stress of the target, pa,rt of the
cellulose or nitrojute in its properties. It may
rear surface is “thrown off’ as a span
be prepared by nitrating hemp with mixed
Development of HEP ammo based upon this
nitric-sulfuric acid. Trench (Ref 2) proposed
principle was initiated in England during WWH
using it as a basic ingredient in commercial
after “wall buster” shell were found capable of
“explosives. Other components were collodion
scabbing armor. These shells were named HE/SH
cotton, resin, ozokerite, glycerin etc
(High Explosive/Squash Head) since they
Rej Daniel (1902), 773
“squash” against the target prior to deton of
the filler
Hemp Hurds. The refuse from hemp (stems of
cannabis sativa) fibers. A US patent claims their The US Army became interested in this
use as absorbents for liquid explosives such as method of defeating armor in 1947. Chamberlain
NG Corp, Waterloo, lows prepd in 1960 an
Refi A.S. Fox & F. Rape, USP 1979681 “Annotated Bibliography of HEP Information”
(1934) & CA 29, 346 (1935) which provides the first centralized source of
info on HEP ammunition
Hengstit (Hengstite). A smokeless powder Ref S.G. Smith, Editor, “State of the HEP
patented by Hengstin 1888 in Germany and Ammunition Art. Basic HEP Research and
France. IL was prepd from nitrated “strawpulp” Development Program,’; Chamberlain Corp,
by treatihg it first with potassium perman- Waterloo, Iowa Summary Rept (Ott 1960)
ganate and then with sodium carbonate. In (Contract DA-1 1-D22-501-ORD-2140)
order to render the mass cohesive and plastic
it was mixed with glue prepd by boiling Hept-RDX. See 1,3 ,5-Trinitro-l ,3,5 -triazacyclo-
‘\ crushed flaxseed with dextrin. Finally to this heptane listed under Triazacycloheptane
were added KN03, KC103 and ZnSOq
When intended for use as a military pro-
pellant, the mass was either granulated or HEPTANE AND DERIVATIVES
used in the form of fibers. When used as a Heptane, Dipropylmethane, Heptylhydride,
mining explosive, it was a plastic pressed CH3(CH2)5CH3; mw 100.23, colorless liq,
into boreholes mp -90.5°, bp 98.4°, flp 25”F, d 0.684 at 20°,
The same inventor proposed a propellant RI at 20°, 1.3876, insol w, sol org iolvs. Obtd
prepd by nitration of esparato grass (matweed) by fractional distillation of petroleum. Irri-
or of fibers covering coconut shells tating to respiratory tract; narcotic in large
Rej Daniel (1902), 373 cones. Dangerous when exposed to ht or flame
Refs: 1) Beil 1, 154 2) Sax (1968) 806
3) Cond Chem Diet 8th Ed (1971), 437
 H 62

Azidoheptanes, C7H15 N3: mw 141.25, N 29.75. , Prepd from 1,7-diodoheptane + AgONO in eth; the
The following derivs are described in Beil: decarboxylation of 2,8-dinitrononanedicarboxylic
l-Azido-heptane. N3CHC6H14 ; liq, bp 74° at acid (Ref 2)
18mm, d 0.868 at 20°, RI at 20°1.4343. Prepd Refs: 1) Beil 1, (57) 2) H. Feur & C. Savides
by action of NaN3 on l-chloro or l-iodo heptane USP 2963515 (1960) & CA 55, 20958 (1961)
(Ref 1)
3,5-Dinitroheptane. CZH5CH(N02)CH,CH(N0,)-
2-Azido-heptane. H3CCH(N3)C5 HI 1 ; liq, bp
65–66° at 20mm, d 0.862, RI 1.4323 at 20°. Prepd C2H5; needles (from MeOH), mp 33°, bp 115–1 16°
from 2-chloroheptane & NaN3; NaN3 + Hg(OAc)2 + at 3nlm, d 1.09, RI 1.4453 at 20 °(Ref 4). Prepd
l-heptane (Ref 2) by reaqting l-nitropropane with 2-nitro-a-butene
3-Azidoheptane, 3-Triazoheptane or 3-Heptyl- in ale; heating 1-nitropropane with paraformaldehyde
azide. ~ H5CH(N3)C4H9; liq, bp 79–810 at 43mm in presence of Et2NH; from 2-nitrobutene and K-salt of
(Ref 2), d 0.858 at 25°, RI at 25°1.4298 (Ref 3); l-nitropropane in alc soln at 10° (Ref 4);
AHfO = –29kcal/mole (Ref 4) prepd in sealed tube EtCH(NOz)CHzOAc in MeOH, HZO, NaOH soln
reaction of 3-iodoheptane with NaN3 in aq MeOH reactd with PrNO & Triton-B catalyst (Ref 2)
(Ref 2) Refs: 1) Beil 1 t434 } <396> 2) G.L.
Refs: 1) Beil 1 {434} <396> 2) P. Levene Shoemaker & R.W. Keown, JACS 76, 6374
et al, J Biol .Chem 120, 759 (1937) & CA 32, (1954) & CA 49, 15891 (1955) 3) H. Feiver
487 (1938) 3) P. Levene & A. Rothen, J & R. Miller, JOC 26, 1348 (1961) & CA 56,
Chern Phys 5, 985 (1937) & CA 32, 1151 1334 (1962) 4) V.P. Tsybasov & V.F. Petrovich
(1938) 4) J.W. Murrin & G.A. Carpenter, Mem- Izv Vyss Uchebrr Zav Khim i Khim Techn 5,
Rept No 129, US Nav. Powd Fact, Feb 1957 942 (1962) & CA 59, 3756 (1963)
2,4-Dinitroheptane. H3CCH(N02)CH2CH(N02).
4–Azidoheptane. (C3H7)2CH(N3); liq, bp 64–
65° at 20mm, d 0.864 at 20°, RI 1.4327 at 20°. C4H9; bp98°at 3mm, d l.10at 20”, RI 1.4482at
Prepd from 4-chloro-heptane + NaN3 20°. From 2-nitropropane and K-salt of 1-nitro-
butene in alc at 10°
Refs: “1) Beil 1 <396 & 397> 2) C.H.
Refi V.P. Tsybasov & V.F. ‘Petrovich lzvVysS-
Heathcock, Angew Chem Intn Ed 8, (2), 134
UchebnZavKhim i KhimTechn 5,,942 (1962)
(1969) & CA 70, 86930 (1969)
& CA 59, 3756 (1963)
1,7 Diazidoheptane (called Heptandiyidiazid in
Heptanedinitrile, 4,4-Dinitro or 4,4-Dinitro-
Ger). N3(CH2)7N3; mw 182.27, N 46.12%; li~ pimelonitrile. CN(CHZ)3C(N02)2 (CHZ)3CN;
bp 116° at 5mm, RI 1.4700 at 20°. Prepd from
mw 240.25, N 2333Yo; tryst, mp 79°. Prepd from
1,7-Dibromoheptane + NaN3 HC(N02)2 :N02K & CH2 :CHCN in water at 35–4s0
Ref’ Beil 1 <397> (Ref 1); or (N02),C(CH,0H)2 & CH,:CHCN in
Many nit ro and nitroso derivatives are also aq KOH (Ref 2). Claimed as an ingredient in
known:
rocket propellant charges (Ref 3)
4-Nitroso-4-nitroheptane. H3C(CH2)C(NOz)NO-
Refs: 1) L. Herzog et al, JACS 73, 749 (1951)
(CHZ)2CH3; mw 160.20, N 1749%,rh trysts,
& CA 45, 5609 (1951) 2) H. Fever & S.M.
mp 72-73° with decomp, S1sol in eth. Prepd
Pier, JACS 76, 105 (1954) & CA 49, 2313
from C3H7C:NOH + N02 in cold eth in dark.
(1955) 3) M.H. Gold & L. Herzog USP
Oxidation with Cr03 in HAC gives 4,4-dinitro- 2918489 (1959) & CA 54, 8637 (1960)
heptane. No expl props mentioned for either
Ref Beil 1, 156
Dinitroheptanes, C ,H14(NO*)’2, mw 190.23, N Trinitroheptanes, C7HIs (N02)3, mw 235.23, N
14.73%. The following derivs are known: 17.87%, ob to C02 –9,8.6%. The following isomers
1,2-Dinitroheptane. (N02)2CHC6H1 ~; liq, bp are known:
810 at 1 mm, d 1.091 at 20°, RI 1.4432 at 20°. 1,1,1-Trinitroheptane, (02 N) SCC6H1S; liq, bp
Prepd by reacting 2-hexylacetoacetic acid–Et 80°, d 1.212 at 20°, RI 1.4482 at 2(P. Prepd from
ester with aq nitric acid C6H13 I + AgC(N02)3 in MeCN
Ret Beil 1, <396> Refs: 1) Beil, not found 2) G.S. Hammond et al,
1, 7-Dinitroheptane. 02 NC7H1 ~ N02; pale yellow Tetrahedron 19, Suppl 1, 185 (1963)&CA 59,
liq, bp 198–200°at lornm, RI 1.458 at 20 °(Ref 2). 11237 (1963)
 H 63

3,3,5-Trinitroheptane. C2H~C(N02)2CH2CH- Re~s: 1) BeiL not found 2) M.B. Frankel &

L.T. Carleton, Aerojet-Engineering Corp Rep 4,
(N02)C2H5; liq, bp 108–1 10° at 0.005 mm, RI-
No 499, March 1951, Explosive Research –
1.4685 at 250. Prepd by heating 1,1.dinit ropro-
cent’d N7 onr 46208 3) D.V. Sickman & W.F.
pane in a soln of 2-nitrobutylacetate in MeOH,
Sagerj NAYORD Rept 486, (1954) Res & Devel in
w & NaOH at 40–45” for 2 hrs. Claimed to be a
high explosive N> Chemical High Explosives 4) George
Note: Among the polynitroheptanes this is Washington Univ, Rep 4 Nos. 14, 15 and 16 on
the only found reference to their being ex-, Con’t NORD 9951, Task No 3 5) M.B.
plosive Frankel & K. Klager USP 3139461 (1964) &
CA 61, 5517 (1964) 6) K. Klager & M.B.
Refs: 1) Beil, not found 2) K. Klager, USP Frankel, Monatsh Chem 99 (5), 1438 (1968) &
3000968 (1961) &CA 56,3715 (1962)
CA 69, 95857 (1968)
2,6-Dichloro-2,4,6-trinitroheptane. CH3CCl(NOz)- Heptanedioic Acid, 4,4-Dinitro also called 4,4-
C~CH(NOz)CHzCCl(NOz)CH3; mw 304.11, N Dinitropimelicacid. [HOOCC2H4C(N0,),] ~;
13.82%; tryst, mp 73–1 19°. Prepd by adding the mw 354.22, N 15.82%; tryst, mp 137°. Obtd
product of reaction of aq base & C1CH2CHZN02 from its di-methylester, by refluxing with
to a soln of 2-nitroallylacetate in CH2C12 and HC1, which is formed by reaction of HC(N02):
heating 3 hrs at 53°. Further chlorination with N02K and CH2:CHC02Me in water (Ref 1). It
Clz in basic MeOH gave the 2,4,6-trich/oro- is claimed to be useful in propellant composi-
2,4,6-trinitroh eptane tions (Ref 2)
Refs: 1) Beil, not found 2) M.B. Frankel et al, Refs: 1) Beil, not found 2) L. Herzog et al,
USP 3440282 (1969)&CA 71,91105 (1969) JACS 73,749 (1951)&CA 45,5609 (1951)
3) USP 2918489 (1960)&CA 54,8638 (1960)
Tetranitro derivs were not found in the literature

CH3C(N02)2CH2-
2,2,4,6,6-Pentanitroheptane. N,2,2,2,2’,2’,2’-Heptanitrodiethylamine. Designated
CH(NOZ)CHZC(NC) 2)2CH3;mw 325.23, N 21 .54%, as HOX, also called Bls-2,2,2-trinitroethyl-
nitrazine or Bis(2,2,2-trinitroethy l)-nitrazine,
OB to C02 Prepd by reacting 2-nitro-3-
–46.7%.
abbr as BTNEN. It is listed as an expl deriv of
acetoxy- l-propene with 1,1.dinit roethane
Diethylamine in Vol 5, p D1224-R
Refs: 1) Beil, not found 2) M.B. Frankel, Tet
19, Suppl 1,215 (1963) &CA 59, 11236 (1963)
Heptanitrohydrocellulose. See under Hydro-
cellulose in this Vol
Hexanitroheptanes, C7HIO(N02)6; mw 370.23,
N 22.’)WO, OB to C02 –30.2%. The following Heptanoic Acid and Derivatives
isomers are known: Heptanoic Acid or Enanthic Acid. CH3(CH2)5 -
1,1,3,3,5,5-Hexanitroheptane. (OzN)zCHCHzC- COOH; mw 130.21, colorless, oily Iiq, mp – 1.OO,
(N0,),CH,C(N0,)2 C,H5. Claimed to be a bp 223.5°, d 0.913 at 25°, RI 1.4216 at 20°; S1
burning rate accelerator for rocket fuels; no prepn sol in water; sol in alc &’ eth. Prepd by oxidi-
given in CA zing heptanal with bichromate & sulfuric acid.
Refs: 1) Beil, not found 2) M.B. Frankel, USP Low toxicity and flammability. Used in
3000970 (1961) &CA 56,4618 (1962) organic synth & production of special lubri-
2,2,4,4,6,6-Hexanitroheptane. CH3C(N02)2CH2- cants & brake fluid for aircraft
C(N02)2CH2C(N02 )2CH3; trysts, mp 132°, d Refs: 1) Beil 2,338, (144), [294] & {762}
1.70. Prepd from 2,2,4,6,6-pentanitroheptane 2) CondChemDict, 8th Edit (1971), p 437
K-salt & N204 in CC14at–15 to –25° for 4 hrs; The following nitro deriv is described in the
or by nitric acid nitration of the pentanitroheptane literature:
(Refs 4 & 5); also from MeNH2 & dichlorotetra- 4,6,6-Trinitroheptanoic acid, Me ester. MeoOC-
nitroethane (Ref 2). Its hot bar ignition temp is (CH,),CH(NO,)CHZC(NO, ),CH,; mw 279.24,
338° & its sensitivity is approx that of pentolite N 15.05%; needles (from eth), mp 56°. Prepd from
(Refs 3 & 4) 4-nitro-4-pentanoate + MeCH(N02)2 + NaOMe
 H 64

in MeOH at 40-45°; no explosive props are Heracline. British explosive (1875), containing
mentioned, but it must be expl about equal amounts of each of the following
Refs: 1) Beil, not found 2) K. Klager, JOC compounds: KN03, NaN03, sulfur and saw--
20, 650 (1956) & CA 50, 8576 (1956) dust, to which was added about 0.5% of Picric
3) E.E. Hamel, Tetrahedron 19, Suppl 1, 85 Acid
(1963) & CA 59, 11228 (1963) Rejl Daniel (1902), 373

Heptanone and Derivatives Heraklin (Ger). An expl patented by Dickerhoff,

4-Heptanone, Dipropylketone or Butyrone. was prepared by soaking sawdust in a coned
(C3H7)2~O; mw 114.21; colorless liq, mp aqueous soln of equal parts of Picric Acid &
–32.6°, bp 144°, fl p 120°, d 0.817 at 20°, RI Amm nitrate. The resulting product was dried
1.4073 at 20°; insol in water, sol in alc & eth. and mixed with various amts of pulverized
Toxicity undetermined; moderate fire hazard; sulfur and K or Na ‘nitrate
used as a solvent and in poly.mers”& resins Refs: 1) Cody (1907), 551 2) PATR 2510,
Refs: 1) Beil, Dinitro, ClHIzN205, Trinitro, (1958), Ger 88-1
C7H1 ~N307, Tetranitro, C7H10N409, and
Pentanitro, CTH9N501 ~ , derivs were not found Hercoblastings. (C~led Kamrnerminensprengungen
2) CondChemDict, 8th Edit (1971), p 325 in Ger and Cifmaras de mina in Spah). In this
1,1,1 ,7,7,7-Hexanitro-4-heptanone. (N02)3C-
method which might be translated as Chamber
Mines Blasting, a large area consisting of the
(CH,),C0(CH2),C(N0, )3; mw 384.21, N
material to be mined is selected and horizontal
21 .88%, OB to C02 –20.8%; wht trysts (from
tunnels are drilled under it, deep,.in the ground.
aq MeOH), mp 1210. Prepd by heating Then charges of explosives are placed in the
(H2C:CH)2C0 with HC(N02)3. Explodes with tunnel, as shown, for example in Figs 259 &
hammer biow
260 copied from Ref 1, p 388. The layout of
Refs: 1) 13eil not found 2) P.O. Tawney..USP
3038011 (1962)”& CA 57, 7512 (1963) the’ Figs is for a basalt quarry blasting
3) M.. Graff & W. Gilligan, JOC 33, 124,7 conducted in 1931 in Pfalz, Germany. All
(1968) & CA 68, 77654 (1968) the shown charges were exploded simultaneously
This method also proved to be popular in
Heptryl. See 2-(2’,4’,6’-Trinitro-N-nitranilino)- blasting old asphalt or macadam pavements,
2-nitrotymethyl-l ,3-di-nitroxypropane under where in order to obtain large pieces of mater-
2-Anilino-2-hyd roxym&hyl- 1,3-dihydroxy- ial, expls of low detonation velocity and large
propane in Vol 1, p 1A441
See ADDENDUM, p III in this Vol

.:,,,
I
f
!,
‘

x’
Lugep/an r:250 SChlf duru$’diw Dngungssfolleq t230
Abb 259 Abb 260
Abb 259 und 260. Kammerrninensprengung in Basaltgestein mit insgesamt 5300 kg
Armnonit 1 und Ammongelatine 1 im Verh~ltnis 4:1
 H 65

volume of gases produced on expln should be “A” Blasting and Sporting Powder Mills
used. When blasting hard rock, expls with high
deton velocity shorAd be selected Hazardville, Corm
In Refs 2 & 3 it is suggested that for Valley Falls, NY
blasting hard rock, tunnels can be dug deep
underground and the charges are uranium- Black Powder mills began operating as early
plutonium atomic, devices instead of conven- as 1843 and the dynamite plants began opera-
tional explosives tions in about 1872, producing explosives for
Re~s:l) Stettbacher (1933), 397-88 2) Stett- the iron, copper, gold, silver, and anthracite
bacher (1948), 168 3) Stettbacher, P61voras coal industries. During the intervening years
(1952), 212 between the 1870’s and founding of Hercules
Powder Company in 1912, many advancements
Hercules Incorporated. Hercules Incorporated, in products and process technology had taken
known as Hercules Powder Co prior to 1966, a place. Low-freezing Nitroglycerin was known,
diversified, world-wide chemical company with gelatin dynamite was a commercial product, the
estimated annual sales of about $1 billion in use of active “dope” (sodium nitrate, coal,
1973, began its corporate history on October sulfur, rosin) was common. Ammonium Nitrate
17, 1912. On that date, a decree of the federal dynamite (extra dynamite) was also an
court, under the Sherman Act, ordered the important product. The importance of safety in
dissolution of the E.I. duPont de Nemours and coal mining had been recognized and use of
Company, and a regrouping of the properties hydrated cooling salts such as sodium carbonate,
into the same company plus two new corpora- or. magnesium sulfate had begun. Equipment
tions. Hercules Powder Company and the Atlas for manufacture of dynamite such as the Talley
Powder Company were the new corporations mixer, and the Hall packing machine were
(Ref 3) operational. In principle at least, this equip-
The name Hercules Powder was originally ment design is still in use today
given to a dynamite manufactured by the In addition to dynamite manufacture, the
California Powder Works as long ago as 1870 Kenvil plant was equipped shortly after the
(Ref 1). This was obviously done with the assignment to Hercules to manufacture about
object of comparing the strength of the 1500 lbs/day of smokeless shotgun and rifle
dynamite to that of the mythological Hercules. powder. The brands which became Hercules
Later, there existed a Hercules Powder Company, property included Bullseye* and Unique*.
formed by Lammot duPont in 1882. It oper- These brands still exist today
ated two dynamite plants whose operations In 1914 the. Independent Powder Company
were assumed by others, and its charter was of Missouri was acquired, with its dynamite
cancelled in 1904. This historic name, and the plant near Joplin, Missouri
brand name of the principal dynamite assigned In 1914’-1915 a new dynamite and black
to the new company were influential in the blasting powder plant was constructed and
chosen name Hercules Powder Company began operation at Bacchus, Utah
At the opening of business on January 1, During the years of World War 1 the Kenvil
1913, Hercules Powder Company, incorporated and Hercules plants were equipped to manu-
in Delaware, began with nine black powder facture TNT. Capacity eventually reached
pills and two active dynamite plants: 7,000,000 lbs/month. In addition, Hercules
operated the Nitro, West Virginia smokeless
Black Blasting Powder Mills Dynamite Plants
powder plant for a short time. The Union
Rosendale, NY Kenvil, NJ plant in Gillespie, N J,, was also acquired by
Ringtown, PA (2 milk.) Hercules, Calif Hercules for production of smokeless propellant
Youngstown, Ohio and later, for manufacture of nitrocellulose for
Pleasant Prairie, Wis dynamites and lacquer as well. Total Hercules
Columbus, Kansas production of smokeless propellant during World
Santa Cruz, Calif War 1 was over 100,000,000 lbs. h addition,
 H 66

A gaslessdelay fuse which did not require and mortars. In addition Hercules operated the “
. venting was developed for electric caps. This new New River bag loading plant, and Volunteer
design improved, water resistance and helped TNT plant. Hercules continued as the con-
prevent misfires or burning of the explosive tractor for Radford and Sunflower after the
charge. [n addition, semi-gelatin, permissible, war, and in addition, assumed responsibility
dynamites containing sodium chloride as a for the operation of the Allegany Ballistics
coolant were developed. A broader range of Laboratory for the Navy. Propellant charges
Hercomite* brands of low-cost ammonium for such operational missiles as Nike, Honest
nitrate dynamites was introduced. The practice John, Little John, Tales, Terrier, and Rat
of seismic exploration required explosives with were designed and developed at ABL (Ref 4)
reliable performance after exposure to high In about 1953, ANFO (ammonium nitrate
water pressures for long periods of time, and so and fuel oil) figuratively exploded on the scene
the Vibrogel* seismic gelatins were developed. of the blasting industry. The market for large
Red Dot* smokeless shotgun powder was first diameter, low cost dynamites was rapidly
used, and has been used by champions in trap taken over by the even lower cost ANFO.
and skeet shooting ever since Hercules and other explosives suppliers faced a
In the late 30’s and early 40’s blasting caps diminishing dynamite market, and excess capa-
for seismic use, were developed wl-ich enabled city. Hercules Black Powder plants had all been
the user to determine to within a few tenths of closed by this time” due to lack of a market,
milliseconds the instant of detonation by and dynamite came under pressures of excess
monitoring the cap circuit. These caps were capacity. However, innovations in explosi~es had
named Vibrocaps*. Dynamite packaging not yet ceased. In the early 50’s, Hercules intro-
improvements also followed. Long lengths of duced long-length small diameter dynamite
thick paper cartridges were developed to enable cartridges (king-size) for improved economy in
them to be threaded, or screwed together to loading into boreholes. Hercules patented the
improve loading into the borehole. This was equipment design for packaging such long
Hercules patented Spiralok*. In addition, the lengths and demand for these products has
paper shell for other dynamites was improved continued. Improvements in static resistance of
so that it could be loaded into boreholes and blasting caps were introduced as Vibrocap SR*
then expanded without previously having been in the mid 50’s. Vibronite B* was introduced
slit with a knife. This so called Tamptite* for a high volume, but short-lived history in off-
method of shooting resulted in better perfor- shore seismic operations. lt is a blasting agent
mance due to better coupling of the explosive packaged in metal cans to withstand ~e rigors
in the borehole to the media to be blasted and of handling storage and use in offshore seismic
had the additional advantage of making the operations
loading operation safer for the miner. Currently Vibrocol*, long length (ca 65 ft or more),
plastic shells have replaced Spiralok in seismic pre-packaged columnar charges of explosives
use were especially suited for some land seismic
In World War II Hercules was called upon to exploration. Low-priced, packaged blasting
conduct research programs to develop new types agents, Dynatex* and Tritex* were usefd in
of ordnance, particularly propellants for guns wet locations where ANFO could not be used
and rockets. The first bazooka propellant grains The Chemical Propulsion Division of Hercules
were extruded at the Kenvil plant, and many was formed in 1958, and began construction of
other propellant processing and application a major facility for design development and
improvements followed. Hercules designed, manufacture of large rockets and propellants at
constructed and operated Radford Arsenal, and the Bacchus, Utah plant. in 1958 Hercules
Sunflower and Badger Ordnance Works for the acquired the design, development, and prtiduc-
U.S. Government. These plants turned out all tion facilities of Young Development Labora-
the rocket propellants fired by U.S. Forces tories of Rocky Hill, N J. The filament-wound, -
during .World War. 11, as well as a substantial glass fiber-reinforced plastic Spiralloy* structures
portion of the conventional propellants for guns
*Indicates registered trademark
 H 67

operations for manufacture of acetic acid and the Polaris and Poseidon Systems
acetone were conducted In 1958 Hercules began producing Nz OQ,
In 1921 Hercules last major acquisition in most of which has been used by the Air Force
the explosives business was Aetna Explosives and NASA as an oxidizer in liquid propulsion
Company. With this acquisition came the systems
following active plants: In the late 1950’s and early 1960’s the
Emporium, Pa – Dynamite entire explosives industry was intensively
Ishpeming, Mich – Dynamite working on a new explosive system, which has
Birmingham, Ala – Dynamite & black powder since become known as water-gel or aqueous
Goes, Ohio – Black powder slurry explosives. Hercules was among the
Port Ewen, NY – Blasting caps leaders in innovation and promotion of water
Prescott, Ontario – Fulminate gels. Packaged Flogel*, an aqueous solution of
Electric blasting caps as well as regular oxidizing salts sensitized with smokeless powder
blasting caps were added to the Hercules pro- became a forerunner of many such products.
duct line with the Aetna acquisition. The The product was packaged in plastic bags. It
plant at Port Ewen, NY had been in operation found ready acceptance on the Iron Ranges of
since 1913. The features of the electric caps Minnesota and Michigan where jet-pierced bore-
which were manufactured at Port Ewen included holes co~ld now be completely filled with this
the insulated wires, copper shell, a base charge gelled explosive, to improve the blasting per-
@ressed fulminate) an electrical heater (bridge formance. The economy, water resistance, and
wire), primer (loose fulminate), plug, water- safety of these water gel systems were a
proofing, and sulfur seal. These caps were significant marketing attraction. Early in the
intended to fire instantaneously when electric 1960’s, Hercules also began to supply water
current was applied. By 1927 delay electric gels in bulk trucks, pumped directly into the
caps had been developed at Port Ewen, and borehole, and due to the added savings in labor
were commercially available (Ref .2). The design costs, the use of this concept rapidly accelerated
of the delay fuse required venting of the delay nationwide
element A highly significant technological improve-
In its first 25 years, (ie from 1912 to 1937) ment in blasting technique, called pre-splitting,
Hercules Powder Company introduced many using dynamite was introduced by Hercules in
additional innovations. In 1929 Hercules 1961. Through the use of precise drilling and
Powder Company introduced a patented semi- special blasting procedures this technique could
gelatin dynamite called Gelamite*. It was an produce very precise shearing to improve the
advance in the art due to its ability to replace appearance & durability of the remaining rock,
gelatin dynamites where extreme water resistance and the economy of construction blasts. This
was not required, with substantial cost savings. has become a standard technique where over-
produced at Rocky Hill proved to be of great break is undesirable, and is widely used in
importance for rocket cases, motor housings, highway construction
nose cones, and fuel tanks because of their In the late 1960’s Hercules water-gel explo-
strength and light weight. From this beginning, sives were being used nationwide in bulk opera-
Hercules developed the Spiralloy* rocket cases tions and packaged products. Slurrex” was a
into production scale rockets. Along with the Hercules patented method of gasifying water
cases, Hercules high energy propellants achieved gels to produce improved performance due to
a breakthrough in mass fraction for high per- increased sensitivity and energy output
formance space motors and upper stages of SuperSeis* a patented explosive system for
ballistic missiles. The Minute Man missile system offshoie seismic exploration, jointly developed
was one of major importance to the nation and by Hercules and Western Geophysical Company,
to Hercules Chemical Propulsion Division in became operational in 1971. It consists of
these early days. Following the success of the small explosive charges that are ejected from
Minute Man, Hercules has also dope significant the exploration boat via a long pressured tube
design, development and production work on and detonate after an appropriate delay, at
 H 68

water depths of ca 40 feet. Because these from 25 through 500 milliseconds. Firing
charges are percussion initiated they are safer times are printed on blasting cap shell as posi-
than the conventional electrically initiated tive and permanent identification of delay. In
seismic charges (Ref 5) addition, Coaldet electric blasting caps are
The product outlook for the future includes furnished with water-resistant tags that display
the Trident 1, C-4 underseas long-range missile, the delay number in easy-to-see numerals and
which is a joint effort of Hercules and Thiokol leg wire insulation is color-coded in a brillant,
Chemical Corporation. The work is carried on high gloss that is color-distinguishable in an
at the Bacchus and ABL facilities. In addition underground coal mine environment. AU Coaldet
work continues on Polaris and Poseidon blasting caps have iron leg wires for magnetic
missiles, land-based minuteman missiles and removal and all conform to the U S Bureau of
other rockets. Advanced composites are finding Mines permissible recommendations
increasing use in structural applications re- Instadet*: bronze shell No 6 strength, static-
quiring high strength and modulus with minimum resistant, waterproof, instantaneous initiators
weight. Explosives water-gel products will pro- for explosives set off by an electric current.
bably accelerate “in market acceptance and use Available with various length leg wires of
because of increased safety in handling and copper or iron as required
shipping. Their future use in small cartridges to Millidet*: bronze or aluminum shell No 8
replace NC dynamites is likely to increase strength, static-resistant, waterproof, milli-
The third 25-year span of Hercules explo- second delay electric blasting caps with delay
sives, smokeless powder and propulsion activities elements supplying 18 controlled (O to 17
is continuing with the following principal periods) firing times from 12 to 700 milli-
manufacturing facilities: seconds with no overlapping of delay periods.
Bacchus, Utah – Propellants; rockets Available with various length leg wires of
Bessemer, Ala – Dynamite, nitric acid, PETN, copper or iron as required
water gel Superdet*: No 8 strength bronze or aluminum
Cdrthage, Mo – Dynamite, water gel shell static-resistant, waterproof, approximately
Donora, Pa – Ammonium nitrate, nitric acid ‘A-second delay electric blasting caps with
Hercules, Cal – NzOq nitric acid, ammonium delay elements supplying 19 coritrolled (O to
nitrate 15 periods plus %, %, and % fractional delay
Ishpeming, Mich – Water gel periods) firing times from 12 milliseconds to
Kenvil, N J – Smokeless powder, diazo 15.6 seconds with no overlapping of delay
Louisiana, Mo – Ammonium nitrate, nitric acid periods. Available with various length leg wires
Parlin, N J – Nitrocellulose of copper or iron as required
Port Ewen, N Y – Detonators, initiators Vibrodet* SR: static-resistant, No 8 strength
Rocket Center, W Va – Propellants E B. caps designed to meet the requirements
Radford, Va – Government owned, company of the seismographic industry for a high-
operated quality, no time lag, waterproof E.B. cap.
Sunflower, Kansas – Government owned, Vibrodet SR WW is a self-disarming Vibrodet
company operated SR designed for offshore blasting work. Vibrodet
which manufacture the following products: types are available with copper leg wires only
BLASTING CAPS BOOSTERS
No 6 Strength Initiators: aluminum shell No. 6 Titan* Booster 25, 150, 225, 350, 500, and
strength init~ators for explosives set off from 2500: high-strength, relatively insensitive ex-
the spit by the safety fuse plosive initiators designed for use with
ELECTRIC BLASTING CAPS commercial explosives, slurries, and blasting
Coaldet*: copper-bronze alloy shell, static- agents. The Titan Booster 25XT is a specially
resistant, waterproof, millisecond delay electric designed, self-disarming booster for offshore
blasting caps designed especially for use in the seismographic work
coal mining industry. Available in eight accu- The self-disarming Titan Booster 25XT and
rately timed delays with nominal firing times Vibrodet SR WW, aimed at eliminating the
 H 69

possibility of primed offshore blasting charges Blasting Gelatin Hercomite*

being washed ashore, have proved very effective Ditching Dynamite Hereon*
and, as safety devices, were quickly adopted Extra Dynamite Hercosplit
by the offshore seismic industry Gin-Well Explosives High-Pressure Gelatin
DETONATING CORD Gelamite* Nitroglycerin
Detonating Cord: core of pentaerythritol tetra- Gelatin Dynamites
nitrate (PETN) contained within a waterproof Gelatin Extra Oil-Well Explosives
covering of textile or plastic; available in ‘ Hercol* Stumping Dynamite
several grades, each on spools of 500 or 1,000 Unigel
feet. Manufactured by the Ensign-Bickford Permissible Dynamites:. Nit roglycerin-based ex-
Company, Coast Fuse, Inc and Austin Powder plosives tested and approved by the U S
Company Bureau of Mines as safe for use in blasting in
SAFETY FUSE gaseous and dusty coal mines, provided they
Safety Fuse: internal burning fuse with black are stored and used in accordance with condi-
powder core for conducting flame from collar tions established by the Bureau of Mines:
of blasthole to blasting cap or to black Collier-C* Red H C
powder charge. Hercules Incorporated markets Hercogel*-A Red H D
various grades manufactured by The Ensign- Red H*A Red H F
Bickford Company and Coast Fuse, Inc Red H B Red H L
BLASTING MACHINES Seismograph-Grade Explosives: for use in
Condenser-Discharge Type:Hercules Incorporated seismic prospecting on land and offshore.
markets five condenser-discharge blasting Various grades are available in diameters from
machines: VME 450, VME 225 Blasters: manu- 2 to 8 inches packaged in fiber cartridges,
factured by Vibration Measurement Engineers, metal cans, or plastic:
Inc., Evanston, 111 60204 Gelamite S Vibrogel 5
Hercules Permissible 20-Shot Blaster: manu- Vibrocol* Vibronite* S Primer
factured by Femco, Inc , Irwin, Pa 15642 Vibrogel* 3
SD-SO, SD-100: manufactured by Safety BLASTING AGENTS
Devices, 650.5 Lignum Street, Springfield, Va Ammonium Nitrate Prill and Fuel Oil Mixtures
22150 (AN/FO): available in 50- and 80-pound multi-
Generator-Type: manually operated electric wall paper bags, packages from 5 to 12 inches
generators for initiating electric caps. Four in diameter, and in bulk deliveries to field
styles: two 10-cap, a 30-cap, and a 50-cap storage bins or direct to the blasthole:
machine manufactured by Fidelity Electric Freemix 3 Hercomix 1-4
Company, Lancaster, Pa 17604, for Hercules Freemix 33 Hercomix T
Incorporated Hercomix*
SQUIBS Nitro Carbo Nitrate Blasting Agents: a series of
Electric Squibs: means for initiating black “ low-cost blasting products containing no “high
powder electrically; supplied with leg wires of explosives” ingredients. They have limited
4- and 6-foot lerigths water resistance and are available in varying
BLASTING ACCESSORIES cartridge strengths and packages with diameters
Blasting cap crimpers, blasting galvanometers, of 3 inches and up:
connecting wire, explosives magazines, fuse Dynatex* Tritex* 2
lighters, Ignitacord* and Quarrycord * Dynatex WR
connectors, leading wire, detonating cord clips Seismograph-Grade Blasting Agents:
and connectors, Quarry cord, rheostats, tamping Vibronite B Vibronite” S
bags, and V A O blasting meters Vibronite B High Vibronite S-1
EXPLOSIVES Energy
Nitroglycerin Dynamites: in cartridges ranging Super AN/FO: ammonium nitrate and fuel oil
from 7/8 to “8-inch diameter with varying mixtures with metal additives to obtain
weight strengths: increased strength. Super AN/FO is available
in packages or can be delivered direct to the
blasthole in bulk form
 H 70

BLASTING AGENT INGREDIENTS Must be detonated by adequate-strength Titan

Herco-Prills*: ammonium nitrate prills designed Boosters. Available in various grades in either
for use with No 2 diesel fuel oil to produce a polyethylene bags or bulk, both of which offer
nitro carbo nitrate blasting agent. Herco-Prills the Slurrex blasting technique
are readily absorbent, nonsetting, and offer PROPELLANTS
excellent fuel oil absorbency. Available in bulk, GRANULATED DOUBLE-BASE TYPES
and in 50- or 80-pound multiwall, moisture- (for use in guns)
resistant bags Blue Dot*: a premium powder designed especially
SLURRY BLASTING MATERIALS for magnum shotshell loads
Slurrex: is a major technological breakthrough Bullseye*: for use in loading pistol and revolver
by Hercules in blasting with slurry explosives. cartridges
Developed through the Hercules Energy Green Dot*: designed for use in medium shot-
Management concept, Slurrex provides a varying- shell loads for all gauges, also some revolver and
density technique to any slurry formula for pistol loads
obtaining a precise amount of volume energy in Herco*: coarse grain, for use in heavy and
the borehole. This is caused by the injection magnum shotshell loads, also some revolver and
of a chemical reagent at the time of bulk pistol loads
loading or packaging. This chemical reagent Hercules Red Dot*: especially suited for use in
provides millions of tiny gas bubbles that act light and standard shotshell loads in all gauges,
as “hot spots,” or initiating surfaces, to also some revolver and pistol loads
improve the efficiency of the detonation Hercules 2400*: progressive-burning; for use in
reaction. Hercules is able to design very pre- small-capacity center-fire rifle cartridges, for
cisely a formula for maximum energy and reduced loads in larger capacity rifle cartridges,
then vary the volume energy with no signi- for 410-gauge shotshells, and high-velocity loads
ficant formula change. As an example of the in some revolvers
value of this dnergy control, Hercules is able HiTemp*: for use in oil-well perforator guns
to provide any level of measured volume energy when exposure to high temperature is important
from 50 million to 110 million ft-lbs/cu ft. Military Propellants: a wide variety of composi-
The Slurrex technique is usually applied to tions for standard or special applications
produce the maximum measured energy at the Unique*: an all-around propellant for use in
bottom of the hole. There the gas bubbles, or ,pistol and revolver cartridges, light or gallery
“hot spots,” are more highly compressed than rifle loads, and light through heavy shotshell
they are at the top—hence, an optimum loads
energy and density result, where these factors ELECTRIC INITIATORS, EXPLOSIVE
are most needed. Each succeeding foot up the DEVICES, ASSEMBLIES, SUBSYSTEMS,
borehole has a different energy level, and this Actuators Gas generators
directly meets the blast requirements at each Bellows motors Igniters
horizon on the face. This patented technique, Blasting caps Indicators for EEDs
exclusive with Hercules, can be applied to any Blasting supplies Piston actuators
of its slurry products Bolts, explosive Primers
Nitro Carbo Nitrate (NCN) Slurries: plastic, Boosters Safe and arm
water-resistant products that consist essentially Cartridge actuators systems
of inorganic nitrates, fuels, and metals, in which Destruct units Separation devices
none of the ingredients are classified as ‘explo- Detonators Simulators
sives; must be detonated by adequate-strength Dimple motors Squibs
Titan Boosters. Available in various formulations Electroexplosive devices Switch modules
in either packaged or bulk forms, both of Explosive actuators Switches
which offer the Slurrex blasting technique Flame initiators Thrusters
Flogef*: water-resistant, highly plastic, non- Flash squibs Time-delay
nitroglycerin slurry explosives classified as a Fuze subassemblies devices
Propellant Class B for shipping purposes. Gas actuators
 H 71

CHEMICAL PRODUCTS generators for all applications from tiny

Ammonium Nitrate: special purified product fo~ satellite spin-control rockets to propulsion
industrial chemicil use, available in solution, for large ballistic missiles, such as Poseidon,
prill, and grained form. Also high-density Polaris, and Minuteman. A wide variety of
grained material for formulation of military systems are in development and production
explosive compositions using metal and Spiralloy* motor cases and
Composition D-2 Wax: a densensitizing com- both composite and double-base solid pro-
pound containing wax, nitrocellulose, and a pellants
wetting agent; used in military explosive formu- Hercopel: a unique all-epoxide cure compo-
lations site solid propellant with excellent mechanical
Diazodinitrophenol (Diazo): yellow, crystalline and ballistic properties. Its outstanding per-
compound used as priming charge in blasting formance in extended environments makes it
caps well suited for tactical missiles
Mixed Nitrating Acids: a mixture of nitric and Double-Base Solid Propellants: a wide variety
sulfuric acid in various ratios and adjusted to of physical and ballistic properties which can
the desired DVS values (dehydrating value of be tailored to meet specific performance
sulfuric acid) requirements. Their high specific impulse and
Mixed Oxides of Nitrogen (MON): mixtures of excellent reproducibility are two of the many
N20A and NO in various proportions as re- reasons Hercules double-base ,propellants are
quired Up to 40% NO found in many of our rocket motors and gas
Nitric Acid: basic chemical of commerce generators used for both military and space
available in strengths 57 to 98% applications
Nitric Acid, Red Fuming: strong nitric acid ADVANCED SYSTEMS
containing free N02. Available in strengths ADVANCED COMPOSITE MATERIALS
up to 30$Z0NOZ. Also made with and with- Advanced composite materials from Hercules
out HF corrosion inhibitor consist of high-strength, high-modulus graphite
Nitric Oxide (NO): powerful nitrosat ing agent fibers that have been preimpregnated with
in organic reactions. Available under 500 psig polymer matrices. These materials possess
in cylinders and tube trailers. A conversion strength-to-weight ratios greater than steel;
unit is also available for the manufacture of uses include fabrication of aerospace and air-
NO from NzOq at the point of use. This is craft structures, industrial equipment, and
attractive to the large user because it reduces other structures or systems requiring high
the freight cost strength and modulus with minimum weight.
Nitrogen Tetroxide (N2O4): an energetic and Hercules capabilities include production of the
versatile oxidizer, nitrator, and nitrosator. graphite fibers and materials as well as research,
Available as a liquid in steel cylinders and development, design and production of the struc-
tank cars under moderate pressure (O to 10 ture or systems that utilize them
psig) Written by C. W. El LO
Nitrogen Trioxide (N2O3): especially useful for “Refs: 1) Mining & Scientific Press, San Francisco,
organic nitrosations and the in situ manu- Ca, April 23, 1870 2) Hercules Detonators Book-
facture of nitrosyl sulfuric acid and sodium let, 1927 3) A.P. Van Gelder & H. Schlatter,
nitrite. Also used as an oxidizing agent. “History of the Explosives Industry in America,”
Available in same shipping containers as nitro- Columbia University Press, 1927 4) W. Haynes,
gen tetroxide “American Chemical Industry, Van Nostrand,
Pentaerythritol Tetranitrate (PETN): white, NY (1949) 5) H.L. Fitch, Hercules Explosives
crystalline compound used as a detonating Engineer (1) (1971), p 2
agent in blasting caps and detonating fuse
CHEMICAL PROPULSION’ SYSTEMS Hercules powder. No 1: NC KN03 2.10,
75.00,
PROPULSION SYSTEMS
MgC03 20.85, KC103 1.05, sugar 1.00%. No 2:
AND GAS GENERATORS NC 40.00, KN03 31.00, MgC03 10.00, KC103
Complete solid-fueled rocket motors and gas 3.34, sugar 15 .66%
 H 72

Thorpe (Ref 3) gives two formulas for Her- Hertz Theory of Impact is described in the
cules powders: (1) NaN03 1, wood-
NC 77, Mathematical Theory of Elasticity by A.E.H:
pulp 2, MgC03 20, strength 106% of Guhr Love, Dover Publications, NY (1944), p 198.
Dynamite No 2. (2) NC 42, NaNO, 43.5, wood- This theory was applied by M.P. Murgai,
pulp 11.0, MgC03 3.5, strength 86% of Guhr JChemPhys 22, 1687-9 (1954) & CA 49,
Dynamite No 1 2073 (1955) te calculate detonation properties
Refs: 1) Cundill (1889) in MP 6, 12 (1893) of explosives
2) Daniel (1902), 374 3) Thorpe (191 7), 438
4) Giua, Trattato VI (1) “(1959 ),, 345 Herz, E. von ( ? – ? ). German scientist who
specialized in explosives. He was the author of
Herculite. A perchlorate explosive which was at numerous publications and patents. He proposed
one time on the British “Permitted List”. KCIOQ nitro-bis-diazobenzene perchlorate as an initiator
27/NG 33/collodion cotton l/woodmeal 9/NHq and patented the use of Lead Styphnate in ini-
oxalate 29/H20 1; limit charge 16 oz tiating compositions
Rej Barnett (1919), 137
Herz’s Explosives. Patented in 1923 CA 18,
Herculine. One of the old mining explosives 1573-4 (1924) Brit P 207563, several compo-
containing KN03 together with sawdust and sitions, such as ortho-, and para-nitrated quinone
camphor. Other ingredients were also added diazides of the polymeric phenols or their
Refi Daniel (1902), 374 metallic salts either (1) as a top charge over a
main (base) charge such as Tetryl, TNT, or
HERO (Hazards of Electromagnetic Radiation to
PETN, or (2) in admixtures with other com-
Ordnance). Any Ordnance Item is defined as pounds. Following are the primary and nitrating
being “HERO UNSAFE ORDNANCE” when: compounds proposed by von Herz:
1) Its interr@ wiring is physically exposed; 1) Bis [Dinitro-hydroxy-azo-quinone] , called by
v. Herz sym-Tetranitro-dioxy -diphenol-quinone-
2) Tests are being conducted on the item that
result in additional electrical connections to tetrazide, or Tetranitro- diresorcin-diazo-anhydride
the item; 2) Dinitro-dihydroxy-azo-quinone, called by
v. Herz Dinitro-3 ,5-di-oxy-quinone-diazide, or
3) EED’s (Electroexplosive Devices) having exposed
wire leads are present, handled or loaded; Dinitro-phloroglucin-diazo-anhydride
3) Dinitro-hydroxy-azo-quinone, called by v.
4) The item is being assembled or disassembled; or
Herz Dinitro-m-oxy-quinone-diazide, or Dinitro-
5) The item is in a disassembled condition (Ref 1)
resorcin-diazo-anhy dride
If such unsafe ordnance is exposed to RF
4) Mono-(and di-)nitro-hydroxy-azo-quinones,
(radio frequency) fields above a certain amplitude
called by v. Herz Mono-(and di-)nitro-para-
level, sufficient RF energy can be induced into
oxygenone-diazides, or Mono-(and di-)nitro-
the fning circuits to explode the EED’s. There-
hydroquinone-diazo-anhy dride
fore, for the handling of HERO UNSAFE ORD-
NANCE, restrictions of field intensities to cer-
HES 4138. One of the Hercules Powder Co
tain levels, such as the o.g volts per meter maxi-
solventless sheet double-base, proplnts prepd and
mum for the 2 to 32 MHz (mega Hertz) range,
investigated during WWII: NC(13. 13% N) 49.8,
have been established to ensure safe operations.
These criteria levels are specified in Ref 1, which NG 40.0, Et Centr 1.0, K nitrate 1.5, DNT
is confidential 6.0, DBuPh 1.5 & candelilla wax 0.2%
Refs: 1) Anon, “Radio Frequency Hazards Ref R.B. Corey et al, OSRD Repts 1103
Manual”, NAVORDOP 3575/NAVAIR 26-1-529 (1942), 1 and 1558 (1943) 2
2) Anon, “Excerpt from HERO Newsletter No
30, Jan 1970, Commander US Naval Weapons Hesilit. A Rus pre-WWI mining expl: NG
Center, Attn Mr. R.M. Price, Code TE-2, Dalgren, (gelatinized with CC) 30.75/DNT 5.25/AN 18/
Va 22448 3) G. Cohn, Edit, Expls&Pyrots 3 (5), rye meal or dextrine 39%
1970 4) US Spec Ml L-I-23659C, “Initiators, Refi’Anon, SS 12, 409(1917)
Electric; Design and Evaluation of” (Aug 1972)
HE SHELL. Same as High’ Explosive Shell
 H 73

HE/SH Shell. High Explosive Squash Head expl mixtures which would produce increased
Shell. See under HEP in this Vol blast effects in enclosed or nearly enclosed spaces
directed attention to their use for possible mili-
HESS, P. German scientist who designed several tary application. In 1950 PicArsn developed a
tests for explosives, such as Hess’ Crusher Test, “high capacity” filler for 20mm projectiles con-
Deflagration Test etc. Author of several publica- sisting of 85/1 0/5–RDX/Al/desensitizer which
tions on physical testing of explosives: was more powerful than Tetryl filler. However,
Hess’ Crusher Test (Hess’ Brisance Meter). See in comparison with AfOX (Metal Oxidizer Ex-
Brisance Meter of Hess [See Vol3 of Encycl, plosives) Type (described inRef2,pp213-225)
p C492-R, under Compression (or Crusher] there was little doubt as to the superiority of MOX
Tests] mixts. HEX mixts were developed at PicArsn in
Hess’ Deflagration Test. This test, which, is no 1953 by Sheffield & Murray (Ref 1) as superior
longer used, consisted of heating the explosive high blast compns suitable for use in small caliber
at 70° until spontaneous co~bustion (defla: projectiles
gration) took place (Ref 1). In a modified The HEX compns were prepd by blending the
method, the explosive was heated at 75° under appropriate weight of the dry ingredients in a
pressure until deflagration took place Patterson-Kelly Twin-Shell Blender for at least
Note: American investigator, A.P. Sy, also 30 reins
designed a “Deflagration Test” An rdternate procedure for 100 to 200g batches
Hess’ Test. In this test, a sample of an explosive used a Cradle-Roll Mixer. This device consisted
was heated at 70° in a current’ of air which of a half-barrel type container constructed of
was then passed into a solution of zinc iodide wood and lined with an electrical conductive ma-
and starch. The time taken to impart a blue terial. A plastic roll was allowed to move over
color to the solution was noted ~(Ref 2) the ingredients by remote control action. The
Refs: 1) Reilly (1938), 81 2) Ibid, 78 roll action prevented caking of the mixt but had
no adverse effect on particle size of the ingredients.
HET. Abbrev for High Explosive Tracer The period of time to obtn an intimate mixt was
approx 15 reins
Heterocyclic Compounds are ring structure
carbon comps in which one or more of the Compositions and Properties
atoms in the ring are not C. Frequently these Components, % HEX-24 HEX-48
other atoms are N. General refs to hetero-
cyclic comps are: KC104 (17 microns) 32 32
Al, atomized, (20 microns) 48 —
Refs: 1) A., Weissberger (orig editor), “The
Chemistry of Heterocyclic Compounds”, Inter- Al, flaked (1 micron) – 48
science; beginning in 1950 and contin thru RDX (thru 325 mesh) 16 16
present 2) R.C. Elderfield (Editor), “Hetero- Asphaltum (thru 100 mesh) 4 4
cyclic Compounds”, Wiley, NY, Vol 1, (1950) Properties
thru Vol 6 (1957)
Molecular Weight 47.6 47.6
Heuschrecke (Ger for Grasshopper). A series of OB to C02, % –42 –42
weapon carriers (Waffentriger) such as for 105 OB to CO, % –34 –34
Powder, color gray gray
mm Gun, developed by the Germans early in
the WW II. They are described in VO1III of the “Density, apparent, g/cc 1.39 0.69
Density, pressed at 2.1 1.62
Illustrated Record of German Army Equipment
at 20000 psi
1939-1945, War Office, London (1947)
Ballistic Mortar Not Given Not Given
Blast Effects Not Given Not Given
HEX (High Energy Explosive). Two types of
Brisance by Sand Test, 12.5 23.7
these expl compns, HEX-24 and HEX-48 are de-
g sand crushed
scribed in Ref 2, pp 164-69
Brisance for TNT 48.Og
Origin: The development of “slow-burntig”
Detona~ion Rate Not Given Not Given
 H 74

Properties (cent’d) (sublimes),bp 185.5° at 777 rnrn,d 2.091 at

Explosion Temp, “C 520 545 20°/40. Exi~ts in three crystalline forms;
(5 see) usually as colorless rhombic crystals with a
Flame Temp, “K 2552 2382 camphor-like odor. May be prepd by the
Fragmentation Not Given Not Given pressure chlorination of tetrachloroethy lene in
Friction Test, steel shoe Detonates Partially an enamel vessel and in presence of light
deton (Ref 3). Nearly insol in w (0.005 at 22°)
Friction Test, fiber shoe Unaffected Unaffected very sol in alc and eth. It is toxic, being
Gas Volume, cc/g 159 200 similar in action to’ CClq and results in
Heat of Combstn, cal/g 4197 4119 lowered blood pressure, kidney and liver
Heat of Expln, cal/g 1858 1735 injuries. Explodes in mixtures with Zn powders,
Heat Test at 100° and to lesser extent Al powders (Ref 3). Used
%1OSS in 1st 48 hrs 0.15 Not Detd in smoke screen compositions (Ref 2), in ex-
%1OSS in 2nd 48 hrs 0.00 Not Detd plosive mixtures and pyrotechnics, and as a
Expln in 100 hrs None – camphor substitute in celluloid and other NC
Hygroscopicity, % None Not Given plastics. Techn grade MIL-H-235A (See also Ref 5)
Impact Sensitivity 16 inches Not Given Refs: 1) Beil 1,87, (26)& [58] 2) G. Reure,
PicArsnApp, 2kg wt (TNT 14) MP 38,419-21 (1956)” 3) A. Lamouroux &
Rifle Bullet Test Not Given Not Given J. Meyer, MP39,435 (1957) &CA52, 21107
Sensitivity to Initiation LA 0.20g LA 0.20 (1958) 4) Kirk& Othmer 3,773 (1949); 2nd
(Min priming charge) Tetryl 0.25 Tetryl 0.25 edit 5, 166 (1964) 5) CondChemDict (1971),
Storage Dry Dry 440
Trauzl Test Not Given Not Given
Vacuum Stability Test 1.25 1.52 Hexachloronaphthalene or Chloronaphthalene
at 100°, cc/g/48 hrs (Chlorinated white CIOH,C1,; mw 334.82.
tar).
Usage, press-loaded at HE filler for Crystals; prepd by chlorination of naphthalene
20000 psi small caliber (Ref 2, 185). This compd is highly toxic (Ref
shells 3). It was proposed as an addition (4–5%) to
Note: Above expl props are listed in Ref 2 explosives containing large amounts of NaN03
Refs: 1) O.E. Sheffield& E.J. Murray, “Develop- together with NG, sawdust, etc. It is supposed
ment of Explosives – Metallized Explosives – High to act as a sensitizer in these mixtures
Blast Fillers for Small Caliber Shell”, PicArsn Refs: 1) Beil, not found 2) J.W. Dawson &
Memorandum Report No MR-49, (Dee 1953) W.M. Dehn, USP 2255653 (1941) and CA 36,
2) US Army Materiel Command, “Explosives 272 (1942) 3) CondChemDict (1971), 440
Series, Properties of Explosives of Military In-
terest”, AMCP 706-177 (Jan 1971), pp 164-69 2,4-Hexadiyne-1,6-dihydroperoxide. See under
Note: There are no US Military Specifications Diacetylenic ,Dihydroperoxides, Vol 5, p D1 120-R
for HEX’s
Hexaethylidenetetramine (called Tricrotylidentet-
ramin in Ger). CIZHZQNa; mw 224.40, N 24.97%;
Hexa, Hexamin, Hexamit, Hexyl or Hexanitro-
diphenylanine (HNDPhH). It is described in
trysts (from hot water; forms numerous salts, some
VO1 5, pp D1434-R to D1438-R, under of which are unstable on heating (Ref 1)
DIPHENYLAMINE AND DERIVATIVES. ~SO It is reported that the compd is formed by
in PATR 2510 (1958), p Ger 88-R the reaction of acetaldehyde-ammonia &
ammonia (Ref 1). This reaction yielded a max
Hexa S-22, S-26 ‘and E4. German “Substitute of 87% gum from which the separation of
Explosives” used during
(Ersatz-sprengstoffe) not more than 370 of Hexaethylidenetetramine
WWII (See Vol 5, Table E15, p E122) was possible. Nitration attempt of the product
was not considered practicable. The above
Hexachlorethane, Perchlorethane or Carbon reaction is analogous to the hexamethylene-
Hexachloride. C13C”CC13;mw 236.72, mp 185° tetramine from which RDX is prepd by
 H 75

nitration, and was considered to yield a sequentially poured into MeOH & EtzO. It is
product which might be nitrated to Cyclo- then dried & recryst from chlf. The intermed
triethylidenetrinitramine (Ref 2) thus formed, [C1CH2N(N02)CH2] ~, on standing
Refs: Beil 1, 730, [789] & {2980} 2) F.A. gives the subject product
Smith, “Study of the Nitration of Hexaethy- Refs: 1) Beil, not found 2) W.J. Chute et al
lidenetetramine,” PATR 414 (Sept 1933) CanJRes 27B, 503 (1949) & CA 43:9074
(1949) 3) J. Majer & J. Denkstein, CollCzech-
Hexahydrobenzene or Hexamethylene. See ChemCommun 31, (6), 2547 (1966) & CA 65,
Cyclohexane and Derivatives in Vol 3, pp 7042 (1 966)
C595-L & R
Hexahydro-1,3-dinitro-1,3,5-triazine Nitrate, PCX,
Hexahydrocatechol. See Cyclohexanediol and
Derivatives in Vol 3, p C595-R – C596-L
Hz? ‘L’\CH ,.2
; mw 239.16, N 35.1570
Hexahydro-l,3-dinitro-5-nitroso-5-triazine, HN03 N NN02
NO. ‘.C’
H2
trysts, mp 99° (decomp); insol in cold alc &
eth. Prepd by adding hexamine dinitrate to 9370
ONN , c /NN02 nitric acid at -40°, then adding water and
filtering ppt (Ref 4). PCX reacted with sulfuric
H2
acid gives RDX (Ref 4)
mw 206.15, N 40.78%; mp 165°(Ref 3) & 177” PCX is claimed to be an intermediate in
(Ref 2); sol in ale. Prepd by adding Cyclotri- RDX synth (Ref 2) but this claim is refuted in
methylenetrinitrosamine to a soln of AN in Ref 3
coned sulf acid at -25°. Mixt is kept at -15°
Refs: 1) Beil, not found 2) A.H. Vroom &
until all solid has dissolved and then warmed C.A. Winkler CanJRes 27B, 828 (1949) & CA
and filtered at 0° (Ref 3); 1,9-Diacetoxy- 45, 4727 (195 1) 3) L. Berman et al Ibid 29,
2,4,6,8 -tetranitro-2,4,6,8 -tetrazanone is reacted 767 (1951) & CA 46.767 (1952) & CA 46,
with a sohr of 99% nitric, hydrogen peroxide 2084 (1952) 4) C. Holstead et al, JChemSoc
& water at -40° to ppt subject material (Ref 2). 1953, 3341 & CA .49, 8311 (1955)
Nitration of subj mat produces RDX (Ref 3)
Refs: 1) Beil, not found 2) A.F. McKay et Hexahydro-1-(methoxymethyl)-3,5-dinitro-s-
al, CanJRes 27B, 462 (1949) & CA 43, 9073 triazine or 1-Methoxymethyl-3,5-dinitro-1-,3,5-
(1949) 3) J. Simecek, ChemListy 51, 2367 triazcyclohexane.
(1957) & CA 52, 6367 (1958) CH20CH3
/N\
Hexahydro-3,6-dinitro-1,3,6-oxadiazepine or Hzf ~H2
3,6-Dinitro-1-oxa-3,6-diazacycloheptane, ;mw221.21, N31.67%
NN02
02 NN\cH/
.
trysts (acet-chl~ ,mp 134°. Prepd by addn of
3,5-Dinitro:l ,3,5 -triazocyclohexane nitrate to a
soln of MeOH and 40’% aq formaldehyde (Ref
2); HNC)3 in S02 (at -30°) + (CF CO)20 to
N 2?.1 5%; trysts, mp 148-155 °(Ref 3) & 154- give subject compd, mp 138° (Re~ 3). Nitra-
155°(Ref 2). Prepd from [CH2NHN02] ~ in tion of subj comp with HN03 was studied in
40% formalin reacted with acet anhyd at 20.0, Ref 4
Refs: 1) Beil, not found 2) K.W. Dunning &
followed by digestion & hydrolysis at 65°
W.J. Dunning, JChemSoc 1950, 2920 & CA 45,
(Ref 2); N,N-bis(piperidinomethyl)-ethylendi- 6643 3) R. Reed Jr. JOC 23, 775 (1958) &
nitramine refluxed in acetylchloride, then CA 53, 14113 (1959) 4) J.A. Bell et al, JCS
poured into iced water, the pptate is then (C) 1969, 1556 & CA 71, 49908 (1969)
 H 76

Hexahydro-1-methyl-3,5-dinitro-s-triazine or Hexahydro-2-oxo-1,3-dinitropyrimidene or
1,5-Dinitro-3-methylhexahydro-1,3,5-triazine. N,N’-Dinitro-N,N’-trimethyleneurea.
CH, ,CH2N(N0,),\” “
,N\ H2C.\ CO ;mw 190.14, N29.47%
H$ ‘CH2 CH,N(NOO)”’
;mw 191.18, N36.64$% OB to COZ –50.5%; ndls (from ale), decomp in
OzNN\ ,NNOZ
CH2 boiling water. Prepd from N’N-trimethylurea and
coned nitric acid
colorless rhomb trysts (from ale), mp 100-
Refs: 1) Beil 24,5 2) A.P.N. Franchimont &
104° decomp. Prepd by adding alc soln of
MeNH2 to a soln of methylene dinitramine in H. Friedrnann, Rec 26,218 (1907)&CA 1,2881
40% aq formaldehyde at OO. No mention of” (1907)
expl ‘props
Refs: 1) Beil, not found 2) F. Chapman et
Hexahydrophenol. See Cyclohexanol and Der-
al, JChemSoc 1949, 1838 & CA 44, 1412
ivatives in Vol 3, pp C596-R & C597-L
(1950)
Hexahydromethyl-s-triazatriborine, 1,3-Dimethyl-
borazine, 1,3-Dimethylborazole or Dimethyl- Hexahydropyrogallol. See Cyclohexanetriol and
triborinetramine, Derivatives in Vol 3, p C496-L & R
H

~/ B\ NcH_
Hexahydroterephthalic Acid Diazide; 1,4-Cyclo-
s ;mw108.58, N38.71%
Hi\ bti hexanedicarbonylazide (called Trans-Hexahydro-
N’ terephthalsaurediazid in Ger),
CH3 CON3
/\
colorl bp 108° (Ref 2), AHvap 8275 cal/
liq, Hz C CHZ
mole, Trouton’s const 21.9 eu, hydrolyzes in ; mw 196.20, N 42.84%
Hz b ~Hz
water. Prepd by adding dimethoxyethane \/
(DME) at 0° to a mixt of NaB~, CH”,NH ,HC1 CONS
& NHqCl, when Hz evolution ceases excess DME needles,mp 63° with decomp, insol in cold w;
removed by vac dlst and product pyrolyzed at sol in ligroin, benz & eth. Prepd by reacting the
150° and distilled (Ref 4); BZH6 + CH3NH2 + 1,4-dihydrazid with NaN02 in s dil HAc
NH3 htd in bomb at 200° for % hour and Product decomp slowly on standing. On
fractionally distilled heating, decomposition becomes rapid and
An isomer, 2,4-Dimethylborazine, almost explosive. The 1,3 isomer may have
CH3 been an intermediate in a synth of diamino-
, B\ cylohexane (Ref 2)
HN” ‘NH Refs: 1) Beil 9, (318) ,2) F.W. Hewgill &
; mp -48°/bp 107/AHvaP P.R. Jeffries, JChemSoc 1956, 805 & CA 50,
H+\ ,~CH3
N 14571 (1956)
H
Hexahydro-3,5,7 -trinitro-l ,3,5,7 -tetrazocine-l (2 H)-
9230 cal/mole was prepd by reacting an excess
methanolacetate, or 1 Acetoxymethyl-3,5,6-
of H3B3N3H3 with CH3MgI in eth and purified
trinitro-1,3,5,7 -tetrazacylcooctane.
by fractional distillation (Ref 3) & by heating
monomethyldiborane with ammonia at 190° in Iyo2
a bomb (Ref 2) 02N~- CH2– N- CH2– ~NOz

Refs: 1) Beil, not found 2) H.1. Schlesinger H-C — N — CH. ‘

et al, JACS 58,409 (1936) &CA 30,4421 (1936)
3) H.I. Schlesinger et al, JACS 60, 1296 (1938)&
CA 32, 6570 (1938) 4) O.T. Beachley, Inorg- mw 335.28, N 29.25~o; trysts, mp 152–53°(Ref 4),
Chem 8, (4), 981 (1969)&CA 70, 111260 (1969) no recryst sol found. Prepd by adding 98%
HN03 rapidly to 1,5 methylene-3 ,7, dinitro
 H 77

1,3,5,7 tet razacyclooctane in acet anhyd (Ref ment of the chlorine atoms of cyanuric
2); or adding (in increments) 1 acetyl-3,7- chloride,
dinitro-5-nitroso- l,3 ,5,7-tetrazacyclooctane to a /N\
soln of 30% H202 in 98$Z0HN03 at -50° and cl-f :-cl
raising temp to 0° for 12 hrs (Ref 3) by bis-(~rinitroethyl)-
NN’
.
Refs: 1) Beil, not found 2) W.E. Bachmam & \c/-
E.L. Jennet, JACS 73, 2773 (1951) & CA 46, C1
2085 (195 1) 3) W.E. Bachmann & N.C. Deno, amine, [(0 N)3C”CH2] NH, in the presence of
JACS 73, 2777 (1951) & CA 46, 2085 (1.951) pyridine; b ~f reaction o cyanamide with 2
4) R.A. Marcus & C.A. Winkler, CanJChem 31, molar equivalents of trinitroethanol to give bis-
602 (1953) & CA 47, 12219 (1956) (trinitroethyl)-cyanamide, followed by tri-
merization of the latter
Hexahydro-1,3,5-trinitro-1,3,5(1H)-triazepine or Refs: 1) Beil, not found 2) N.K. Sundholrn,
1,3,6-Trinitro-1,3,6-triazacycloheptane, Cyclonite T.C. Richards& D.L. Schoene, Naugatuch Chem
Homolog. See Vol 3, p C630. data:Additional Div, US Rubber Co Progress Rept (15 Feb 1950
nmr spectra (Ref 1); differential thermal to 15 April 1950), NORD 10121, p 4
analysis (DTA) gives 2810 as the exotherm
max (Ref. 2) Hexal. A Swiss explosive consisting of RDX &
Refs: 1) J.A. Bell & I. Dunstan, JChemSoc(C) Al, particularly suitable for AA ammunition.
(1966) 870 & CA 64, 19616 (1966) 2) Y.P. lts d is 1.8, expln temp 225 (RDX 2250),
Carignan & D.R. Satriana JOrgChem 32, (2), Trangl value 420 cc (RDX also 420) & deton
285 (1967) & CA 70, 10960 (1969) vel 7900 m/see (RDX 8500) (Ref 1)
The Al is coated with a water-insol-wax to
Hexahydro-3,5-trinitro-1,3,5-triazine. See Cyclo- make it impervious to water-Al reactions that
trirnethylenetrinit ramine in Vol 3, p C6 11 liberate hydrogen (Ref 2)
Refs: 1) PATR 2510 (1958), p Ger 88-R ‘
Hexahydro-1,3,5-trinitroso-1,3,5-triazine. See 2) P. Aubertein, FrF 1180530 (1959)&CA 54
Cyclotrirnethylenetrinitrosamine in Vol 3, p 20210 (1960) 3) M. Freiwald, Explosivst 6,
C630 133 (1961)
Hexahydroxylamine Cobalt Nitrate, [CO(NHZOH),]
(N03)3; mw 443.20, N 28.45%. Decomposes ex- 3,3,7,7,11,11-Hexamethanol-1,5,9-trioxacyclo-
ploswely with a violent evo~utioh of gas. See Refs dodecanehexanitrate or 1,5,9-Trioxacyclodecane-
Refs: 1) A. Werner & E. Berl, Ber 38, 897- 3,3,7,7,11,11-hexamethanolhexanitrate.
98 (1905) 2) V.I. Belova & Ya. K. Syrkin, ~HzONOz ~HzON02 ~HzON02
AkadNauk 30, 109-19 (1955) & CA 50, 9803
~ 0-CHz-C-CH2-O-CH2 -~-CH2-O-CHz-~-CH2 1
(1956) (Magnetic susceptibility of Co+++ com- I
plexes in temp range 349-377”K) I CH20N02 6H20N02 CH20N02 /

Hexahydroxymethylbenzene Hexanitrate. See mw 624.45, N 13.46%,’OB to C02 –53.870; tacky

Hexamethylolbenzene Hexanitrate solid. Pentaen”thritol is polymerized with dil
sulfuric acid and nitrated with 98% nitric acid at
Hexakis (2,2,2-trinitroethyl)-melamine, OO. Used as sensitizer for AN explosives
Refs: 1) Beil, not found 2) J.A. Wyler, USP
[(O, N), CCH,] ,N-~’N<C-N [CH,C(NO,),] , 2465776 (1949) &CA 43,6223 (1949)
NN
\/ 2,3,5,2’,4’,5’-Hexamethylazobenzene-6-azide or
c
6-Azido-2,3,5,2’,4’,5’-hexamethylazobenzene.
N [CH,C(NO,),] , ; (CH3),(N,)C6H.N: N:C,H,(CH,),; mw 307.44, N
mw 1104.51, N 30.QQYO; red oil, which flashes 22.78%; red ndls (from eth); mp 90~91 o(dec);
on a hot plate but cannot be detonated by explodes mildly on rapid heating or on con-
impact. Two synthetic routes to its prepn tact with coned HZSOO.May be prepd from
were considered to be unsuccessful: a) replace- 6-amino-2,3,5 ,2’,4’,5’-hexamethylazobenzene as
described in Ref 2
Refs: l)Beil 16, 76 2) T. Zincke, H. Jaenke,
Ber 21, 546 (1888)
 IH 78

,
Hexamethyldiphenylmethane and Derivatives GazzChimIta184, 1114 (1954)&CA 52,3707
Hexamethyldiphenylmethane also called 3,5- (1958) 3) Sax (1 968), 813 4) CondChemDict,
Dimethylphenylpropane 8th Ed,443 (1971)
OH
Hexamethylenediaminedinitrate or 1,6 Hexane-
diaminedinitrate. 03 NH. Hz N(CH2 )6 NHZ. HN03;
m. 116.24, N 24.lwo; wh trysts, mp 107.5°,
252.43; crysts (from alc), mp 174.5°. ~epd by AHcomb 998 kcal/mole, AHfO = 184.2 kcal/
treating m-xylene with 2,2-dichloropropane in mole (Ref 3). Prepd by reacting HMDA with
the presence of AlC13. Nitration with 65% nitric acid. It is used in castable propellants,
nitric acid gives the mononitro and dinitro in admixture with RDX & inorg nitrates,
derivatives, neither of which is explosive, either as, principal ingredient or as a flux (Ref
although the latter decomposes at 256°. 5). Dissolved in anhyd nitric acid it gives
Further nitration with 97% nitric acid pro- N’N’’-Hexamethyl-1,2,3-propanetriaminetrinitrate,
duces the tetranitro derivative which decom- rnp 104-106°, which is used in two-component
poses at 295-300° monopropellan~s (Ref 4)
Hexanitrohexamethyldiphenylmethane or 2,2-
Bis[2,4,6-trinitro-3,5-dimethylphenyl] propane, The final product of the action of nitric
acid on hexamine or hexamine dinitrate is RDX
[(CH3)2C6(N02)3] *C(CH3)2; mw 522.43, N we Vol 3, p C614. At low temps, however a
16.09%, OB to C02 –1 07,.2%; yellowish trysts number of other compounds are produced
(from isoamyl ale), color deepens on exposure (Ref 2). Dilution of the hexamine dinitrate-
to light; S1sol in warm isoamyl ale; decomposes nitric acid reaction mixture at low tempera-
with a slight explosion at 205°. Prepd by ni- tures with ethyl ether and subsequent treatment
trating 2,2-Bis[2,4-dinitro-3 ,5:dimethy1-phenyl] of the gum so obtained with methyl and ethyl
propane with fuming sulfuric acid mixed with alcohols and water severally leads to l-alkoxy-3:
97% nitric acid. It is an expl 5-dinitro-l:3 :5-triazacyclohexane (IV), 1 :3-di-
Refs: 1) Beil 5, [527] 2) H. Goudet & F. nitro- 1:3: 5-triaza-n-pentane 5-nitrate (V), and
Schenker, Helv 10, 134, 139 (1927) methylenedi-1 -(3: 5-dinitro-l: 3: 5-triaza-cyclo-
hexane) (VI). Dilution of the reaction mixture
with methyl and ethyl alcohol produces mainly
3,3,6,6,9,9-Hexamethyl-1,2,4,5-1,2,4,5-tetroxo-
3:5-dinitro-l:3 :5-triazacyclohexane nitrate (II).
nane. See Acetone Compounds under 2,5-
1-Methoxymethyl-3: 5-dinitro-l: 3: 5-triazacyclo-
Bis(hydroperoxy )-2,5-dimethyl-hexene in Vol hexane (IV; R = Me) has been synthesized
2, p B144-R from (II), methyl alcohol, and formaldehyde.
1:3: 5-Trinitro-l: 3: 5-triazacyclohexane (I) has
Hexamethylenediamine and Derivatives
been synthesised from (V), acetic anhydride,
Hexamethylenediamine, 1,6 Hexanediamine and formaldehyde
(HMDA). H, N(CH2) NH2; m. 116.24, N 24.10%
silk-like leaves, mp ~2~ bp 205° (subI), sol in ,N”NO
water; S1sol in h eth. Prepd by hydrogenation 2‘~H2
of adiponitrile over Raney Ni or Co; chlori- (I.) %:
nation of butadiene then reactn with NaCN & 02N”N NN02
hydrogenation. Acute local irritant-mod flame \ CH2’
hazard. Used’ in high polymer synth & as a
cross-linking agent (Refs 1, 3 &4) ‘/N”N02
In alc soln HMDA reacts with TNT to give (11.) H’;
‘CH2
,
the following derivs: 02N”N NH2 + }N02-
/3TNT = 3,3’-dimethy1-2,2 ‘-6,6‘-tetranitrodi-
‘CHz’
phenyl-N,N’-hexamethy lenediamine, mp 176-.
177°
~TNT =. 4,4’,6,6; deriv, mp 187-190° ,NNO
With 2,4 (N02)2C6H3C1, HMDA reacts to (Iv.) H*:
2=CH2
give 2,2 ‘,4,4 ‘tetranitrodiphenyl-NN’-hexarnethyl- 02N”N\ N“CH20R
enediamine, mp 206-208° (Ref 2) CH2’
Refs: 1) Beil 4, {597} 2) M. Giua &G. Musso,
 H 79

(V.) NO, “NHC~ “N(NO,)”CH,”NH,,HNO, The impure product may be purified by

dissolving it in H20, and saturating the solution
CH ,CH, \ with NH. gas (Ref 3). The commercial product
/ NN02 is usually about 99% pure, containing about
(VI.) 02 N”: 2= N–CH2–N
H2C> bH2 H2C< , ~H2 0.3% H20 and 0.3% ash. There is also a USP
N“N02 product, which is nearly 100% pure
‘NN02’
Hexamine readily dissolves, in water with
Refs: 1) Beil, not “found 2)” K.W. Dunning & evolution of heat, producing a mildly basic
W.J. Dunning, JChemSoc (1950) 2920 & CA solution; somewhat sol in alcohols and S1sol
45, 6692 (195 1) 3) L. M~dard & M. Thomas, ‘ in ether and aromatic hydrocarbons
MP 35, 172 (1953) 4) H.M. FOX, USP 3212254 Walker (Ref 4) gives the following volu-
(1957) &CA 64,521 (1966) 5) G. KnUffler & bility values:
A. Rest (1959), GerP 1059333 &CA 55,9880 Water (grams of hexamine in solution)
(1961) Temp (“C) O 25 50 , 70
Volubility 47.3 46.5 45.0 43.4
Hexamethylenediamine Peroxide. , Solubility in other solvents (grams of hexa-
[(CH2)3NH2] 2.H202; mw 150.26, N 18.64%; mine per 100 rrd of solvent)
trysts. HMDA reacts with aq or ethereal H202
to give a solid adduct Room Temp Elevated Tems2
Refs: 1) Beil, not found 2) Ya.A. Fialkov &
Petroleum ether in sol insol
A.A. Shokol, UkrainKhimZhur 15,318 (1949) &
Ethyl ether 0.06 0.38
CA 48,5091 (1954) —
Absol ethanol 2.89
Methanol 7.25 11.93
Hexamethylenetetramine and Derivatives. Hexa- Chloroform 13.40 14.84
methylenetetram irre (HMTA ), Hexamethyleneam ine, Acetone 0.65 —
Hexin, Urotropine, Hexamine, Formincystogen, Benzene 0.23 —
Amino form, Hex, Naphthamine or Uriton (Ger) Glycerol 20.9 —

When hexamine is ignited it burns with a

2 pale blue flame. Its std heat of formation is
21 I 12; mw 140.19,
N-~2–~- CHA~ +29 .65 kcal/mole for the solid and 47.6 for the
gas (Ref 2)
Pure hexamine may be taken interrially by
N 39.9770; colorless, ~dorless and sweet-tasting some persons in small amounts and it is used
rhombic crystals; d 1.27 at 25°, mp 280°, when in medicine as a urinary antiseptic, but with
heated in a sealed tube it decomposes with some persons jt is toxic.” It can also be a skin
charring at a temp above 280°; when heated in irritant
air, it decomposes without melting; when heated Hexamine serves as a “parent compound for
in vacuum, it sublimes at 230-270° without the preparation of RDX, HMX & Hexamethyl-
appreciable “decomposition, fl p 482°F enetriperoxidediamine. It is also used in a
Was first prepd by Butlerov in 1860 by the mixture with sodium phenate, as an adsorbent
action of gaseous ammonia on paraformaldehyde, of phosgene in gas masks. Its use as a cross-
also discovered by Butlerov. Hexamine was linking agent for guar gum in AN-slurry explo-
later studied by Duden and Scharf and other sives has been patented (Refs 9 & 10)
investigators, and a structural formula was
An early review of the uses of hexamine in
assigned to it (Ref 1)
the explosive industry is given by Konrad
It is made continuously from gaseous NH3
(Ref 2). Also, see further under “Hexa-
and HCHO (Ref 5) or in parallel flow of these
methylenetetramine Explosives”. other more
ingredients. in the Iiq state (Ref 6). Another
recent reviews are Refs 7 & 9. For the nitro-
method involves the reactn of paraformaldehyde
sation of hexamine see Vol 3, pp C611 -624
with liq NH3 in an autoclave at 100° (Ref 8) ,
According to requirements of the U S
 .

H 80

Armed Forces as covered by Spec’ MIL-H-502A yel trysts; was prepd by Hofmann (Refs 1 &2)
(June 1968), there are two grades of Hexamine by the interaction of hexamine with chromic
(1 & 11) both of which must comply with the acid and 30$Z0hydrogen peroxide
following requirements: Very S1sol in water. Explodes (but not
1. Pun”ry – minimum 99.5%, maximum violently) on heating
100.2% (as determined by the method Hexamethylenetetramine-Dichromic Acid.
described below, ‘under Tests) [(CH 2)6fi LI] *. H*Cr207; rnw 498.46, N 22.48%;
2. Formaldehyde – none yel trysts; was prepd by Cambier and Brochet
3. Ammonia – max 0.02% (Refs 1,2 & 3). Explodes violently
4. Chlorides – max 0.02%
5. Ash – max 0.05% Hexamethylenetetramine-Tetrachromic Acid.
6. Water insoluble material – max 0.05% [(CH2)6N4] z .HzCrqO1s; mw 698.46, N 22.48%;
7. Volubility in glacial acetic acid – trysts; was prepd by Cambier and Brochet (Refs
completely soluble without turbidity 1, 2 & 4). Explodes more violently than the
In addition, there are specific requirements for previous compd
each grade Lit search in CA (1947-71) revealed no other
8. Moisture–max, Grade I, 0.50%, Grade 11,0.25% expl hexamine Cr compds
9. Granulation – through U S Standard Refs: 1) Beil 1, 586 2) R. Cambier &A. Brochet,
sieves, conforming to Federal Spec BullSocChim, France (3) 13,394 (1895) 3) K.A.
RR-S-366; Hofmann, Ber 39,3183 (1906) 4) Walker, (1953),
Grade I – sieve No 16 – 100% (rnin), 288
No. 60- 30% (max), No 100 – 10% Hexamethylenetetramine Explosive. A powerful
(max) solid explosive was claimed to have been prepd by
Grade 11 – sieve No 16 – 100% (rein), oxidizing hexamine with a solution of hydrogen
No. 60 – 50% (max), No 100 – 20% peroxide, treating the resulting product with nitric
max) acid and then, deoxidizing with Hz Oz (Ref ‘1).
Refs: 1) Beil 1, 583 (306) & 648 2) Dr After drying, this was mixed with AN, castor
Konrad, Nitrocellulose 5, 123-4 (1934) & CA oil and turpentine (Ref 2)
29, 1250 (1935) 3) T. Ohara JSocRubberInd ~e/s: 1) E. I.d’AsteCk, USP 1835697, (1931)
Japan 10, 438 (1937) 4) J .F. Walker, “Formal- & CA 26, 1125 (1932) 2) L.E. d’Asteck
dehyde”, 1.12, 120, 276-301, Reinhold Publ CaIlerY, BrtitP41 5900 (1934) & CA 29, 929
Corp NY (1944) 5) F. Meissner et al, IEC
(1935)
46, 724 (1954) & CA 49,3797 (1955) 6) M.
Hexamethylenetetramine Explosives. Several ex-
Weimann (GER) & CA 50, 5041 (1956) ‘.7) P.W. plosive compositions containing hexamine in
Sherwood, Petrol Refiner 37 (9), 351 (1958) & admixtures with oxidants or as chromium,
CA 52, 18959 (1958) 8) M. Amagasa et al, copper nitrate, perchlorate, & peroxide comps
BullChemResInst Non-Aq Solns, Tohoku Univ are known. .Several hexamine/oxidant mhtures
7, 7 (1957) & CA 53, 18849 (1959) 9) F. have been patented as explosive& propellant
Eiden, Deut’ Apoth Ztg 42, 1348 (1 961) & CA compositions:
56:9355 (1962) 10) D.S. Partridge USP
3496040 (1970j & CA 72, 91877 (1970) 11) 91/9% AN/HMTA used dry or as slurries
Y. Wakazono & Y. ‘Otsuka USP 3524777 & (Refs 3 & 5); HMTA/A120,”9H20/KO0,
CA 73, 100647 (1970) 12) E.F. Westrum et al, (Ref 1); an HIKTA-AN adduct prpd from aq
JACS 92, 7296 (1970) & CA 74, 57970 (1971) solns or ,melts and mixed 1 part adduct to 4
parts AN (Ref 2); compositions that are
Hexamethylenetetramine-Chromium Compounds. detonator-sensitive consisting of 90/9/1%
There are several explosives containing hexa- AN/HMTA/ abietic acid; prepd by making a
mine combined with either chromic oxide or homogeneous melt at ca 145° and quickly
chromic acids: coo~ng it to get finely crystal AN. This
Hexamethylenetetramine-Chromium Tetroxide, compd passed thru 16 mesh screens; and
(CH,),No”CrOq; mw 256.11, N 21 .88%; reddish brn loaded into 1.5 inch diam steel tubes, deto-
 H 81

nates at 18,700 ft/sec at d 1.24 & 13,400 ft/sec and then neutralized to a pH of 5.6, 3,7 Di-
at d 1.44 g/cc (Ref 4) nitropentamethy lenetetramine is claimed to
The use of HMTA in AN slurry explosives be formed (Ref 12)
is claimed in “Refs 6 & 7 HDN is readily sol in water; but decomposes
Refs: 1) M.R. Zhivadinovich & R. Zhiva- on standing. It is sol in ale, eth, chlf & CC14
dinovich, USP 3066139 (1962) & CA 58, It is an explosive tompound, which is less
6640 (1963) 2) W.E. Gordon, USP 3166555 powerful and much less brisant than TN’T
(1965) & CA 62, 7580 (1965) 3) W.E.
Power (by Trauzl Test) – 65% TNT; Brisance
Gordon, Ger P 1186792 (1965) & CA 63,
(by Sand Test) 18.1 g against 48 g for TNT,
4090 (1 965) 4) W.E. Gordon, Brit P
or 38% of TNT; Impact Sensitivity (with 2 kg
1014071 (1965) & CA 64, 7962 (1966)
weight), Picatirmy Arsenal App 13“ against
5) W.E’. Gordon, USP 3247033 (1966) & CA 14” for TNT and 9“ for Tetryl; Bur of Mines
65, 566 (1966) 6) G.L. Griffith, USP 3344743
App ?0 cm against 60+ for TNT and 26 cm
(1967) & CA 67, 118752 (1967) 7) D.S.
for Tetryl; Pendulum Friction Test – negative;
Partridge, USP 3496040 (1970) & CA 72,
Minimum detonating charge for 0.4 g HDN is
91877 (1970)
0.24 g. Tetryl when initiated with 0.24 g MF;
Thermal Stability, as determined by the 120?
Hexamethylenetetramine Nitrates. The following
Heat Test – S.P. (salmon pink) 145 rein,
nitrates were reported to have been prep~ by
Red Fumes 300+ reins; no explosion in 5 hrs,
various investigators: ‘
which might be considered satisfactory; Heat of
Hexamethylenetetramine Mononitrate. (CH2)6 N4. Combustion 948.4 kcal/mole
HN03; was prepd by Delepine by the action of HDN is one of the intermediate products
dilute HN03 on aqueous solns of hexamine at obtained during preparation of Cyclonite from
0° (Ref 4) hexamine. It has also been proposed for use in
When more concentrated acid is irsed, the the manufacture of an explosive, tentatively
dinitrate is obtained considered to be 1,3,5-trinitrohexahydro-s-
Hexamethylenetetramine Dinitrate (HDN) (Hex- triazine (Ref 7). Its use in an AN-slurry expl
amine (CH2)6Nq .2 HN03; mw 266.22,
Dinitrate). has “been patented (Ref 12)
N 31.57, OB to C02 -78.1%; white crystals; d Refs: 1) Beil 1, 586 (308) 2) Walker (1953)
1.63) ‘lp 160-165~ ‘Hcomb 3583 cal/g~ A~f” 288 3) H. Moschatos & B. Tollens, Ann 272,
-92.8 kcal/mole (Ref 9). UV spectra for both 280 (1893) 4) M. Del{pine, BullSocChim
the mono and dinitrates are given in Ref 11. France (3), 13, 353 (1895) and (3), 17, 110
May be prepd by nitration of hexamine with (1897) 5) R., Cambier & A. Brochet, BuIISOC
mixed nitric-sulfuric acid. For this, Hale (Ref 6) Chim France (3) 13, 394 (1895) 6) G.C. Hale,
gradually added nitric acid (d 1.42) to a 25% JACS 47, 2754 (1925) 7) M. Elbe, Ger P
aqueous solution” of hexamine at 0°. The pre- 479226 ,(1927) & CA 23, 4822 (1929) 8) Dr.
cipitated salt was separated from the acid by Konrad, Nitrocellulose 5, 123-4 (1934)
filtration through glass wool and dried after 9) M. De16pine & M. Badoche CR 214, 774
washing with cold 50/50 alcohol-ether (1942) &CA 38,5138 (1944) 9a) Blatt, OSRD
It. may also be prepd by passing formalde- 2014 (1944) 10) Avogadro di Cerrione, Ann-
hyde into a cold or alcoholic soln of NH3 and ChimApplicata 38,255 (1948)&CA 43,4633
treating the resulting product with nitric acid (1949) 11) Honorary Advisory Council for
(Ref 7) Scientific & Industrial Research,BritP615419 &
The obsd low ylds in the nitration of hexa- 615793 (1949) &CA 43,9079 (1949) 12) H.R.
mine have been ascribed to the formation, of Fee & R.W. Lawrence, USP 3318740 (1967)&
Trinitrodiaminodimethylamine, 02 NN(CH2 NN02 )2 CA 67, 55844(1967)
(Ref 10). Further nitration of hexamine-dinitrate
with coned nitric acid gives RDX (See Vol 3, Hexamethylenetetramine-Nitroform Salt.
p C614) (CH2)6N4.HC(N02)3; mw 291.27, N 33.70%,
If hexamine is treated with nitric acid, or OB to C02 –79.6%; trysts, mp 145° (dec). It was
Cyclonite Dinitrate with AC2O in sulfuric acid, prepd by refluxing for 1-.5hrs a mixt of hexamethyl-
 H 82

ene tetramine & nitroform in abs alc until a yel Note: If instead of treating the free hexamine
flocculent formed. The ppt was filtered, with peroxide, its salts are used (such as the
washed twice with abs alc and once with ether. citrate), or if hexamine is treated with peroxide
The product was not analyzed. Detonates in the presence of substantial quantities of
weakly and burns easily acid, the resulting product is Hexa~ethylene-
Refs: 1) ‘Beil, not found 2) I.J. Schnaffner, triperoxidediamine (qv)
US Rubber Co Quarterly Progress Rept No 5, Another peroxide compound was prepd by
(1 Ott 1948-1 Feb 1949), p 47 Leulier (Ref 4) and repeated by v. Girsewald
(Ref 5) ‘on treating hexamine first with hydro-
Hexamethylenetetramine Perchilorates. An ex- gen peroxide and then with nitric acid. The
plosive perchlorate was first prepd in 1916 ‘by resulting white crystals were presumed to be,
Riedel (Refs 1 & 3). It was the monoperchlo- HN:(CH2CH2”O”OH) 2,; mw 137.14, N 10.21%.
rate.’ Later, Hassel (Ref 4) prepd the mono-, It is insol in w, ale, eth & other organic sol-
hi-’ and triperchlorates by treating an aqueous vents. When wet, it is inactive, but when dry
solution of hexamine with perchloric acid, it is detonated violently by the blow of a
with or without alcohol hammer or when heated to about 130°
Following are the properties of the mono- Refs: 1) Beil 1, (308) 2) Walker (1953) 289
and diperchlorates: 3) C. von Girsewald, Ber 45, 2574 (1912) &
Hexamethylenetetramine Monoperchlorate. CA 7, 346 (1913) 4) A. Leulier, JPharmChim
(CH,),NQHCIO,; rnW 240.65, N 23.28%, OB to 15, 222 (1917) & CA 11, 2277 (1917) 5) C.
C02 & C12 -96.4%, mp 158°. Crystals; easily von Girsewald, Ber 54B, 490 (1921) & CA
sol in w imparting an acidic reaction to it 15, 2416 (1921)
It is an explosive about 65% as powerful as
TNT and less sensitive to impact (Ref 4) Hexamethylenetetramine Styphnate or Hexa-
Hexamethylenetetramine Diperchlorate. mine Styphnate. Probably C ~2H ~5N,0 ~ (struct
(CH,),Nq”2HClQo; msv 341 .12,N 16.43%, OB formula unknown); mw 385.34, N 25.45%; trysts
to C02 & C12 -28. 1%. Crystals. It is ari explo- [from NM] , mp 197-198° by fast heating
sive about 12570 as powerful as TNT and Richmond et al (Ref 2) prepd it by adding
comparable in sensitivity to ~mpact to Tetryl. one equivalent of hexamine to a satd aq soln
Lit search of CA (1947-71) uncovered no new of Styphnic Acid. The pptn of hexamine mono-
refs to explosive HMTA Perchlorates styphnate was quantitative; if the Styphnic
Refs: 1) Beil 1, (308) 2) J.B. Riedel, GerP Acid was saturated into ethanol instead of
292284 (1916) 3) O. Hassel, Norwegian water, the loss by volubility in 1:1 water-
57831 (1937) & CA 31, 6466 (1937) ethanol was only 0.25 g per 100 cc of soln.
4) Blatt, OSRD 2014 (1944) 5) Walker (1953), The mp was 196° (6° per minute rise). This
283 & 331. styphnate is much more useful than picrate as
a hexamine derivative largely because Amm
Hexamethylenetetramine Peroxides. The first Styphnate is sol in water or water-ethenol.
compound ,of this type was prepd by von Thus a soln contg one mole hexamine as a 50%
Cirsewald (Refs 1, 2 & 3) in 1912 by evapora- soln plus 2 moles of ammonia gave a 98%
ting under vacuum at 40-50°, the solution yield of Hexamine Styphnate, mp 196°
obtained by dissolving hexamine in a slight Refs: 1) Beil, not found 2) H.H. Richmond
excess of 30Y0 H202 containing a smrdl amount et al, JACS 70, 3663 (1948) & CA 43, 1316
of mineral acid, and then concentrating the (1949)
product in vacuum. The resulting Hexamethylene- Hexamethylenetetramino-Tetrazido-Copper.
tetramine Hydroperoxide (Hexamethylen- (Ns ), CU(CHZ)6 N. CU(NS)2; mw 435.33, N
Wasserstoffperoxyd in German) was a colorless 51.49%; is described by Cirulis & Straumanis,
crystalline compound, readily sol in w & ale. JPrChem 162,321 (1943)&CA 38, 1970 (1944),
It is an extremely explosive material which It is sol in aq ammonia, in Et diamine & in boiling
deflagrates on rapid heating or when brought dil nitric acid. It burns quietly in a flame but
in contact with coned H2SOa. It is stable only confined it explodes at 180–1 85°. With 1 kg
to about 70° falling weight it explodes at 10cm
 H 83

Hexamethylenetetramine-Trinitro-m-cresylate. /CH2-N:CH2 acid

(CH,),N,”C,H(CH, )(OH)(NO,),; mw 383.32,N 2N-CH2.N:CH2 + 3H202 —+
25.58%, trysts, mp 175°. Was first prepd by \CH2”N:CH2
Datta et al (Ref’2) by mixing hot benzene-.
alcohol solutions of 1 mol of hexamine and 1 ,./CH2”O”O”CH2\
mol of trinitro-m-cresylate and then allowing N-CH2”O”O”CH2-N + 2(CH2:NH)
to cool. The resulting compound exploded at \CH2”O”O”CH2’
325° HMTD
Refs: 1) Beil, not found 2) R.L. Datta, L. Trimethylenetriamine Ammonia also forms
Misra & J.C. Bardhan, JACS 45,2432 (1923) during this reaction, but it is absorbed by acid
3) Walker (1953),331 with formation of a salt
c) After all the acid has dissolved and the
Hexamethylenetetramine Triperoxide and Hexa- temperature starts to drop, stop the agitation
methylenetriamine Triperoxide. Depending on and allow the beaker to stand overnight in a
conditions HCHO + Hz 02, + oxalic acid (sic) bath at room temperature
give the tetramine or triamine peroxides. Their d) Separate the crystals by fiitering through
use as primary explosives has been patented a Bi-ichner funnel and rinse them with distilled
Refs: 1) Beil, not found 2) G4velot and Gaupilat, water, followed by 9570 alcohol (to facilitate
FrP 893942 (1944)&CA 47,8373 (1953) the drying) and then dry in air
e) Mow the filtrate to stand until the next
Hexamethylenetriperoxidediamine;3,4,8,9,12,13- day. and if there are any additional crystals,
Hexaoxa-1,6-diazabicyclo-[4,4,4]-tetradecane separate them out and purify as above
(HMTD)(formerly called by Langler, Hexa- This m@hod gives yields between 68.5 and 7 1%.
oxymethylenediamine). N; (CH2”O”O”CH2)3~N; Davis (Ref 15) uses a method of prepn which
mw 208.17, N 13.46%,0B to C02 -92.2$ZO; requires about 5 hours and cooling to 0° & below.
d (tryst) 1.57; loading density 1.05 at 100 Leulier (Ref 5) prepd HMTD from hexamine,
atm, 1.15 at, 200 and 1.30 at 800 atm /mp hydrogen peroxide and nitric acid. Konrad
145° Colorless plates or rhombic crystals., (Ref 11) used the same procedure as of
IR spectra are given in Ref 19. Was originally Taylor &. Rinkenbach and also by treating 50
prepd by Baeyer and Villiger (Ref 2) by g of ammonium sulfate with 50 g of 30% hydro-
adding 40% formaldehyde to a solution of gen peroxide and 5 g of 40% formaldehyde.
ammonium sulfate in 370 H202 at 55°. Later Properties of HMTD were examined in detail
C. von Girsewald (Refs 3, 4 & 5a) prepd it by by Taylor & Rinkenbach (Refs 6 & 7) and also
dissolving hexamine and citric acid in 30% by Konrad (Ref 11)
hydrogen peroxide Volubility at 22° (g per 100 g of solvent):
Taylor & Rinkenbach (Ref 6) modified the water 0.01; abs alc less than 0.01; ether 0.017;
Girsewald procedure and prepd HMTD as CSZ less than 0.01; CClq 0.013; glacial acetic
follows: acid 0.14; chloroform 0.64; acetone 0.33;
a) Dissolve, with stirring, 56 g of powdered glycolacetate 0.90
hexamine in a liter beaker containing 185 g HMTD is much more sol in hot water,
of 30% hydrogen peroxide (or its equivalent especially on long standing. Its aqueous solns
of stronger solution up to 40%) are stable
b) While cooling the beaker in water, Solubilities in hot water:
gradually add, with stirring, 84 g of powdered, At 60° after 2 hours 0.10%; 8 hrs 0.35; 24 hrs
crystalline citric acid, keeping the temperature, 0.50; 48 hrs 0.50
in the beaker below 30° At 75° after 2 hours 0.25%; 8 hrs 0.60; 24 hrs
The following reactions taken place, as was 1.30; 48 hrs 2.25
suggested by Marotta and Alessandrini (Refs At 100° after 2 hours 3.25%; 8 hrs 39.00%;
7a and 16, p 289) 24 hrs 68.00
 H 84

It is v slightly hydroscopic and does not g without reinforcing cap. Tetryl required
seem to be toxic. HMTD is not compatible 0.05 g using reinforcing cap and 0.06 g with-
with most metals even when it is dry. It out reinforcing cap. When 0.05 g HMTD was
attacks Al, Sn, Zn, brass, Cu, Pb and iron pressed.at 1000 psi into a No 8 capsule, it
(Ref 16). Mixtures of HMTD ‘with PA, RDX, detonated a stick of ordinary 40% dynamite
PETN and Tetryl appeared to be stable at 50° and a stick of Blasting Gelatin which had
Mixtures of HMTD with TNT or KC103 were become insensitive through age
less stable (Ref 16) HMTD is very unstable in storage. Its weight
HMTD is destroyed by caustic soln with loss is 79% in 300 days at 50°, 150 days at
liberation of ammonia (Ref 16). It can be 70° and 5 to 20 days at 90°, for material
nitrated at low temps using HN03 to give ca stored dry. Even under water it showed con-
26% RDX (Ref 18) siderable decomp” in 4 months (Ref 16)
~TD is an explosive of the initiating Although C.V. Girsewald patented the use
type; it is more powerful and brisant than MF, of HMDT as a primary explosive for deto-
rather being comparable to LA and Cyanuric nators, its sensitivity to heat, friction and
Triazide. It does not become dead-pressed even impact, its incompatibility with metals and its
at pressures of 11000 psi (an advantage over poor storage qualities make it unsuitable for
MF) practical use (Ref 16)
Explosive properties: Refs: 1) Beil 27, 771 & (647) 2) A. Baeyer
Behavior Toward Flame; when a small quantity & V. Villiger, ‘Ber, 33, 2479 (1900) 3) F. C.
is ignited, it flashes like NC, giving a flame v. Girsewald, Ber 45, 2571 (1912) & CA 7,
several inches in height 346 (191 3) 4) F.C. v. Girsewald, Ger P
Brisance by Sand Test; 0.5 g at 1000 psi 263459 & CA 7, 3843 (1913) and 274522
pressure criushes 42.5 g compared with 44.2 g & CA 8, 3122 (1914) 5) A. Leulier, JPharm-
for Cyanuric Triazide and 16.5 g for MF Chim 15, 222 (1917) & CA 11, 2277 (1917)
Power by Trauzl Test, about 60% of TNT or 5a) F.C. von Girsewald & H. Siegens, Ber 54,
230% of MF (Ref 11) 490 (1921) 6) C.A. Taylor & W.H. Rinkenbach,
Explosion temperature; explodes instantly at Army Ordnance 5, 463 (1924) 7) C.A. Taylor
200° or open flame; ignites in 3 sees at 149° & W.H. Rinkenbach, JFrankInst, 204, 369
when thrown on a heated metallic surface; (1927) 7a) D. Marotta & M:E. Alessandrini,
explodes at 130°when heated gradually (Ref Gazz Chim Ital 59, 942 (1929) 8) E.L.
16) d’Asteck, Brit P 339024 & CA 25, 2569
Friction Sensitivity; extremely sensitive (1931) and USP 1835697 & CA 26, 1125
Heat of Combustion; 4295 cal/g at constant (1932) 9) H. Muraour, Bull Soc Chim,
volume, H20 liq [4] , 51, 1156 (1932) & CA 27, “603 (1933)
Heat of Formation, 385 cal/g or 80 kg cal/mol 10) A. Schmidtj SS 29, 263 (1934) 11) Dr.
(Ref 10) Konrad, Nitrocellulose 5, 124 (1934)
Impact Sensitivity, it is v sens to impact even 12) Nuevos Expl’osivos Industrials, SA French
when wet (Ref 16) P 783682 (1935) 13) M. Patry, SS 32, 177
Velocity of Detonation, 4511 m/see at d 0.88 (1937) 14) Bebie (1943) 81 15) Davis (1943)
in column 0.22” diam 5100 m/see at d 1.1 451 15a) Blatt, OSRD 2014 (1944) 16) H.
Initrirting Action, The minimum amounts of Ficheroulle & A. Kovache, MP 31, 18,25, 26
HMTD required to detonate 0.4 g of the (1949) &CA 46,11687 (1952) 17) Walker
following HE were determined by increasing (1953), 289-331 18) K. Szyc-Lewanska & T.
the, amounts of HMTD until the amount of Urbanski, BullAcadPolonSci 6, 165 (1958)&
sand crushed was at a maximum. “(Explosives CA 52, 18464 (1958) 19) E. Ferroni et al,
and initiator were loaded in No 8 cap at 1000 ProcInternatMeetingMolSpectry, 4th, Bologna
psi pressure) (1959) 2, 762&CA 59,8267 (1963)
TNT required 0.08 g using reinforcing cap
and 0.10 g without reinforcing cap. PA re-
quired 0.05 g using reinforcing cap and 0.06
 H 85

Hexamethylolbenzene and Derivatives detonates from the impact of.30 cal bullet,
Hexamethylolbenzene or Benzenehexamethanol. fired from a distance of 90 ft. It is stable and
C(CH90H)Z; mw 198.25; trysts,’mp 302-311° does not attack metals, but it is very toxic
(Refs-2 &v3), sol in w. Prepd from C,(CH,O&.), Uses:
+ alc KOH (Ref 2); by trimerizing HC; CH.OH Germany: in mines, torpedoes, depth charges
with Ni(o) bistrimethyl catalyst u~der N (fief 3) and Naval demolition containers
or CO(C03)N0 cajalyst (Ref 4) Japan: As type A explosive it was intended
Refs: 1) Beil, not found 2) M. Chaigneau, to be used in underwater ammunition to
CR 233, 692 (1951) & CA 46, 7071 (1951) replace the type 97 explosive, TNT 60,
3) N. von Kutepow & F. Meier, Cer P 1159951 HeNDPhA 40
(1963) & CA 60, 9198 (1964) 4) Anon, FrP Refs: 1) A. Stettbacher, Protar 9, 33-45
1397654 (1965) & CA 63, 8255 (1965) (1943) 2) H. Muraour, Protar 9, 62-63 (1943)
Hexamethylolbenzene Hexanitrate or Benzene- 3) PBL Rept 53,045 (1945) 4) Op Nav 30-3M
hexamethylhexanitrate. C6(CH20N02)6; mw (1945), p 32 5) Allied and Enemy Explosives,
528.30, N 15.91%, OB to C02 –36.3%; wh powd, ml Aberdeen Proving Ground, Md (1946) p 106
176° decomp, AHcomb 2653 cal/g. Prepd. by 6) A. Stettbacher Spreng-und Schiesstoffe,
HN03 nitration of hexamethylolbenzene Rascher, Ztirich (1948) p 78
(Ref 2)
HEXAMMINES are Arnmines or Ammoniates
Impact sensitivity 3 cm or less with 2 kg (described in Vol 1, pp A275-L to A286-R)
wt on B of M machine; wt loss in 100° heat contg six NH3 groups. The following explosive
test: 0.70% first 48 hrs, 0.32% second 48 hexamrnines are described in Vol 1:
hrs, no expl in 100 hrs Hexamminecadmium (II) Bromate,
Refs: 1) Beil, not found 2) H.J. Backer, [Cd(NH, ), ] (Br0,)2 (p A277)
RecTravChim 54, 833 (1935)&CA 30, 1367 Hexamminecadmi~m (II) Chlorate
(1936) 3) Blatt, OSRD 2014 (1944) 4) Pic- [Cd(NH,),] (C10,)2 (p A277)
ArsnChemLabRepts 123718& 123975 (1948) Hexamminecadmium (II) Perchlorate
[Cd(NH,), ] (C1O.), (p A277)
Hexamminechromium (III) Azide
Hexamine. Same as Hexamethylenetetramine, de- [Cr(NH, ),] (N,), (p A277)
scribed on p H 79ff Hexamminechromium (111)Nitrate
[Cr(NH,), ] (NO,), (p A277)
Hexamminechromium (111)Perchlorate
Hexamine Derivatives are described under Hexa- [Cr(NH, ), ] (CIO,), (p A277)
methylenetetramine on pp H80 to H84 Hexamminecobalt (III) Chlorate, Monohydrate
or “Luteocobalttriammine Chlorate,”
[CO(NH,), ] (C1O,), .H2 O (p A280)
Hexamine Explosives are described as Hexa- Hexamminecobalt (111)Chlorite, Monohydrate,
methylenetetramine Explosives [CO(NH,), ] (CIO,), .H20 (p A280)
Hexamminecobalt (III) Hexanitrocobalta{e,
[CO(NH, ), ] Co(NC),), (p A280)
Hexamit. See Novit
Hexamminecobalt (111)Iodate,
[CO(NH,), ] (10,), (p A280)
Hexamite (Called Hexanite or NTD2 by the
Hexamminecobalt (111)Nitrate
U.S. Navy; Schiesswolle TSMV 1-101 by
8 and
[CO(NH,), ](NO,), (p A280)
the Germans; OtsuB or Type A by the
Japanese). It consists of TNT 60/HeNDPhA Note: Addnl info is given be(ow
24/Al 16; greenish-gray solid,d 1.72, mp 80-90° Heramminecobalt (III) Perchlorate, Monohydrate
(can be cast loaded); Ballistic Strength 130% or “Luteocobalttriammine Perchlorate
TNT (due to the addn of Al); Brisance ca 46 [CO(NH, ), ] (C1O.), .H,O (p A280)
g sand crushed vs 43 g for TNT; Explosion Hexamminecobalt (III) Perchlorate,
Temp 200-260°; Deton Vel 6900, m/see; [CO(NH,), ] (CIOQ), (p A280)
Impact Sens (Pie Ars app with 2 kg wt) 1o“ Hexamminecobalt (II) Perchlorate,
vs 14“ for TNT; Rifle Bullet Sensitivity [CO(NH, ), ] (C1O. )2 (p A280)
 H 86

Hexamininecopper (II) Chlorate, ounces for materird dried over Ca sulfate

[CU(NH, ), ] (C1O,), (p A281) (Ref 4)
Hexamminenickel “(II) Azide, See also Table A in Vol 1 of Encycl, p
[Ni(NH, ),] (N,), (p A281) A277 and the following Refs
Hexamminenickel (11) Bromate Refs: 1) .W.R. Tomlinson, “Explosive pro-
[Ni(NH, ), ] (BrO,), (p A281) perties of Complex Compounds,” PATR 1364
Hexamminenickel (II) Chlorate, (Nov 1943) 2) Ibid, PATR 1632 (Ott 1946)
[Ni(NH, ),] (CIO, ), (p A281) 3) J.E. Abel et al, “Development of A New
Hexamminenickel (II) Iodate, Ignition Temperature Apparatus,” PATR 2093
[Ni(NH, ), ] (10,), (p A281 ) (Nov 1954) (Activation Energy 29.82 kcal/mol
Hexamminenickel (II) Perchlorate, vs 23.74 for Lead Azide & 29.81 for Mercury
[Ni(NH, ), ] (C1O, ), (p A281) Fulminate) 4) A.C. Forsyth, S. Krasner &
Hexamminezinc (II) Chlorate, R.J. Gaughran, “An Investigation Concerning
[Zn(NH, ), ] (CIO,), (p A282) Stab Sensitivity Versus Loading Density of
Hexamminezinc (11) Nitrate, Some Initiating Compounds,” PATR 2146
[Zn(NH, ), ] (NO, ),, listed on p A282 but (Feb 1955)
not described. It refers to Ref 23, which is D.B.
Donskaya & M.A. Portnov, ZhObshchKhim 9, Hexamminecobalt (III) Nitrate. [CO(NHJb] (N03)3
526-31 (1939) & CA 33, 9091 (1939) mw 347.20, N 36.32Yo; sol in hot s] acid w; in-
Refi See Vol 1, pp 1, 3, 7, 8, 10, 11, ha, 14, SO1in ale; AHfO = -311.5 kcal/mole (Ref 2).
15, 16, 22, 23, 24, 39, 41, 42, 43, 46, 49, 67, Prepd by reacting a cobalt nitrate hexahydrate
68, 69, 71, 72 soln with AN and coned ammonia and then air
Note: Destruction of cobaltic ammines, such as oxidizing Co (II) to Co (HI) or treating hexam-
of hexammine by means of thiosulfate in acid mine cobalt (II) chloride with coned nitric acid
soln was described by L.M. Orlova, ZavodLab (Ref 1); by reacting CO(NH,)3 with AN in liq
8, 502 (1939) & CA 36, 6935 (1942), which is ammonia at 100° in an autoclave (Ref 3)
listed in Vol 1, p A286-R DTA and gas evolution curves are given in
Ref 4. Explosive characteristics such as: output,
Hexammine, Calcium. Probably Ca(NH3)6. The impact sensitivity, and autoignition temp are
compd decomposes explosively when heated in given in Ref 6. Addtional impact and friction
vacuum. The temp of explosion depends on sensitivity data are found in Ref 5 which also
the degree of vacuum. Products of the decomp gives confined deton vel as 3000 m/see &
are Ca nitride & hydride and hydrogen (Ref 1) unconfined deton vel as 2700 m/see
However, later studies (Ref 2) suggest that Refs: 1) J. Bjerrum et al, Inorg Synth 2, 218
Ca Hexammine explosions are due to impurities (1946) 2) K.B. Yatsimirskii & L.L. Pankova,
which catalyze its decomposition JGenChem (Russ) 19, 61 7-22(1 949)&CA 43,’7805
Refs: 1) E. Botolfsen, BullSocChim 31, 56 (1948) 3) O. Schmitz-Dumont, et al ZAnorg-
(1922) & CA 16, 4154 (1922) 2) A.C. Pappas, Chem, 253, 118 & CA 43, 7805 (1948)
ActaChemScand 3, 36 (1949) & CA 43, 785 4) W.W. Wendlandt, JInorgNuclChem 25, 545
(1949) (1963) & CA 58, 12157g (1963) 5) Hartmut
Preller, Explosivstoffe 12, (8), 173-4 (1964) &
Hexammine Chromic Perchlorate. [Cr(NH3)J CA 61, 14455 (1964) 6) C.W. Hoppesch, et
(C104),; mw 452.57. This inorg coordination al AmChemSoc, Div Fuel Chem, Preprints 7,
compd was studied from the standpoint of its (3) 235-41 (1963) & CA 63, 2839 (]965)
stab sensitivity vs loading density for possible
use as an initiating compd. It was found to Hexammons. See Gheksamony in Vol 6, PG73-R
increase in sensitivity until an apparent max
point was reached. The stab sensitivity of the
compd also appeared to be affected by
humidity. The compd exhibited a sensitivity
of 28 inch-ounces /as compared to 12 inch-
 H 87

HEXANE AND DERIVATIVES liq, bp 193– 194”, d 0.949 at 20°; insol in water;
n-Hexaine (called Hexan’in Cer); CH3 (CHZ )4. sol in ale. IR and UV spectra given in Ref 2.
CH3; mw 86.17; colorless vol liq, mp -94.3°, bp Prepd by reacting hexane with fuming nitric
68 .7~flp -9”F, auto ignition temp 500”F, d of acid which also gives:
liq 0.659 at 20°, vap press .100 mm at 16°, 2-Nitrohexane, CH3 CH(N02 )C4H9; liq, bp 176°,
AHfO = -39.96 kcal/mol, refr index 1.3749; S1 d 0.936 at 20°. It pyrolizes unimolecularly with
sol in w; sol in ale, acet, eth, and chl. Mod an activation energy of 40–45kcal/mole (Ref 3)
toxic in inhalation and ingestion; pure hexane Refs: 1) Beil 1, 147 & {395} 2)R.N.
reacts explosively with 02 at 227° (Ref 2). Haszeldine, JChemSoc 1953, 2525 & CA
Hexane occurs in crude petroleum and can be 48, 1812 (1954) 3) V.V. Dubilkin et al,
obtained by fractional distillation. It is used as Izv Akad Nauk SSR (1971), 1554 & CA 75,
a solvent, in low temp thermometers, as a 98016 (1971)
paint diluent, and as a polymerization reaction
medium. It is the parent comp for the following Dinitrohexanes, C6H ~2(N02)2; mw 176.20, N
potentially expl derivs: 15.90%. The following isomers are known:
Refs: 1) Beil 1, 142, (51) [105] & {374} 1,1-Dinitrohexane, (OzNh CHC5 HI ~ ; yel oil,
2)” C.F. Cullis, Bull Fr 1950, 863-8 & CA 47, bp 80.5°at 1 mm, d 1.091, RI 1.4432 at 25°
2689 (1953) (Ref 2), insol in w, sol in alc & eth. Prepd by
nitrating methylhexylketone or hexane
Azidohexanes, C6H13 N3, mw 127.22, N 33.04%. Refs: 1) Beil 1, 147& <357> 2) L. Ershova
The folIowing isomers are known: et al, IzvAkadNauk, SSSR 943 (1 959)&CA 54,
l-Aziddhexane, Triazohexane or Hexyl Azide. 259 (1960)
N3CH2C5HII ; liq, bp 156–157°, RI 1.4325 at l,2-Dinitrohexane, NOZCH2CH(NOZ)C4H9; liq.
20° (Ref 2), sol in eth, Qcomb 1045kcal/mole, Prepd by reacting 1-hexane with an equilibrium
AHfO –36.2kcal/mole (Ref 6). Prepd by heating mixt of N02 & N204 to give 1,2-dinitrohexane
hexyl bromide, NaN ~, aq MeOH in sealed tube & 1-nitro-2-hexanol nitrite
for 6 hours; adding dropwise hexyl iodide to aq Refs: 1) Beil, not found 2) G.A. Bonetti et
NaN3 in aq PrOH & refluxing (Ref 4). LOW al, USP 3192248(1965)&CA 63, 11361 (1965)
toxicjty less than NaN ~ (Ref 3) 2,4-Dinitrohexane, CH3CH(N02)CH2CH(N02 )C2H5 ;
Used as a foaming agent in caprolactam liq, bp 177-79° at 0.5mm, d 1.100, RI 1.4482 at
polymerization (Ref 5) 25° (Ref 2)
Refs: 1) Beil 1, <357> 2) V.P. Tsybasov &
Refs: 1) Beil 1, {2533} & <358> 2) K.
V.F. Petrovich, IzvVysshikhUchebnZavedenii,
Henkel & F. Weygand, Ber 76B, 812 (1943) &
Khim iKhimTechnol 5,942 (1962) & CA 59,
CA 38, 1743 (1944) 3) F.E. Roth et al, Arch-
InternPharmcol 108,473 (1957)&CA 51, 10730 3756 (1963)
3,4-Dinitrohexane. C2H5 CH(N02)CH(N02)C ZH5;
(1957) 4) E. Lieber et al, JOrg Chem 22,
pale yellow liq, bp 50–54° at 0.3mm, RI 1.4512
238 (1957) & CA 51, 16279 (1957) 5) Belg-
at 25°, sol in chlf. Prepd by reacting 1-nit ropro-
P 663494& CA 60, 13411 (1964) 6) J.W.
pane in an alkaline chloroform mixt with an aq
Murrin & C.A. Carpenter Mem Rept No 129,
soln of Na.persulfate, Na-acetate & Ag-nit rate
US Nav Powd Fact (1957)
(Ref 2)
2-Aztiohexane. CH3CH(N3)C4H9; liq, bp 96– Refs: 1) Beil 1, f 357> 2) A.H. Pagano & H
98° at 160mm, RI 1.4353 at 20°, d 0.857, opt Shechter, JOrgChem 35 (2), 295 (1970) & CA 72,
rot +27.8° at 25” (Ref 2). Prepd by adding 2- 78205 (1970)
iodohexane to NaN3 in aq MeOH and heating in
sealed tube Tetranitrohexanes, C6HION408; mw 266.20, N
Refs: 1) Bed 1, {396} 2) P.A. Levene et al 21.05%. Two isomers are known:
1,1, 1,3-Tetranitrohexane,
CH~(CH2)2CH(N02 )CH2 C(N02 )3; trysts (from
Nitrohexanes, C6H13 N02; mw 131.20, N 10.68%, hexane), mp 37.7–38°; was prepd by addg 1,1,1-
The following isomers are known: trinitro-3-aci-nitrohexane to a vigorously stirred
l-Nitrohexane, 02 NCH2C5 HI ~ ; colorless fluid soln of urea in MeOH (Refs 1 &4)
 H 88

3,3,4,4- Tetranitroh exane, Refs: 1) Beil, not found 2) Aerojet-General

c2H5c(N02)2C(NOz) zCz&; wh waxy C@S, STIP Corp FP 1319705 &CA 59, P9791 (1963)
106–07°; was prepd by treating 3 ,4-domotrp- 3) G.B. Linden, USP 3101378 (1956)&CA 60,
hex-3-en with liq N205 at 85° (Refs 2 & 3) P1589 K1964) 4) H. Gold, Nitro Compds Proc
Refs: 1) Beil 1, z 357> 2) Beil 1, <358> Intern Symp, Warsaw 1963, 449–61 &CA 64,
3) C.E. Grabiel, JACS 77, 1293 (1955) & CA 50, 1184(1966)
1571 (1956) 4) S.S. Novikov et al, BullAcad- Tetranitrohexanediols, (HO)zCIjH~(N()~)~; mw
Science(USSR) 1959, 1765 (Engl) 298.20, N 18.79%, OB to C02 –37.6%. The fol-
lowing isomers are known:
1,1,6,6-Tetranitro-2,5-hexanediol.
Hexanediol and Derivatives (N02)2CHCH(OH)CH2 CH2CH(OH)CH(N02 )2;
1,6 Hexaneciiol or 1,6 hexamethylenegly col. brown liq; sol in CH2 C12. Prepd by suspending
CHzOH(CH2)qCHzOH; mw 118.17; low melting di-K salt of Me(NOz )2 in water and adding
needle-like solid or colorless liq, mp 42°, bp (CH2CHO)2 & then neutralizing with sulfuric
250~fl p266°F, d 0.953; sol in water & ale; acid. Used as an intermediate. It is exnl
s] SOl in hot eth; low toxicity. Prepd by Refs: 1’) Beil, not found 2) H. Plaut, USP
reduction or hydrogenation of adipic acid esters. 2544103 (1951) & CA 45, 7587 (1951)
Used as solvent and resin intermediate. It is the 2,2,5,5-Tetranitro-l,6-hexanediol.
parent compd, for the following derivs, none of 0HCH2C(N02)2CH2 CH2C(N02)2CH20H; crysts,
which appears to be explosive mp 126–27° (recrystd from w); sol in Et20 & w.
Refs: 1) Beil 1, 484 (251) [551] & {2201} Prepd by mixing MeOH soln of tetranitrobutane
2) Cond Chem Diet (8 Edit) (1971) p 443 with formalin and adding small amount of NaOH;
adding 1,4-dinitrobutane to aq NaOH & then
Dinitrohexanediols, (H0)2C6H’10(N02)2; mw adding formalin & finally an aq soln of NaN02 &
208.20, N 13.46%. The following isomers are AgN03. No expl props mentioned, but it is expl
known: Refs: 1) Beil, not found 2) H. Feuer et al,
2,5-Dinitro-3,4-h exanedwl. JOrg Chem 27, 3598 (1962) & CA 57, 14921
H3CCH(N02)CH(OH)CH(OH)CH(N02)CH3 ; (1962)
trysts, mp 111-112° (from EtOH/ water), 163- 2,5-Hexanedioldinitrite. CH3CH(ONO)CH2CH2
165° (from EtOH) (Refs 2, 3 & 4). Prepd by CH(ONO)CH3; liq, bp 56° at 33mm, d 1.042, RI
treating glyoxal in alk soln with EtNOz, 1.3978, at 25°; insol in w. Prepd by treating aq
neutralizing Na-salt with HOAC, & extracting (CH3 CHOHCH2)2 at 0° with aq NaN02 and then
with nitromethane (Ref 1); by adding OZN adding 6N HC1. The kinetics of its decompn were
(CH,)qNO, to aq NaOH, and when salt form is also studied
complete treating with aq foimald and HOAC
Refs: 1) Beil,, not found 2) L.P. Kuhn et al
(Ref 2 & 3)
JACS 78, 2719 (1956) & CA 50, 14506 (1956)
Refs: 1) Beil, not found 2) H. Plaut, USP 2,5-Hexanedioldin itrate, or 2,5 Dinitroxyhexane.
2616923 (1952) & CA 49, P 1170i (1955) CH3CH(ON02)CH2CH2 CH@NOz)CH3; mW 208-20~
3) H. Feuer & R. Miller; JOrgChem 26; 1348-57 N 13.46%, OB to C02 –92.2%; trysts, mp 50.4°,
(1961) & CA 56, ‘1334 (1961) 4) H. Feuer
vap press 0.98–1 .33, 6.1–9.4 & 19–31 at 20, 30
A.T. Nielsen & C.E. Colwell, Tetrahedron, 19, & 40° resp, heat of fusion 13.2kcal/mole, heat of
SUPpl 1, 57-64 (1963) & CA 59, 11229 (1963)
vaporization 13.0 kcal/mole. Prepd by nitration
5) E.S. Lipina, V.V. Perekalin, Ya. S. Bobovich,
of 2,5 hexanediol. No expl props mentioned
ZhObshchKhim 34(1), 3635-40 (1964) & CA
62, 9043 (1965) Ref 1) Beil, not found 2) M.D. Kemp et al,
JPhysChem 61, 240 (1957.) & CA 51, 8524
5,5-Dinitro-l,2-hexanedio 1.
(1957)
H2C(OH)CH(OH)C2 H4C(N0 z) *CH ~; liq, RI
1.4804 at 250, sol in CH ~C12. Prepd by adding 2,3,4,5-Hexanetetro ne-tetraoxime Diperoxide or
Dimethyltetracetone tetraoxime Diperoxide
MeOH soln of CH3C(N02),(CH2)2 COCHZOH
to cold alk soln of NaBHQ & acidifying with N“o” O“N
H2SOA (Refs 2 &3) Has anti-bacterial, fungi- H3 CC . C CCH3 ; mw 186.15, N 30.10%
cidal & anti-inflammatory props (Ref 4) NOON
 H 89

OB to C02 –77.4%; trysts (from eth), mp 181R Prepd Hexanitroazobenzene. See under Azobenzene
by reacting (CZN202)C(NOH)CH31 in ether with Vol 1, p A649
N20q; or reacting the above oxime with 50%
nitric acid and aq KMnOq. No explosive props Hexanitrocarbanilide or sym-Dipicrylurea. See
are mentioned N,N’-Bis(2,4,6-trinitrophenyl)-urea in Vol 2,
Refs: 1) Beil, not found 2) G. Ponzio & p B156-L
V. Bernardi, AttiAccadSciTorino 59, 693
(1924) & CA 19, 469 (1925) 3) G. Ruggeri, Hexanitrocompounds are described under cor-
Gazz chim ital 54, 72 (1924) & CA 19, 2187 responding parent substances
(1925) 4) Nothing more recent found in CA
Hexanitrodiphenylamine. See under Diphenyl-
Hexanetriol and Derivatives amine in Vol 5, p D1 434-R
l,2,6-Hexanetriol. 0HCH2CH(OH)(CH2) 3CHZOH;
mw 134.20; colorless liq, fl p 32.8°, bp at 5mm Hexanitrodiphenylsulfide. See under Diphenyl-
178: flp 380° F,d 1.10, RI 1.476 at 20° (Ref 3); sulfide in Vol 5, p D1477-R
s61 in w; low toxicity. Prepd by hydrogenation
of 2-hydroxyadipic aldehyde over Raney Ni Hexanitrodiphenylsulfone. See under Diphenyl-
(Ref 2). Used as resin intermed, softener & sulfone in Vol 5, p D1480-L
solvent
Refs: 1) Beil, not found 2) V.1: Karzhev & Hexanitrodipheny loxide. Same as Hexanitro-
B. Ya. Rabinovitch, Neftekhimia 3 (2) 267 diphenylether, Vol 5, p D1453-R
(1963) & CA 59, 6240 (1963) 3) H. Meister.
Ber 98, (9) 2862 (1965) & CA 63, 13233 2,4,6,2’,4’,6’-(Hexanitrodiphenyl)-ethylene-di-
(1965) nitramine or N, N’-Di(2,4,6-trinitrophenyl-
1,2,6-Hexanetrioltrinitrate (HTTN). 02 NOCH2 nitramino)-ethane (Code named Bitetryl,
CH(ON02)C ~H6CH20N02; mw 269.20, N 15.61%, Ditetryl or Octyl). See 1,2-Bis(2’,4’,6’-trinitro-
OB to C02 –50.5%; light tan liq melts below –5 10, d nit ranilino)-ethane in Vol 2, p B131 -R
1.39, S1sol water, v sol eth, acet, non-
hydroscopic. Obtained by mixed acid nitration Hexanitrodiphenyl Guanidine. ” See N, N’-Bis
of hexanetriol at 0°, separating HTTN, washing (2,4,6-trinitrophenyl)-guanidine in Vol 2,
and stabilizing with NaHC03 soln. Proposed as p B154-R
a substitute for NC in dynamites
It, has an impact sens of 76 cm on B of M 2,4,6,2’,4’,6’-Hexanitrodiphenylmethylamine.
machine with 2 kg weight & will not explode See under Diphenylmethylamine in Vol 5,
in friction pendulum test. Its vacuum stability p D1468-L
is 0.8 cc of gas in 40 hours at 100° N,N’-Hexanitrodiphenylpropane-1,3-dinitramine.
Refs: 1) Beilj not found 2) J .B. Bronst ein Jr, One of the names for Methylene Ditetryl
USP 2683164 (1954)&CA 48, 11062 (1954) described as 1,3-Bis(2’ ,4’,6-trinitro-N-nit ranilino)-
propane in Vol 2, p B1 33-L
Hexanhexol. See Dr.dcitol and Derivatives in
Vol 5, p D1567-R N,N’-(Hexanitrodiphenyl)-propylene-1,3-dinitra-
mine (Code named Methylene Di$etryl). ,See
Hexanites or Schiesswolle (in Cer)
neuer Art, 1,3-Bis(2’,4’,6’-trinitro-N-nitranilino)-propane in
are cast charges of 60/40 TNT/Hexanitrodi- Vol 2, p B133-L
phenylamine
Ret Anon “Explosivstoffe” Wasag-Chemie AC. Hexanitrodiresorcin or 2,4,6,2’,4’,6’-Hexanitro-
Essen, (1961) p 76 3,5r3’,5’-tetrahydroxy diphenyl. See Hexanitro-
biresorcinol under 13iresorcinol and Derivatives in
Hexanitrate Dulcitol. See Dulcitol Hexanitrate Vol 2, p B127:L
in Vol 5, p D1567-R
 H 90

Hexanitrodiresorcinol. See Hexanitrobiresorcinol be useful in the prep of high energy poly-

under Biresorcinol and Derivatives in Vol 2, urethane propellants
p B127-L Refi 1) Beil, not listed 2) K. Klager USP
2978475 (1961) ,& CA 55, 19799 (1961)
Hexanitrodulcite. See under Dulcitol Hexanitrate
in Vol 5, p D1567-R Hexanitrooxanilide or N,N’-Dipicryloxamide.
See under Oxarnide
Hexanitroethane. See under ethane and deriva
tives, in Vol 5, p E149-L ‘ Hexanitrophenolanthrone. The name given in
JCS 100(1), 656 (1911) for the compd listed
Hexanitrohydrazobenzene or N, N’-Dipicryl- in Vol 2, p B147-L as 10,10-Bis(4-hydroxy-
hydrazine. See Vol 5, p“D1463-L phenyl)-x,x,x,x,x,x-hexanitro-9-anthranone

Hexanitrohydrocellulose. See under Hydro- Hexanitrosobenzene. See under Benzene and

cellulose Nitrates in this Vol Derivatives in Vol 2, p B45-L

Hexanitroinositol. See under Inositol and Hexanitrosorbitol. See Sorbitol Hexanitrate

Derivatives in this Vol under Sorbitol and Derivatives

Hexanitromethylphenylether or Hexanitro-4- Hexanitrosulfobenzide. Same as Hexanitrodi-

methyldiphenyl (02 N)3C6HzOCbH(CH3)
ether. phenylsulfone, Vol 5, p D1480-L
(N02), (Note -The position of the NO,
groups has not been established); mw 452.23,
N 18.59%, OB to C02 –53.1%, mp 103.5°. Hexanols and Derivatives
Crystrds (from hot alcohol); may be prepd by Hexanols, C6H14 O, mw 102.17. The following
boiling 4-nitro4’-methyldiphenylether (or 4- isomers are known:
nitro-2’-methyldiphenylether) with strong l-Hexanol or n-Hexyl A Icohol,
nitric acid for 45 minutes and then pouring H3C(CH2)4CH20H; colorless liq, sp gr 0.822
the solution into a large amount of cold (15/40), fr p –51.6°, bp 157.5°, RI 1.4169 (25°)
water. This separates a light yellow oil which 2-Hexanol or Butylmethylcarbinol,
turns into crystals that are very slightly sol H3CCHOHC4H9; colorlessliq,spgr0.818
in w; sol in bz, eth, acetic acid, carbondisulfide (16.8 /49, bp 140°, RI 1.4126 (Ref)
and hot alcohol; difficultly sol in cold alcohol. 3-Hexanol, ~ & CHOHC4 ~ ; colorless liq, sp gr
When ignited in the flame of a lamp it 0.818 (20/40), bp 135°
deflagrates Ref 1) Beil 1, 407–08, (202), [437–38] &
Recently the 3’-Methyl-2,2 ‘,4,4‘,6,6!-hexanitro- {1660}
diphenyl Ether, mp 141-42°, has been prepd by
the mixed acid nitration of the corresponding Dinitrohexanols, C6H12N205; mw 192.20, N
pentanitro diphenyl ether (Ref 4) 14.58%. The following iwmers are known:
Refs: 1) Beil 6, 394 & (200) 2) A.N. Cook, 2,6-Dinitro-l-hexarw 1.
JACS 25, 64 (1905) 3) A.N. Cook & F.N. OHCHzCH(NOz)(CHz)~ CHzN02; yel liq, bp
Sherwood, JACS 37, 1836 (1915) 4) G. decomp, RI 1.4745 at 20°; sol in CH2C12. Prepd by
Adamska & K. Okon, Rocz Chem 42, (10), reacting 1,5 dinitropentane with aq NaOH then
1681 (1969) & CA 70, 37355 (1969) formalin (37% soln) and acetic acid
Refs: 1) Beil, not found 2) A.T. Nielsen,
3,3,5,5,7,7 Hexanitro-1,9-nonane Diisocyanate. JOrgChem 27, 1993 (1962) & CA 57, 45569
mp 127 ~ 1°. Prepd by heating at 80° (1962)
4,4,6,6,8,8 hexanitro-1 ,11-undecandioicazide 5,.5 Dinitro-2-Hexanol. H3CCH(OH)(CH1)2C(N02)2
(mp 84 f 1°) which in turn is made by CH3; yel liq, bp 104° at 0.6mm, RI 1.4636 at 20°,
treating the corresponding dibasic acid with d 1.24; sol in eth. Prepd by adding aq NaBH4 to
sodium azide. The diisocyanate is claimed to MeOH SOlnof CH3CO(CH2)2CH3 with the pH of
 H 91

mixt constantly adjusted with H 2S04 at 3–4 ~.NHI N.N:N.N:N.N:C 0 NH.~ ;mw 224.16,
XNH.N
NNH-C:
Refs: 1) Beil, not found 2) H. Shechter et al,
JACS 74, 3664 (1952) & CA 47, 5886 (1953) N 87.49%
l-Nirro-2-Hexyl Nitrate. ‘02 NCH2CH(ON02)
(CHZ)SCHS; prepd by first obtaining l-nitro-2- (of all known organic compounds, this is the
hexylperoxynitrate by reacting 1-hexene in CC14with richest in nitrogen), mp (explodes at
Oxygen & N20q and then treating with N02. about 900). Leaflets, was prepd by Hofmann
It is used as a fuel additive & intermediate in et al from 5-diazotetrazol hydrochloride, hydra-
preps of surfactants, insecticides, etc zine hydrochloride and sodium acetate at a
Refs: 1) Beil, not found 2), D.R. Lachowicz very low temperature
& K.L. Kreuz USP 3282983 (1966) & CA 66, According to Karrer (Ref 4), it may be
10577 (1967) prepd by diazotizing 5-aminotetrazole and
coupling the resulting compound with hydra-
zine
Stable at room temp; powerful explosive. If
Hexanones and Derivatives some dry crystals are scattered loosely on a
Hexanones, C6H12 O; mw 100,16. The following piece of cardboard and one of the crystals
isomers are known: touched with a flame or heated object (rod etc),
2-Hexanone or n-Butylmethyl Ketone, the material will detonate with such brisance
CH 3COC4H g, colorless liq, SPgr 0.816 (15/40), fr p that each crystal will puncture the cardboard
–56.9; bp 127.2°, fl p 95.8°F.. Very toxic Refs: 1) Beil 26, (123-24) 2) K.A. Hofmann
Ref Beil 1,689, (354), [745] & {2826} & H. Hock, Ber 44, 2953 (1911) 3) F.R.
3-Hexanone, C 2H5COCH2C2H~; colorless liq, sp gr Benson, Chem Revs 41, 9 (1947) 4) Karrer
0.813 (21 .8/40), bp 123–24° (1950, ed) p 803 (under Tetrazole)
Ret Beil 1,690, (354), [746] & {2830}
Hexazidocuprate-Lithium Salt. [CU(N3 )6] ; mw
L4
Dinitrohexanones, C ~H lo N2 05; mw 190.18, N 343.49, N 73.42%; trysts with 3H20 which is
14.73%. The following isomers are known: lost above 120°. The anhydrous compound ex-
5,5-Dinitro-2-h exanone, plodes at 224-5°. Prepd by dissolving Cupric
HSCCO(CHZ)ZC(NO*)ZCHS ; hq, Spgr 1.264, ~ Azide in aq or alc soln of Lithium Azide
1.4607 (200), bp 110° at 1.3mm; sol in CH2C12.
Refs: 1) Gmelin, Syst No 60, Teil B, 150 (1958)
Prepd by adding dioxane solns of CHZ(NOZ)Z 2) M. Straurnanis & A. Cirulis, ZAnorgChem 252,
& PhCH2NMe30H to C2H5CH:CH2. After 9 (1943)&CA 38,3563 (1944)
65 hrs stirring mixt is poured into w & acidi-
fied and product extracted with CH2C12. It is iXPl Hexazidostannate-Sodium Salt. Na2 Sn(N3 )Ij,
Refs: 1) Beil, not found 2) H. Shechter’& probably Sn(N3)a “2NaN3; mw416.85, N 60.50%0
L. Zeldin, JACS 73, 1276 (1951) & CA 45, white solid, S1sol in eth or benz. Prepd by heating
9459 (195 1) a tetrahydrofuran soln of SnC14& NaN3. Hydro-
4,4-Dinitro-3-hexanone, lyzes in moist air. Explodes on boiling over an
H5C2COC(N02)2C2H5; liq, bp 69–71 “at 1 mm, RI open flame
1.4548. Prepd by reacting EtC :CEt with N204 in
Refs: 1) Gmelin, Syst No 46, Teil 61, 145–46
dry Et20 and distilling the resulting oil. It is expl
(1972) 2) E. Wiberg & H. Michard, ZNatur-
Refs: 1) Beil, not found 2) J1. Freeman &
forsch 9b, 500 (1954)&CA 49,768 (1955)
W.D. Emmons, JACS 70,1712 (1957)

Hexazobenzene. See Diazidobenzene in Vol 2,

HEXAZADIENES (Hexazdien in German). p B42-R
Hexazadienes are derivatives of NH: N. NI-LNH.
N:NH Some of them are explosive, for instance:
1,6-Bis- [tetrazoiinyiidene- (5)] -hexazadiene or
1,6--Di- [tetrazolyl-(5) -hexazadiene] (Bisdiazo-
tetrazolhydrazide old German),
 H 92

Hexenes and Derivatives phthallic anhydride (Ref 3)

Hexenes or Hexylenes, C~Hl~;mw84.18. Six Refs: 1) ‘Beil 1, {806}& <836> 2) H.B. Hass et a],
isomers are described in Beil. Three of them: 1-, JOrgChem 15, 8 (1950) & CA 44, 4412
2-, and 3- are described below together with their (1950) 3) T.M. Khannanov et al, Trudy Kazan-
nitrated derivs Khim Tekhnol Inst 26, 59 (1959) & CA 54,
l-Hexene or Hexylene, C6H10 :CH ; mw 84.16, 24345 (1961) 4) F.I. Carroll et al, JOrgChem
colorless liq, fr p –139.8°, bp 63.6°, fl p –1 ST, ,28, 1236 (1963) & CA 58, 12408 (1963)
d 0.673, RI 1.3876 at 20°; insol in w; sol in ale. 5) W.D. Deichrnan et al, Ind Med Surg 34
Prepd by reaction of PrMgBr & allylbromide. (10), 800 (1965) & CA 64, 4153 (1966)
Highly flammable and moderately toxic 3-Nitro-2-hexene. H3CCH:C(N0,)C ,H,;
Refs: 1) Beil 1,215, (89), [191], {800} & c 828> liq, bp 70.9° at lornm, d 0.9797, RI at 25°1.4545
2) CondChemDict, 8th Edit (1971), p 444 (Ref 3), sol in benz. Prepd by refluxing C3H7-
l-Nitro-l-hexene. HC(NOZ):CHC4H9; mw 129.18, CH(N02 )CH(OAC)CH3 with dry benz containing
N 10.84%; liq, bp 54–55°at 1.5 mm, R] at 25° Na-carbonate (Ref 2). Toyicity about same as
1.4581. Prepd by refluxing BUCH(OAC)CHZN02 2-nitro-hexene
in benzene containing Na-carbonate Refs: 1) Beil 1, <836> 2) Same as 2
Refs: 1) Beill, 433> 2) N.L. Drake & above 3) K.F. Lampe et al, JChemEngData
A.B. Ross, JOrgChem 23, 717 (1958) & CA 53, 7 (1) 85 (1962) & CA 57, 8414 (1962)
12215 (1959) 3) F.I. Carroll et al, Ibid 28, 4) Same as 5 above
1236 (1963) & CA 58, 12408 (1963) 4-Nitro-2 hexene. H, CCH:CHCH(NO,)C,H,;
2-Nitro-l-hexene (called 2-Nitro-hexen(l ) in Ger), mw 129.1, N 10.8%; yellow-green liq, bp 72°
H2C:C(N02)C4H9; liq, bp 81–2°at 50mm at 10mm, d 0.9833, RI at 25° 1.4572, sol
(Ref 1), RI at 25°1.4462. Prepd by treating in benz. Prepd by refluxing CH3CH(OAC)CH ~
Et2NH aq with aq HCHO (37%) & then with CH(N02)CZH5 in dry benzene containing Na-
C5HI ~N02 to give 2-nitrohexyldiethy lamine carbonate
whose HC1 salt is pyrolyzed to yield the desired Refs: 1) Beil, not found, 2) same as 2 above
nitroalkene (Ref 2); also by distilling under re- 5,5 Dinirro-2-hexene. H, CCH:CHCH,C(NO,),
duced pressure 2-nitro-l-hexanol & phthallic- CH3; mw 174.18, N 16.08%; liq, bp 60–70° at
anhydride (Ref 3) l-2mm, RI at 25° 1.4555, sol in hexane.
Refs: 1) Beil 1, {804} 2) A.F. McKay et al, Prepd by heating 5 ;5-dinit ro-2-hexanol with a
JACS 70, 430 (1948) & CA 42, 2228 (1948) few drops of coned sulfuric acid
3) M. Masaki & M. Ohta, Bull Chem Soc Refs: 1) Beil, not found 2) G.B. Linden,
Japan 35, 1808 (1962) & CA 59, 424 (1963) Brit P 936087. (1963) & CA 61, 6920 (1964)
2-Hexene, &Hexylene or I-Methyl 2-propyl 3-Hexene, s-Diethylethylene or y-Hexylene.
ethylene. CH3CH:CH(CH ~)~CH~; mw 84.16; CzH5CH:CHC2H~; mw 84.16 liq, bp 70°, d
colorless liq, frp -136°, bp 68”, flp -5” F, d 0.693 at 20°. Prepd by reacting 3,4-dibromo-
0.686 at 20°, RI 1.3948, insol in w; hexane with Zn dust; or by partial hydro-
SO1in alc or dil HZS04; low toxicity. Prepd genation of 3-hexyne over Raney nickel
by reacting 3-iodohexane with sodamide; by Refs: 1) Beil 1, [192], {806}& <837>
hydrogenation of n-heptylalcohol over finely 2) CondChemDict, 1971, p .444
divided nickel. Used as chemical intermediate 3-Nitro-3-hexene (called 3-Nitro-hexen(3) in
Refs: 1) Beil 1; (89), [1921, {8(P} & <833> Ger). C2H5C(NOZ):CHC2H5; mw 129.18, N 10.84%;
2) CondChemDict (1971), p 444 yellow liq, bp 70.6° at 10mm, d 0.9736, ~
,2-Nitro-2-hexene (Called 2-nit ro-hexen(2) in 1.4510 at 25” (Ref 2); sol in benzene. Prepd
Ger). H3CC(NOZ):CHC3H7; mw 129.18, N 10.84%; by refluxing CZH5CH(N02)CH(OAC) C2H5 in
yellow liq, bp 82.3° at 10mm, d 0.9824, nD dry. benzene containing Na-carbonate (Ref 1)
at 25° 1.4572 (Ref 2); sol in benz (Ref 4). Refs: 1) Beil 1, {808} &f840> 2) K.F. Lampeet
It is an eye irritant and is moderately toxic al, JChemEngData 7, (l), 85 (1962) & CA 57,
(Ref 5). Prepd by refluxing MeCH(NO,)CH(OAc) 8414 (1962)
Pr in dry benzene containing Na-carbonate 3,4 Dinitro-3 hexene (called 3,4 Dinitro-hexen(3
(Refs 2 & 4); by heating 2-nitrohexanol with in Ger). C2H5C(NOZ):C(N02 )C2H5; mw 174.18, !
 H 93

N16.09%; light yellow needles, mp 29-32°, bp Deutsche Spengchemie GmbH was a type of NC-
53-5° at lmm, “RI at 25° 1.4640 (Ref 3). DEGDN-PETN proplnt or expl. Two compns are
IR sp~ctra in Ref 2. Prepd. by reacting EtC; CEt listed in PATR 2510, (1958), p Ger 117-R:
with N20q in ether (Ref 3). Reacting 1-chloro- a) Nipolit in tubes: NC (12.6%N) 34.1, DEGDN
l-nitropropane with aq KOH and then acidi- 35.0, PETN (unwaxed) 35.0, stabilizer 0.75,
fying to a pH of z9. The residue after sepa- MgO 0.05, graphite 0.1 %, calorific, value 1300
ration and washing is distilled, under vac & cal/g
nitrogen atmos to prevent explosion, to get b) Nipolit in sticks: NC 29.1, DEGDN 20.0,
additional product (Ref 4) PETN 50.0, stabilizer 0.75, MgO 0.05 and
Refs: 1) Beil 1, {808}& <840> 2) J.F. gaphite 0“.1% (Ref 1)
Brown, JACS 77,6341 (1955)&CA 50,2297 (1956) Berkovic (Ref 2) states that Hexolit is com-
3). J.P. Freeman & W.D. Emmons, JACS 79, posed of RDX 90 & TNT 10 and “claims that it
1712 (1957) & CA 51, 11267 (1957) 4) Org has low impact sens
Synth 4, 372 (1957) Refs: 1) Dr. H. Walter, formerly’ of PicArsn;
Trinitro, CbH9N3 06, Tetranitro, C6H8N4 08, and private communication (1960) 2) M. Berkovic,
Pentanitro, C6H7N~ 01 ~, derivs of Hexene were not .Explosivst 12,207 (1964)
found in Beil
1,1,1,6,6,6-Hexanitro-3-hexene. (N02)3CCH2 Hexolites (Fr). Mixtures of RDX (hexogene in
CH:CHCH2C(N02)3; mw 354.18, N 23.73%, OB Fr) and TNT (tolite in Fr). Same as Cyclotols
to C02 –13.5%; crystals, mp 128°, d 1.77.
Prepd from 1,4, Dibromo~2-butene and Ag- Hexone T4. Same as Cyclonite or RDX, Vol 3,
nitroform. It is an explosive of about the C611-R
same sensitivity as PETN
Refs: 1) Beil, not found 2)-D.V. Sickman & Hexonite (Swiss). Hexonites are plastic explo-
W.F. Sager, NAVORD Rept 486, (1954) 3) Not sives, proposed by Stettbacher, consisting of RDX
found in CA thru 1971 and NC, with or without Collodion Cotton. For
instance:
a) RDX 20-50 & NC 80-50% b) RDX 50, NC
Hexit. Same as Hexanitrodipheny lamine, Vol 5, 46 & Collodion Cotton 4%
p D1434-R Comparative brisance tests with 50/50 Hexo-
nit and 50/50 Pentrinit by the iron plate test
Hexite. Same as Hexanitrodipheny lamine, VOI showed that Hexonit is not as effective as
5, p D1434-R
Pentrinit (Ref 1). It is also claimed that RDX
in Hexonit does not form such a homo-
Hexo. One of the Ger abbreviation for Hexo- geneousmass with NC and NC as does PETN in
gen (RDX). See Vol 5, p 61 1-L Pentrinit (Ref 2), and it tends to exude. NC
was used lJy the Germans for loading torpedo
Hexo (S-15 and S-22). Ger “Substitute Explo- heads
sives” (Ersatz-sprengsto ffe), contg Hexogen. Refs: 1) A. Stettbacher, Nitrocellulose 4, 224
See Vol 5, p E122, Table E15 (1933) .2) A. Stettbacher, P61voras Y
Hexocire (Fr). Mixture of RDX and Wax , Explositios,G. Gili, Buenos Aires (1952) p 111

Hexogen (H). Ger for Cyclonite or RDX. Also

Hexonyl. Same as Hexanitrodiphenylamine, Vol
known as W-Salz, E-Salz, K-Salz, SH- Salz and KA “5, p D1434-R
-Salz, depending on the method of prepn
Ger WWII methods of prepn are described in Hexoplast 75. A plastic explosive, developed
Vol 3 of Encycl, pp C613-R to C614-R, under during WW II at the Kriimmel Factory of Dyna-
CYCLOTRIMETHYLENE TRINITRAMINE mit AC. It contained RDX” 75, NC 1.2 to 1.4,
liquid DNT 20.0 aid TNT 3.8 to 3 .6Y0. This
Hexolit. Same as Nipolit (See below), but wit~ mixture was prepd by heating the required
Hexogen (RDX) in lieu of Pentrit (PETN) amount of RDX to 90° in a Werner-Pfleiderer
Note: Nipolit developed during WWII by the mixer, and blending it with a small amount of
 H 94

NC. This was followed by the addition of a formulations carbon black, are added. Examples
DNT-TNT mixture arid further blending. By of compns: a) RDX/TNT/Al/Wax-40/44/ 15/1
using this order of addition, lumping was or 40/40/1 5/5; b) RDX/TNT/Al-30/50/20,
avoided plus 1% wax & 1.~y. carbon black. Hexotonal
The mixture was put out” in cylinders about is usually prepd starting from Hexotol 60/40
220 mm long by 28 mm in diameter. Due to or 50/50
difficulty with direct cap initiation, a booster was Hexotonal has been manufd by AB Bofors
provided. It consisted of compressed, phlegma- for use as a cast filling at d 1.68-1.74. Its
tized PETN pellets about 40 mm long by 21 sensitivity to impact and” friction is moderated
mm diam and equipped with a detonator well by an addn of wax, its sensitivity to initiation
20 mm deep is comparable to that of Hexotol, but bursting
Note: This explosive was developed as a sub- effect and fragmentation power are higher
stitute for the plastic explosive, which used (Ref 3, p 203)
RDX plus American vaseline, because the latter The following tests are described in Ref 2,
component was no longer available in Gefmany. pp 203-04: a) Content of RDX, plus Al b)
This vaseline, called “long fibrous” by Meyer, Content of Al c) Content of desensitizer plus
had much greater adherence than vaselines Al d) Content of desensitizer e) Content of
manufactured in other countries TNT f) Acidity g) Explosion temperature
Refs: 1) O.W. Stickland, General Summary of (as described on pp 60-62 of Ref 2), and
Explosive Plants, PB Rept 925, (1945) Appendix h) Moisture content
7 (R. Meyer, Development Work on Explosives Accdg to Ref 1, Hexotonol consisting of
at K.rumrnel) 2) PATR 2510, (1958), p Ger 90 RDX/TNT/Al-40/45 /’l 5 was used in 40mm
shells
Hexose, Pentanintrate. See Glucose Pentanintrate Refi 1) Anon, “Ammunition for 40mm Auto-
in Vol 6 matic Gun L/70 MV 1000 m/see,” Sweden,
(Nov 1953) 2) AB Bofors, same as Ref under
Hexotol, which corresponds to the US & Brit Hexotol, pp 203-204
~clotol, is a Swedish expl mixture usually con-
HEXYL. See Hexanitrodipheny lamine under
taining 60% Hexogen (RDX) & 40% Tol (TNT).
Diphenylamine in Vol 5, p D 1434-R
It has been manufd by AB Bofors-Nobelkrut
in the form of granules. It corresponds to US
Hexylamines. See Aminohexanes in Vol 1, p A
Composition B-2 which is described in Vol 3,
215-R
Table on p C479. When 1% of synthetic wax
is added to 60/40 mixture, the expl becomes
Hexylaniline-2,4,6-Trinitro. (NOz)3Cb H2NHCH,
Composition B. Hexotol has been used in C5HII; mw 312.32, N 17.94%, OB”to C02 –133.2%;
Sweden for cast-loading shells at a density of yellow plates (from CSZ) mp 70-70.5”; sl sol in
1.65-1.70. It is almost as insensitive to impact
eth or ligroin; sol in alc or benz; v sol in chlf.
as TNT, but much more sensitive to initiation. Prepd from Picrylchloride & hexylamine in alc
Its deton velocity is 7800m/s, its fragmentation soln
power is higher than that of TNT and it is as Refs: 1) Beil 12, 764 2) E.V. Behrens, Rec 14,
stable as RDX in the vacuum stability test 38 (1895)
At Bofors, Hexotol is examined for appear-
ance, composition, insol matter in acetone—
CC14, acidity, expln temp, viscosity and moisture Hexylene Ozonide. CbHlz 03; mwl 32.18; mobile
Ref Anon, “Analytical Methods for Powders oil, bp 60” at 12mm, d 0.994 at 23°, nD
and Explosives,” AB” Bofors-Nobelkrut, Bofors, 1.4059 at 25°. S1 sol in water with slow de-
Sweden (1960), pp 201-203 composition; S1sol in pet eth. Explodes if heated
strongly above 60~ Prepd by reacting hexylene
Hexotonal. A Swedish expl mixture of Hexo- (in hexane or EtClz ) with 15% ozone mixture
gen (RDX), TNT, and finely divided Al. Small Refs: 1) Beil 1, (90) 2) C. Harries &K.
amounts of desensitizer (wax), and in some Haeffner, Annalen 374,331 (191 O)
 H 95

Hexylnitrate. H9CH20N02; mw 145.18, N

C5 Refs: 1) Beil, not found 2) D.V. Sickman &
9.65% ;liq, bp 466 at lmm, d 0.9745. RI 1.481 W.F. Sager, NAVORD Rept 486, (1954)
at 25°, sol in eth & EtClz (Ref 2). Prepd by 3) J.C. Conly et al, US Rubber Co Quart Prog
reacting hexyliodide with silvernitrate in dry Repts on Contr NOrd 10129 (NOV 1952–Feb 1954)
MeCN (Ref 3), or directly with 98% nitric
acid (Ref 5); addition of Nz OQ in EtClz to Heyrovsky, Jaroslav (1890-1967) received the
hexanol (Ref 4) 1959 Nobel in Chemistry for his dis-
Prize
Refs: 1) Beil 1, { 1657} 2) L.M. Soffer covery of polarography and for his role in the
et al, JACS 74, 5301 (1952) & CA 48, development of this technique which has
343 (1954) 3) A.F. Ferris et al, JACS 75, become such an important tool in electro-
4078 (1953) & CA 49, 8158 (1955) 4) E.H. chemiit ry, analyt ical chemist ry and many
White & W.R. Feldman, JACS 79, 5832 (1957) other areas of science and technology. He
& CA 52, 4469 (1958) 5) N.V. Svetlakov et was for many years a professor of physical
al, Zh Org Khim 4, (1 1), 1893 (1968) & chemistry at the Charles University of Prague.
CA 70, 28327 (1969)
When the Prague Polarographic Institute was
founded in 1950, Heyrowski became its first
director. Obituary notices for Prof Heyrowski
Hexylnitrite. C5H9CH,0NO; mw 129.18, N
appear~d in many scientific journals attesting
10.84%; liq, bp 50° at 48mm (Ref 2), 64° at
to his widespread recognition and esteem
76mm; RI 1.399 at 20° (Ref 3). Prepd by
heating C6H1 ~ N02 with HCONMe ~ & NaN02 Refs: 1) Anon, C&EN 45, 16&83 (1967)&
(Ref 4); C,~, Br + HCONMe, + NaNO, (Ref CA 67, 17 (1967) 2) P. Zuman, JElectroanal-
5) Chem 15,4 (1967)&CA 67,96692 (1967)
Refs: 1) Beil 1, 407 & {1657} 2) L.M. 3) G.F. Reynolds, JPolarogrSoc 13,2& 50–52
Soffer et al, JACS 74, 5301 (1952) & CA 48, (1967) &CA 68,26800 (1968) 4) J.A.V.
3243’ (1954) 3) N. Kornblum et al, JACS Butler &P. Zuman, BiogrMemFellowsRoy Soc
76, 3209 (1954) & CA 49, 8785 (1955)
13, 167–91 (1967) &CA 68,46098 (1968)
4) N.Komblum et al, JACS 78, 1501 (1956)
& CA 50, 14505 (1956) 5) Ibid, 1497 (1956) Hidrolitas. (Span) Explosives cmtg either PETN or
& CA 50, 14504 (1956) RDX, parraffin and moist N~ N03. They are
less sensitive to impact than either PETN or

I
HEXYLS. Designation for 2,4,6 -Trinitro-tris RDX, but are less powerful
(alkylnitram’ino) benzenes, to be described Rej; Vivas, Feigenspan & Ladreda 2, (1946),
under Nitramines p 288
High-Blast Explosive Filler. A MAX-2 composi-
3-Hexyne and Derivatives tion consisting of aluminum 62, Composition
3-~exyne, 3-Hexine or Diethyiacetylene. A-4 38 & graphite (added) 1.5% gave superior
C2H5C; CC~H5; mw 82.14; colorless liq, positive impulse output in 37mm shell. Positive
d 0.726 at 25, refr index 1.41.12; ins in water; impulse was determined by using piezoelectric
v sol in alc o,r eth. Prepd by reacting 3,4- gages. Max damage occurs if the expl detonates
dibromo-3-hexene with Zn dust in” boiling alc immediately after the shell fully penetrates the
Rejl Beil 1, [229] & {980} skin of an aircraft
No azido or nitro derivatives of 3-hexyne were Ref S. D. Stein, PATR 2523 (May 1958)
found in Beil or CA. However, US Rubber Co
& Navord reports describe: High-Blast Metal Oxygen Expls. Patented expls
1,1,1,6,6,6-Hexanitro-3-Hexyne. (NO,)aCCHz especially designed for aircraft destruction. They
C; CCH2C(NOZ)3; mw 352.16, N 23.87%. OB to achieve enhanced blast effects through metal-O
COZ -9.1%; crystals, mp 129-130~ d 1.73. reactions and are claimed to be less affected
Prepd from 1,4-dibromo-2-butyne and Ag- by altitude than other HEs. The composition
nitroform. It has about the same explosive contains: 54(50/50 A1/Mg), 36 AP, 4 TNT
sensitivity and power as PETN. Its hot bar & 6% RDX or 54 (50/50 A1/Mg), 28 AN,
ignition ternp is 205° 10 Tetryl & 8% TNT
 H 96

Rej S. J. Porter USP 2,992,086 (1961) & difference between detonation and deflagration
CA 55,26447 (1961) lies in. the mode of propagation. Deflagr,ation
propagates via heat. transfer such as conduction
High Capacity (HC) Bombs. These British bombs or radiation, while detonation propagates via
used for general bombardment purposes are a shock wave mechanism. As already stated both
described in Ref modes of action–detonation or deflagration are
Refi Dept of Army Tech Manual TM9-I 985-1, possible in most explosives
“British Explosive Ordnance,” (July 1952), The above classifications are not strictly ap-
pp 33-42 (Conf) plicable to the sensitivity of an explosive. Al-
though it is true that most primary explosives
High Density Explosives. Explosives of high are more “sensitive” than most secondary ex-
density are prepd by heating AN with plosives, certain low explosives, eg Black Pow-
freezing point depressants such as urea to effect der, are more “serisitive” than many secondary
only partial liquefaction of AN and adding to or even primary explosives
the mixture Ca-Si, Fe-Si, Al, or aromatic See also DETONATION, EXPLOS1ON AND
nitrocompounds EXPLOSIVES Introduction and Definitions in
Refi C. A. Woodbury & P. G. Wrightsman, Vol 4, p D2 17-L and also History of Explosives
USP 2,063,572 (1936), CA 31, 865 (1937) and Related Items in this Vol

High Energy Fuels. See under Exotic Fuels Written by J. ROTH

in Vol 6 ,p E350-L
High Explosive Projectile (Shell): The HE pro-
High Explosives (HE). A high explosive ii a “ jectile is one in which the percentage of filler
substance that undergoes extremely rapid to total weight is as high as possible, consistent
chemical reaction, when properly initiated, to with other requirements, such as good fragmen-
produce gaseous products at high temperature tation or demolition. The projectile consists of
and pressure. These products are then capable the shell proper and the fuze. The body of the
of doing useful work as they expand. It has shell is generally in the shape of a steel cylinder,
been custorndry to divide HE into two categories: having a tapered portion near the nose (“ogive”).
prirnury explosives and secondary explosives. Behind the ogive there is a smoothly machined
This distinction is more in kind than in degree. section called “bourrelet”, the diameter of
Small quantities of primary or initiating explo- which is a few thousandths of an inch less than
sives usually detonate when exposed to flames the diameter across the space between grooves of
or high temperatures while secondary explosives the bore (lands) of the gun barrel. The bourrelet
usually burn or deflagrate under these con- rides on the lands and supports the forward por-
ditions. However under slightly altered conditions tion of the projectile as it travels through the
primary explosives can be made to deflagrate bore. In the rear of the body of the shell there
and secondary explosives can be made to is a “rotating band” usually made of gilding
detonate. Examples of primary explosives are: metal: This band acts as an after support of the
Lead Azide, Mercury Fulminate, DDNP, etc shell and at the same time imparts rotation
Examples of secondary explosives are: PETN, to the projectile because its diameter is some-
RDX, HMX, Tetryl, TNT, as single HE compns what larger than that across the lands and there-
and Comp B, Comp C, PBX 9404, Dynamite fore becomes engaged as the projectile travels
ANFO (Ammonium Nitrate/Fuel Oil) as HE through the bore. Due to the tight fit in the
mixtures bore, the band acts as a gds seal preventing the
It has also been traditional to distinguish HE hot propellant gas from passing between the,
from “low” or propellant explosives. Here walls of the shell and the gun, so that the full
again the distinction is not clear-cut. Although expansion of gas is utilized to do the useful
a “low” explosive such as Black Powder work of imparting projectile motion. A tapered
probably cannot detonate, most smokeless section to the rear of the rotating band is
powders can. Conversely, most ,secondar~ ex- called the “boat-tail”, the purpose of which is
plosives can be made to deflagrate. The main to increase the stability of the shell during flight.
 H 97

In order to prevent any hot gas from contacting used as completing agents for the separation of
the explosive charge (in the event that any po- aromatic compounds by employing Thin Layer
rosity exists in the shell base) a thin steel disc Chromatographic (TLC) technique
is welded or brazed to the shell base (“base Nitro compounds form charge-transfer com-
cover”). The shell is filled with high explosive plexes with aromatic donors due to polarization
(TNT, Amatol, Pentolite etc), leaving a cylindri- of the nitro group as in I and 11. According to
cal cavity at the upper part for a booster Mulliken [6, 7] these fl complexes involve hybrid
charge. The neck of the shell is threaded inside structures with only a dative and no bond. It has
so that the fuze (including the booster) can be been more recently suggested [8] that in the for-
screwed on. The outer edge of the fuze is
pointed and both the fuze and ogive meet to
form a smooth contour
The HE shell may be designed primarily for
fragmentation effect, obtained through dispersion
“of the fragments at high velocity, or for demo-
lition effect produced by the blast of the HE, or
mation of 1:1 I_I-complexes of m- Dinitrobenzene
a combination of these effects
(m-DNB) ‘with different aminobenzoic acids only
The fragmentation shell has thicker walls than
one nitrogroup takes part
the demolition shell. The HE bursting charge is
Explosives like s-Trinitrotoluene (s-TNT), s-TNB,
larger for the demolition than for the fragmen-
Tetryl etc being II acceptors make charge-transfer
tation shell
Refs: 1) Hayes (1938) p 562 z) Ohart (1946) complexes with aromatic amines. Only in a few
pp 86, 98-99, 118 & 160 3) Anon, Engineer- cases the II complexes have been obtained in the
ing Design Handbook, Ammunition Series, crystalline state. In large number of cases these
Sec 4, “Design for Projection”, AMCP 706-247, complexes are very unstable and cannot be iso-
pp 4-117ff (July 1964) 4) Anon, “Artillery lated for. the identification of the parent compound.
Ammunition”, Dept of Army Tech Manual The very labile physical linkages between the II
TM9-1300-203 (April 1967) acceptor and the II donor molecules are respon-
sible for their break down. Solvent forces, steric
High Explosives, Detection as II Complexes. We hindrance due to groups, temperature etc weaken
quote from a very interesting paper by Parihar, the charge-transfer linkages. Particularly’ during the
Sharma & Verma (Ref 8) about a novel method study of such complexes by chromatographic tech-
of detecting explosives. niques the absorption forces have a powerful domin-
“A rapid and convenient procedure for the de- ating effect
tection of explosives as II complexes with aroma- When explosives are found singly or as mixtures
tic amines is’ described. The method could be of there is a problem of their rapid identification. It
immense value in places where normal laboratory is particularly significant in field areas where normal
facilities are not available laboratory facilities are not available and unknown
Recently nitroaromatic compounds have been explosives have to be quickly characterized.’ Though
employed as II acceptors in the study of the the II complexes of nitroaromatic compounds with
charge-transfer complexes of a variety of organic hydrocarbons have been studied by TLC [5], yet
compounds. During such investigations several suffer from the disadvantage of their colorless
chromatographic techniques were used. For ex- nature and difficulty of location on the
ample charge-transfer was found to be” effective chromatoplates
during the investigations of substituted anilines The present paper describes a simple and con-
2,4,7 -Trinitrofluorenone systems in Gas venient procedure for the identification of explo-
Chromatography (CC) [1] . CC was helpful in the sives viz: Picramide; Hexyl; 2,4-Dinitropherietole
separation of aromatic compounds on columns (DNP); Tetryl; s-TNT; s-TNB; 2,4,6-Trinitroanisole
containing 2,4-Dinitrochlorobenzene (DNCB) [2] , (TNA); 2,4-Dinitroanisole (DNA); 2,4,6-Trinitro-
and for olefins on 1,3,5, - Trinitrobenzcne (s-TNB) phenetole (TNP); DNCB; m-DNB and Picryl
[3] impregnated columns. Pictric acid [4] and Chloride (PC) in ordnance stores as charge-
other nitro aromatic compounds [5] have been transfer complexes with amines utilizing TLC
 H 98

technique. The resolved II complexes being

highly colored could be easily located from their
Rf values. Thus by running the unknown samples
along with the known compound< or alternative-
ly from the known data of their resolutions as
complexes with different aromatic amines, they
could be readily detected up to 2-4y”
Note: The” term ~ values refers to a relative
rate of movement of the test sample through
the chromatographic column
The authors summarize their findings as
follows:
“The resolutions of the II complexes was found
to be governed by three factors (i) adsorbent, (ii)
nature of the II donor (here aromatic amine), and
(iii) irrigating solvent. In general the migrations of
the explosives were in relation to the effect of
electron attracting or repelling groups present in
them
On diphenylamine treated silica gel plates DNA
moved less than DNP; similarly TNA had lower Rf
than TNP. This is due to more electron repelling
nature of the ethoxyl group compared to methoxyl.
DNCB migrated higher than s,TNB, due to less
electron affinity of chloro than nitro group. Simi-
larly s-TNT had higher migration than s-TNB owing
to electron repelling nature of CH3. s-TNB had
lower Rf than m-DNB due to the presence of a
, third nitro group. Hexyl was most strongly bound
compared to other polynitroamines ie Tetryl and
Picramide
The relative role of the absorbents was found
to be interesting. For example on employing the
same’ amine diethylaniline (DEA) as H completing
agent and same solvent system monochlorobenzene
(MCB) -ethylene dichloride (EDC)/9 : 1, DNA gave
higher Rf than TNA on alumina in comparison to
magnesium silicate plates. On alumina H complexes
of TNA, TNP and PC produced tailings. Mag-
nesium silicate gave excellent resolutions but re-
quired more irrigation time than other absorbents
The nature of the aromatic amine to form II
complexes was important. On silica gel G plates
and MCB-EDC as solvent PC-anisidine complex had
lower migrations than PC-DPA or PC-DEA complexes
The TNA-anisidine, TNP-anisidine complexes had
lower migrations than DNA-anisidine and DNP-
anisidine complexes. This observation was opposite
to the resolutions of the complexes of these ex-
plosives with DPA and DEA’
 H 99

It was seen that irrigating solvent had pronoun-

ced effect on the relative nobilities of the H com-
plexes eg the Rf values of Tetryl and Picramide. were
reversed with petroleum ether–ethyl acetate (9: 1)
compared to MCBEDC system”
Their data in tabular form follows:

Rf Values for Various Explosives

— ——-.—. .-—— .—- —.—

x-COmpl Cxc8 \Vit.h LZip!renyl:+lmlnc
.--————.—.—. ——
S!11C2&e! G Mzignc:it:m Slllcatc Alumfna
—..-.— ——-
htlsorbcnts hlono-
Fiames of the Explosives Solvents
?.fGno- MonO-
dliOrO- Petrol chlOro- chloro- Pctrol
benxne: ether: bcnzc~t: bet:zelle: ether:
Ethylene Ethyl I:lhylc!le Carbon Ethylene E:hyl
dl&hio;ld~ acctatn dichloride tetra - dlchiorlde acetate
(s:1) (%:5) (9:1) chloride ($:1) (9:1)
———

Picramide :31 .09 .22 .04 .40 .34

Tetryl ,32 ,05 .30 .06 .37 .28
FIexyl .00 .00 .06 ,00 .00 .00
s-TrirtitrGtoluene .“‘5 .34 .63 .29 .63 .67
s-Trirtitrobenzene .49 .24 .42 .11 .53 ,61
1,3-Dirtitkobenzel~e .54 .28 .59 .41 .64 .72
Picryl chloride .62 .30 .67 .36 ,62 .62
2,4-Din itrochlorabenzene .66 .40 .70 .6i .65 .68
2,4,6 -Trinitrophenetole .52 .29 .60 .27 .29 .60
2,4-Diiiitrophenetole .39 .12 .39 .17 .51 .33
2,4,6, -Trinitroanisole .48 .23 .54 .34 .26 .44
2i4-DLnitroanisole .35 .09 .31 .21 .46 .37

and for two other solvents the Rf values for the same explosives arranged in the same order as above
are:
x-Complexes with rzlethyl aniIinc a-complexes with p-anlsldlrre
Slllcagel G Magnesium SIllcate Alumina Sllicagel G hf~gneslum slllcale Alumlna
Mono- Mono- Mono- Mono- Mono- Mono-
tiloro- Pctrol chlOrO- chlorO- Petrol chlorO- Petrol chlOrO- tilOro-
benzene: elher: benzene: benzene: ether: benzene: ether: benzene: benzene:
Ethyiene Ethyl ~t!, y,ene Carbon Ethylene Ethyl- Ethylerrc Ethyl Ethylene Carbon Ethylene Carbon
Dlchlorlde acetate Dlchlorlde tetra- Dlchlorlde acetate Dichloride acetate dichloride tetra - dichloride tetra-
(9:1) (9:1) (9:t) chloride [9:1) (9:1) (9:1) (9:1) (9:1) chloride (9:1) chloride
.33 .19 .36 .11 .41 .14 .41 .16 .56 .12 .30 .50
37 .13 .40 .06 .45 .08 .46 .21 .79 .28 .54 .43
.00 .00 .00 .00 .00 .00 .03 .00 .00 .00 .00 .00
.65 .46 .76 .49 .72 .53 .72 .65 .82 .44 .80 .72
.55 .39 .53 .20 .58 .43 .65 .55 .65 .31 .66 .64
.58 .34 .70 .47 .70 .47 .76 .50 .76 .59 .78 .86
.66 .45 .71 :51 .52 .22 .54 .28 .66 .34 .56 .54
.70 .43 .75 .67 .73 .55 .80 .64 .83 .74 1.00 .93
.61 .42 .68 .44 .18 .13 .53 .33 .72 .37 .84 .60
.48 .18 .50 .17 .56 .34 .62 .36 .60 .42 .62 .76
.54 .38 .59 .39 .25 .19 .47 .30 .75 ,46 .91 .69
.40 .14 .42 .22 .60 .21 .49 .48 .67 .52 .82 .82
—- .-— —------
 H 100

Refs: 1) A.R. Cooper, et al, Trans Faraday Sot, The word “detonics” in the title is chosen in
62 (1 O), 2725 (1966) 2) K. Malinowska; Chem- preference to the word detonation to indicate
Anal (Warasaw); 9, 353 (1964) 3) R.J. Cvetan- the physics of detonating high explosives and
ovic et al, CanJChem 42, 2410 (1964) 4) H. their mechanical effects. The major emphasis
Kessler & E. Mueller, J Chromatog 24, 469 is on commercial high explosives for rock
(1966) 5) M. Franck-Neumann & P. Jossang, blasting, with the exclusion of “Permitted
J Chromatog 14, 280 (1964) 6) R.S. Mulliken, Explosives” and the many complicated problems
JAmChemSoc 72, 600 (1950); 74, 811 (1952), connected with these
JPhysChem 56, 801 (1952) 7) R.S. Mulliken The first three chapters deal with the mechan-
& L.E. Orgel, JAmChemSoc 79, 4839 (1957) ism of detonation and the initiation of detona-
8) D.B. Parihar et al, Explosivst 12, 281 tion by means of strong shock waves or mechan-
(1968) & CA 71, 31917 (1969) ical impact at low velocity. Burning and the
effects of heating are treated in Chapter 4, and
High Explosives, Detonics of is a book by
in Chapter 5 is given a systematic discussion of
C. H. Johansson & P. A. Persson, Academic the various phenomena of light emission during
Press, London & NY (1970). Quoting from
detonation. Chapter 6 is devoted to a fairly
the preface: “The authors have been
detailed survey of the mechanical effects in
actively engaged in many of the problems of
surrounding media and a discussion of the work
initiation, detonation and effects of high explo-
performed by the reaction products of a con-
sives encountered. Due to the policy of free
tained charge. Particular attention is paid to
international exchange of results that was
the effects of a charge in rock. The final
followed, they have been able to meet and
chapter is an introduction to such methods and
exchange ideas, on the basis of personal friend-
results of the physics of high dynamic pres-
ship, with scientists from many parts of the
sures in condensed media as have appeared
world engaged in similar work. They have had
essential to the understanding of the mechan-
the opportunity of seeing the problems of
ical effects of detonation
explosives manufacture and application not as
interesting abstract problems of theoretical The authors have felt in their own activity a
science, but as experimental problems to be need for a systematic survey of current experi-
solved in order for technical and economical mental facts and data of real explosives as a
progress to be made complement to existing theoretical treatments of
In the present volume, the authors have idealized explosives and detonation phenomena.
attempted to give a systematic and coherent The theoretical treatment has therefore been
account of the experimental phenomenology deliberately limited and is included mainly with
of the initiation, detonation, and physical the purpose of simplifying the account of experi-
effects of detonating high explosives. In ever- mental results
increasing quantities, explosives are used both Of necessity, the choice of results and data
in rock blasting and in an increasing number has been determined by the experimental work
of new and unorthodox technical processes. and applications in which the authors have been
For all these applications, charge sizes have to engaged. Wherever possible, results published” by
be calculated, effects have to be predicted, workers outside Sweden have been included, but
problems of initiation and safety have to be the authors are fully aware of the difficulty in
solved, and young engineers and scientists have doing justice to the great number of scientists
to be taught the basic principles. Although we in many part; of the world who have made im-
still lack a detailed and completely clarifying portant and beautiful contributions to this field
theory for the complicated explosives phenom- of research
ena involved, the present text may be used by The major part of the experimental work de-
the practicing engineer, scientist, or safety scribed has been done since 1946 in the Physics
inspector as a source-book for essential experi- Research Laboratory (Detoniklaboratoriet) of Nitro
mental facts and figures. The student, if he skips Nobel AB and from 1953 at the Swedish Detonic
the experimental details, may use it as a textboo~ Research Foundation. Some of the work has bee’n
on the physics of explosives and explosive pheno- done since 1960 at the Swedish Research Institute
mena of National Defense”
 H 101

High Explosives, See under HISTORY

History of. Refs: 1) J. D. Hopper, PATR 2592 (Feb 1959)
OF EXPLOSIVES AND RELATED ITEMS 2) B. M. ,Dobratz, “Properties of Chemical Ex-
plosives and Explosive Stimulants,” UC RL-51 319
High-Explosive Train. See Vol 4, p D838 & (Dee 1972)
D839. Figs l-21a & l-21b

High Grade Same as Guncotton

Nitrocellulose. High Nitrogen Content Compounds as Flash
described under Cellulose and Derivatives in Reducing Some aliphatic nitrarnines of
Agents.
Vol 2, p C106-R low carbon content were prepd & studied for use
as ingredients of flashless propellants. Nitro-
High Nitrogen Nitrocellulose. See under Cellulose urethane, Dimethylnitramine (See Vol 5, p D 1306-
and Derivatives in Vol 2, p 108-R L) & Cyclotrimethylene trinitrosamine (See Vol
3, p C630-R) were found to be unsuitable for
High-Low Pressure Gun (H/L Gun). See Hoch- use in proplnt compns. Dinitrodiacetylmethylene-
und-Niederdruckkanone in PATR 2510 (1958), ~ diamine had properties which indicated it offered
p Ger 90-R & in this Vol promise and tests were recommended to determine
the practicability y of using it in proplnts (Ref 1)
High and Low Temperature Tests, for Small Benson (Ref 2) also reported that some success
Arms Ammunition. The purpose of these tests had been achie,ved in the reduction of muzzle
is to determine the effect of high (as high as flash by incorporating high nitrogen compds such
+165”F) or low temperature (as low as as Dicyandiamide .( See Vol 3, p C587-L) &
-70° F) storage upon the ballistic performance Nitroguanidine. In order to extend this approach
of ammunition, or components thereof and to investigate other compds, selected hydra-
The detailed description of the test is given zine derivs were prepd & studied. Cyanuric
in Ref Hydrazide & 5-Amino-tetrazole (See Vol 1,
Ref Anon, Ordnance Proof Manual 7-24 (1945), p A258-L) were of greatest interest because of
p7 their high nitrogen content and other props
Since 5-Amino-tetrazole (ATZ) was not
High Mechanical Strength Explosives. Hopper available commercially at that tilne, Benson (Ref 3)
(Ref 1) evaluated HMX bonded with “Exon 461 ,“ also reported a method for the synthesis of
a Firestone Plastics Co, Pottstown, Pa, fluoro- ATZ of 99% purity in 70-85% yield by reaction
carbon polymer, for an application requiring a of Na nitrate & aminoguanidine bicarbonate
high-energy, high mechanical strength expl. Compns dissolved in nitric acid, followed by treatment
in the range 85-95’?ZO HMX & 5-1570 Exon 461 with Na acetate. Davis (Ref 4) prepd Cal .50
were prepd as granular molding powds and gun proplnts and determined the optimum
compressed into large cylinders in a heated mold. percentage of 5 to 10% ATZ without DNEB
As the percentage of HMX was increased, the d (Dinitroethylbenzene), but coated with 5 to
increased from 1.84 to 1.86 g/cc, and the deton 0.8% DNT, gave acceptable service ballistics.
vel increased from 8388 to 8838 m/see. The The proplnts gave completely flashless rounds
compn 85/15 HMX/Exon gave the greatest in 45-inch barrel rifle and machine gun with
mechanical strength, at RT its compressive an AK-flash hider
strength was 11000-12000 psi and tensile strength Nine new materials of high nitrogen content
of 1100-1500 psi. Storage at 160°F for 100 were studied by Sheffield (Ref 5) and attempts
days had no appreciable effect on mechanical were made to reduce the hygroscopicity of
props measured at RT. Especially noteworthy is ATZ. Of the new compds investigated, Melamine
the excellent thermal stability of HMX/Exon in was found to be the most promising from the
the 120”C vacuum stability test standpoint of its props & availability, but
A number of plastic-bonded expls based on Cyanuric Hydrazide was only slightly inferior
HMX & RDX plus polymeric binders has been in these respects. Physical treatment of ATZ
developed at the Lawrence Livermore Lab, had no significant effect on its hygroscopicity,
University of California, Livermore. Their props and chemical treatment did not yield material
have been compiled by Dobratz (Ref 2) of promise

I
 H 102

Helf (Ref 6) investigated ten hew materials 2) F. R. Benson, PATR 1409 (April 1944)
as flash & smoke suppressants in proplnts. (Hydrazine derivs) 3) F. R. Benson, PATR
Guanylurea Nitrate was the most promising 1548 (July 1945) (Synthesis of 5-Amino-
compd with regard to physical & chemical tetrazole) 4) C. S. Davis, PATR 1615 (July
props, stability, and O balance. Guanylnitro 1946) (Proplnts contg ATZ) 5) O. E.
Urea was unsuitable for proplnts contg NC. Sheffield, PATR 1694 (May 1948) (High nitro-
Carbohydrazide-N-carboxyamide & Carbohy- gen compds) 6) S. Helf, PATR 1752 (Nov
drazide-N, N’-dicarboxyamide showed desirable 1949) (High nitrogen compds). 7) S. HeIf,
promise but depended on a special starting PATR 1841 (Ott 1951) (High nitrogen compds)
material. Ammonium .Nitrourea, Diammonium 8) L. F. Audrieth & P. G. Gordon, “Com-
-methylene-bis-(nitrosohydroxylamine) & pounds of High N]trogen Content,” Final
Guanidine OxaPate were investigated and found Rept, Part 1, “The Chemistry of AIlophanyl
unsatisfactory because of their chemical & Hydrazide and Urazole,” Univ of Ill, Urbana,
stability props 111(March 15, 1954) 9) L. F. Audrieth &
Continuing this investigation Helf (Ref 7) J. W. Currier, Ibid, Part B, “Derivatives of
found Carbohydrazide Oxalate, Dinitrobiuret, 5-Aminotetrazole,” Ibid (June 15, 1954)
Diaminobiuret, Hydrazine Oxalate, & Hydrazine 10) L. F. Audrieth & W. L. Curless, “Prep- ‘
Nitrate were either unsuitable or not com- amtion and Properties of Some Oxalates of
patible with Nitrocellulose. Urazine, N- High Nitrogen Content ,“ Ibid, (1954)
Guanyloxamic Acid and Cyamelide were stable (Contracts DA 11-022 -ORD-33, Proj TA1 -
compds of good physical props but their methods 3601 and W-1 1-022-ORD-I 1329) 11) Fedoroff
of prepn limited large scale production. Nitro- & Sheffield, PATR 2700, Vol 1 (1960), pp A257-R
biuret, although decomposed at 10O°C, was to A262-L (AMINOTETRAZOLE AND DERIVA-
stable & compatible with NC, and was of TIVES) ( Included are more than 100 refs)
particular interest as a non-smoky flash reducing
agent. Guanylamino-tetrazole & Guanylamino- High Pressure Effect on Explosives. Bridgeman
tetrazole Nitrate possess good physical props (Ref 1) determined that purely hydrostatic
& are compatible with NC. Both should yield pressures as high as 10s atms will not initiate
cool proplnt compns with good ballistic po- explosives even as sensitive as Lead Azide. In
tential. Nitroguanylamino-tetrazole, not previously fact there is evidence that high pressures slow
described” in the literature, appeared to have down thermal decomposition of explosives. Bow-
excellent potential as an ingredient of low- den et al found that for Cyarruric Triazide, Lead
temp, high-force propellants Azide & PETN the time to explosion at a fixed
Audrieth et al (Refs 8, 9 & 10) also prepd temp, or conversely the temp at a fixed explo-
& investigated compds of high nitrogen content sion time, increased as the pressure on the
with a view toward their use in propln & HE system increased from ambient to 22,500 atms
compns for PA (Ref 2). For Cyanuric Triazide this effect was
Muzzle flash, which is undesirable in gunnery appreciable but for PETN it was very slight.
because it discloses position, interferes with Bowden suggests that these observations are
vision of gunners, and interferes with guidance understandable in terms of LeChatelier’s
and telemetry, is due to the combustion of Principle since all of these explosives produce
product gases CO & Hz. Current US composite large vols of gas on explosion so that
nonflashing proplnts are based on British application of external pressure is expected
Cordite N, containing Nitroguanidine, while to repress the explosion reactions. The larger
German Nitroguanidine Propellant is considerably degree of repression for Cyanuric Triazide than
cooler because it employs Diethyleneglycol for PETN may be rationalized by the lower
Dinitrate instead of NC as the plasticizer for explosion pressure of the former than the
Nc latter. Thus ‘22500 atms may be a significant
See Flashless Cordites in Vol 3, p C522-R fraction of the explosion pressure of Cyanuric
Refs: 1) F. R. Benson, PATR 1174 (June 1942) Triazide while it is only a relatively small
(Aliphatic nitramines of low carbon content) fraction of the explosion pressure of PETN
 -w,

H 103

Recently Lee et al (Ref 3) re-examinecl the High-pressure operations are conducted in

behavior of PETN under 10 to 50 kbars of special reaction vessels which may be divided
external pressure. They also find a reduction into batch reactors, such as autoclaves (qv) and
in decomposition rate with increasing applied continuous reactors. Continuous reactors con-
pressure. HMX behaves similarly to PETN. TNT sist of long cylindrical tubes, constructed of
whose explosion products contain a high pro- steel in a manner to. resist pressures as high
portion of solid carbon, as expected from as 1500 atms. Inside the thick-walled reactor,
LeChatelier’s Principle, shows little pressure a thin-walled vessel corrtaining a catalyst is
effect on its thermal decomposition. Nitro- placed. The incoming gaseous reaction com-
m,ethane, however, appears to decompose more ponents, previously preheated (by allowing them
rapidly under an external pressure of 50 kbars to flow along the outside of the reactor), enter
than 10 kbars. This effect is not completely the reaction chamber, pass through the catalyst
understood but Lee et al suggest that high where they react, forming the desired product,
pressure may favor the formation of the and exit through the other end of the reactor
thermally less stable aci form of Nitromethane: into a cooler where they are collected as a
OH gas, liquid or solid
H3C”NOZ ~HQC:N.O Refs: 1) H. Tongue, “.Design and Construction of
High Pressure Chemical Plants,” Van Nostrand,
Written by J. ROTH I)W (1934) 2) M.E. Bonyun, Chem & Met-
Engr 42, 260-263 (1935) (Protecting pressure
Refs: 1) P. W. Bridgeman, JChemPhys 15, 311 vessels with rupture disks) 3) V.N. Ipatieff,
(1947) 2) F. P. Bowden et al, DiscFaradSoc “Catalytic Reactions at High Pressures and
“High Pressure Reactions” Sept 1956 3) E. .L. Temperatures,” Mdcmillan, NY (1936) 4).
Lee et al, Proc 5th Detonation Symposium C.W. Seibel, lEC 29, 414 (1937) (Factors ,in
(1970) p 331 high pressure design (32 references) 5) R.
Taylor, JSC1 56, 41T to 50T (1937) (High
High Pressure Pump. See Hochdruckpurnpe (HDP) pressure technique; the design of high-pressure
oder V-3 in this Vol equipment is discussed) 6) A. Eucken & M.
Jakob, Edit, “Der ChernieIngenieur~’ Akademische
High-Pressure Technique (Hochdrucktechnik-in Verlagsgesellschaft, Leipzig, v 3, part 4 (1939)
(Reproduced by Edwards BIOS - Ann Arbor,
High-Pressure Technique (Hochdrucktechnik–in Mich) 7) D.M. Newitt, “The Design of High
German). The term “high pressure”, according Pressure Plants and the Properties of Fluids
to Dodge (Ref 19), refers “to any pressure at High Pressures,” Clarendon Press, Oxford
above a lower limit of about 50 atms (750 psi)” (1940) 8) Roger’s Manual of Industrial
Applications of high pressures in chemical Chemistry, Van Nostrand, NY (1942), v 1,
indtistries dates from the beginning of this Chapt 4 (Article by B.F. Dodge) 9) J. Reilly
ceritury, when the industrial synthesis of & W.H. Rae, “Physico-chemical Methods,” Van
ammcmia from the elements was first achieved Nostrand, NY (1943), v 1, pp 323-345 1o)
by Haber, LeRossignol and others. The Burton D.B. Cooch, IEC 35, 935 (1943) (Autoclaves
process for oil cracking dates from about 1913 for pressure-temperature reactions) 11) D. P.
At present, pressures of the order of 1500 Meigs, TransAmInstChemEngrs 39, 769 (1943);
atms are widely used, but the technique for Canadian Chem Proc Inds 28, 309 (1944)
carrying out reactions under pressures up to (Closures of high pressure vessels) & CA 38,
about 10,000 atms is fairly well developed. In 897, 3515 (1944) 12) P. W. Bridgman, Rev
research laboratories, pressures as high as Mod Phys 18, 1 (1946) (Recent work in the
150,000 atms (3,000,000 psi) have been used field of high pressure. Review of the entire
to a limited degree field between 1930 and 1945 with 647
One of the principal applications of high references) 13) Krase, “Design and Construction
pressure technique in industry is to increase of High Pressure Compressors and Reaction Equip-
the chemical reaction rate ment,” FIAT Final Rept 611 (1945) 14) H. C.
 H 104

Hesse & J. H. Rushton, “Process Equipment & some of the techniques for using them are
Design,” Van Nostrand, NY (1945) 15) C. F. discussed. The present article deals with broader
Bee, Chem & Met Engrg 53, No 3, 114-116 aspects of high-speed photography. Not only is
(1946) (Simplified methods for calculating the information on high-speed cameras brought
stresses in pressure vessels) 16) Reynolds, “A up to date and extended, but other aspects of
Survey of High Pressure Designs in Germany,” high-speed photography, such as illumination,
FIAT Final Rept 1067 (1947) 17) E.L. Clark films & film processing are discussed
et al IEC 39, 1555-64 (1947) (High pressure Advances in Shattering Systems
reactions, 5 references) 18) Collective, Chem High-speed photography serves to extend and
Engrg 53, No 8, 107- I 27 (1 949) (High Pressure; help calibrate other even more rapid systems of
several papers and references) 19) J. H. Perry, data recording. The use of cameras and other
Ed, “Chemical Engineers’ Handbook,” McGraw- optical and electronic devices has kept pace
Hill, ,NY (1950), pp 1233-1262; B.F. with advances in high energy physics. The ex-
Dodge, “High-Pressure Technique”; 4th edit tremely brief exposures required for photo-
(1963), p 5-2ff 20) R.H. Wentorf, “Modern graphing the effects of explosion phenomena
High Pressure Techniques”, Butterworth, London are achieved by regulating the optical, electrical
(1962) 21) R.S. Bradley, “Advances in High and mechanical design of the camera’s shatter-
Pressure Research”, AcademicPress,NY(1966) ing system
22) K.E. Weale, “Chemical Reactions at High The picture taking rate for photographic re-
Pressures”, Spon, London (1 967) 23) D.S. cording of rapid moving or brief duration
Tsiklis, “Handbook of Techniques in High phenomena has steadily increased from “slow-
Pressure Research and Engineering”, Plenum motion” techniques at 64 pictures-per-second
Press,NY K1968) 24) D. Bienek & F. Korte, (pps) to more than millions of pps. Time
Naturwissenschaften 59 (12), 539–53 (1972) resolution has now been extended down to
(Organic High Pressure Chemistry, 21 refs) the order of 10 picosecond or less. Three
classes of high-speed photography are recog-
High-Pressure Test (HPT) Cartridge. See under nized. According to their time and rate of
Cartridge, Ammunition, Vol 2, p C74 picture-taking, they are called: high-speed, very
high-speed and ultra-high-speed photography
High Rate Detonator Production Study. As part High-Speed & Vety High-Speed Cameras
of the overall program to modernize the US Govt The first high-speed cameras accomplished
owned, company operated, Army Ammunition action stopping exposures at more than 1000
Loading and Assembly Plants, it is planned to pps. These rotating prism cameras (Ref 2)
develop fully automatic equipment to manuf eliminated the start-and-stop clawing action
nonelectric detonators at the rate of 1200 per of conventional motion picture cameras. The
minute. The survey of literature sources and 8mnl size film moved continuously and had
industry was undertaken to discover techniques relatively poor resolution. Later models, using
and equipment that may be applicable, as de- 16mnl films, reached speeds of more than
scribed in Ref 1 40) OOOpps.By increasing the number ~f faces
Refs: 1) E.E. Hannum, “Survey of Techniques in the prism shattering device each standard
and Equipment for High-Volume, Automatic 16nlm frame is split into 2 or 4 frames, there:
Production of Non-Electric Detonators”, PATR by increasing the pps. Greatly increased detail
454 I (1 974) 2) G. Cohn, Edit, Expls&Pyrots 7 resolution was achieved at first by going to
(5), 1974 larger film formats such as 35mm and finally
70mnl. In recent years newly developed anti-
reflection lens and prism coatings produced
HIGH SPEED PHOTOGRAPHY
substantially better contrast, higher resolution
Introduction and more effective light transmission by re-
I-Iigh+peed photography provides the main ducing glass interface glare and reflection
observational facility in the study and measure- Prior to World War 11, Dr. C. N. Hickman
ment of explosive phenomena. In VOI 2, pp of Bell Labs invented the “ribbon-frame”
C13- 19, many high-speed cameras arc described camera using the inexpensive 122 size (post-
 H 105

card) amateur roll film. This camera was a Film advance sprocket and image” motion com-
variation of the rotating prism shattering pensation prism are mounted on a single shaft
system that substituted plane-parallel glass to improve precision of registration
plates inside of a variable-slitted rotating cyl- These cameras, generally using standard 16mm
inder running continuously. When a clutch motion picture fiim (although Fastax also made
was engaged a short length of fdm moved 35mm film models as well as the original 8mm
steadily past the shutter slit. Although originally size) are efficient at picture taking rates, from
created to photograph arrows in flight (one of 100pps to 10,000pps. The Photec IV, through
Dr. Hickman’s hobbies was archery), since he an improved yet simplified optical design, per-
was the co-inventor of the portable rocket mits an effective aperture of f:2.8 to be at-
launcher weapon, it proved useful ii-t the study tained. This 2-stop gain over the “competitive”
of rocket trajectories as well as static fired models allows four times as much light to
rocket motors (Dr. Hickman was also the co- reach the fflm. The optical/ mechanica\ design
inventor of the bazooka) advance allows the picture-taking rate to be
A more sophisticated and considerably larger increased, the shattering time to be reduced
version of this type of camera wa$ developed substantially (to one/fiftieth of the picture-
by Drs. Bowen & Knapp and bears their names taklng rate). An additional benefit is the re:
(Ref 14). The Bowen-Knapp camera used 9-inch duction in heat reaching the subject because
wide rolls of aerial camera film. It came into weaker light, and consequently “cooler,” sources”
use late in World War H, but its use was can be used. Thus the Photec IV brings motion
restricted to studies of trajectories, rocket picture cameras into the very high-speed photog-
propellants and low order detonations because raphy group. Further references to the subject
of its limited maximum speed, comparable to of very high-speed cameras are covered in the
that of rotating prism cameras. Its main. dif- Proceedings of the International Congress on
ference from the tine-type cameras was in the High-Speed Photography (HSP), 1 through 10.
film format, which resembles a long “venetian- These excellent surveys have been published
blind” series of pictures. Usually a number of nearly every two years since the First Inter-
studies could be made on each roll since no national Symposium on High-Speed Photography
film acceleration was required. Timing was in- in Ott 1952
dicated by a pulsed light recorded on the High-Speed Video Systems
edge of the film. Space and movement data The next few years should produce effective
was generally reduced by using microscope or high-speed television image sequences. At pres-
projection comparators against fiducial marks ent, video systems are limit ed to a picture
recorded from the pre-surveyed scene field taking rate of less than 200pps and are con-
The newest example of high-speed motion sequently classified as slow motion photography,
picture camera of the rotating-prism type is although the data recovery rate, or read-out, is
the Photec IV–see sketch (from Ref 26) instantaneous. It is expected that an increase
in the framing rate by an order of magnitude
will be forthcoming soon. This will put video
systems in high-speed category
U’tra High-Speed Cameras
It is in the area of ultra high-speed photog-
raphy that the most significant advances are
now taking place. Exposure time has steadily
been reduced from microseconds, through nano-
seconds to 10 or less picosecond (10-12). A
pulse of light has now been photographed with
a movement blurring of the image of less than
two millimeters (Ref 26). This achievement in
ultra high-speed photography is due to a unique

“Mechanism of rotating prism Photec camera

 H 106

electronic shattering system, namely a Kerr Flash X-rays

cell that opens and closes (optically) in 10 Extremely brief flashes of X-rays are useful
picosecond. No electrodes are required and in the study of the movement of “dense
carbon disultide has replaced the heretofore materials, such as bullets, shell and bomb frag-
traditional nitrobenzene. A first-harmonic pulse ments, metal liners and containers, through
of light from a Nd:glass laser is used to drive smoke, turbulence and explosive debris (Ref 9).
the shutter Unaffected by glare, sunlight and other atmo-
Image Dissection Cameras spheric conditions, X-rays (radiographs) pene-
This type of ultrahigh-speed camera (Ref 3) trate, as they do in industrial and medical
also called lenticular camera, high-speed raster applications, to detect and reveal the behavior
camera (in the USSR), continuousaccess camera of explosively driven material (Ref 6). Multiple-
and, more informally, “scrambled” image camera, flashes permit stereo or sequential pictures to
seems to have the greatest potential for high- be made depending on the synchronization,
speed photography in the future. Resembling arrangement and humber of X-ray sources used.
holographic recording (Ref 1) in one sense, in- Cineradiography is particularly useful in investi-
asmuch as it permits the concentration of many gations of such phenomena as explosive welding,
sequential images in a limited space, it offers where the high-speed action takes place within
the prospect of ultra high picture taking rates an optically opaque substance (Ref 10). In
(over 10’pps). After an ordinary development addition, obscuration by the very bright lumi-
process the plate or film can be shown imme- nescence of the detonating explosive charge is
diately as a motion picture or video image. eliminated
Eventually, when the resolution of image con- Along with advances in X-ray technology,
verter tubes improves, the principle of image progress in electronic image enhancement (see
dissection should provide the maximum rates next section on Image Enhancement) permits
of high-speed photogra@y (Ref 23) gains up to fifty times. This permits the ex-
This is emphasized in the following table, tension of flash X-rays into diffraction record-
taken from an excellent summary of state of ing as well as higher rate cinematography (Ref
the art of high-speed photography by Courtney- 11)
Pratt. The data in this table also shows that Electronic Amplification of Light Images &
(Ref 26, p 172) there were no spectacular ad- Techniques of Image Enhancement
vances in image dissection camera performances Perhaps the most important trend at this
in the period 1957 to 1972 time in ultra high-speed photography is in the
Image Dissection Cameras. increased use of image amplification (Ref 25).
.— —
Repetition
Image converter cameras were developed in
rate,p.p.s. recent years not only in the United States but
Type <1972 <1957
;lly_*@ ,@-1~
also in Engl’and, France, Germany, Holland &
‘C!GM lines or holes i“ opaque plate .
FIitplatc androtati”gtirror . . . . 101 101 the USSR (Ref 5)
Lcnticuk plate, apmturc scanning 10* 2.s x 108
Lcnticular plate with nxcchanicd travcrx ( including cime- The benefits of electronic image enhance-
micmqraphyupto 2000 X) . 105 1@
Fibcropt ics dissection, long scrim, low resolution 1~ 1 o~
ment are as follows:
Fitx:oprics, zhort series, resolution of 200 samples pm frame 1. increased sensitivity–2000 to 10,000-fold
width ...,.., . . . . . . . . . . . . ..l Ol—
f.cnticu!:tr plate, rotating mirror, in U.S.S.R. 10* -l@ over the primary image
Lcmticuim plate or slit pla[c and image converter tube .>1OJ >101
— -.—. .. . . ——_ 2. Faster shattering–sub-nanosecond or less
Other ultra high-speed cameras using rotating 3. Memory tube delay permits millisecond
mirrors, rotating slotted discs and optical image camera synchronization
dissection systems ranging from pinholes to len- 4. Reduced distortion–special flattield, dis-
ticular plate arrangements remain in constant use tortion-corrected lenses are used
due to the greater number of frames or pictures 5. Variable contrast control produces higher
produced in sequence. If somewhat less resolution signal/noise ratio
can be tolerated, fiber optic light guides can be 6. Eventual” application to video systems of
used to provide still longer series of pictures high-speed photography
 H 107

At times the image produced in high-speed These same references also discuss photo
photographic studies dealing with explosive chemical image intensification. The prrocessof
phenomena is less than satisfactory. The nature intensifying .a film image is most satisfactory
of the subject, the available instrumentation, the when the image is weak due to underdevelopment
cost, unforseen accidents, such as the failure of in processing. However, even when the faint
a light source to synchronize; all can contribute image is due to underexposure, frequently a
to substantial underexposure. This results in a much stronger and more detailed image can be
low signal to noise ratio making precise film or produced by use of chromium and mercury
picture analysis difficult or impossible type chemical intensifiers
It is customary, when weak images are ex- Occasionally the original, showing an extremely
pected, to employ the most sensitive films avail- weak image can best. be made useful by re-
able, the so-called “superspeed” films, and if printing or rephotographing the film on to
necessary to use chemically vigorous or “forced” extremely high contrast film such as used, in
development (Ref 6a). The gain in sensitivity graphic arts. These “process” or “lithographic”
generally is in the range of two to ten times films are available in all sizes and are convenient
the original (manufacturer’s) rating” of the to use as a contrast and detail enhancing agent
film’s speed. Even color film, such as High- Several photographic feedback techniques
Speed Ektachrome can be exposed at an ex- were used with these procedures. One is to re-
posure speed index (EI or ASA speed) of photograph the original film by reflected light
5000 or more when processed as a negative as it rests against a very black, low reflective
rather than the customary reversal into a background. The positive image seen usually
positive film. Even with the resultant increase shows much more detail than direct observation
of coarse grain, the color differences in the of the original film can reveal. Secondly, there
subject help reveal useful data is a device on the photo market that presses
A technique of “post-fogging” called the weak original film against a front surface
latensification (Ref 2a) can frequently increase mirror in order to gain a doubling of the
the maximum recording rate up to four times. “signal” strength. The third and most effective
This is impractical to attempt with long lengths and unique of these techniques is Michel
of motion picture film but can be successfully Cloupeau’s “optical contrasted.” (Ref 7a) This
employed with a high-speed still, or short strips system places the badly underexposed original
of film. Although the procedure raises the film between semi-reflecting plates, and, by
threshold speed of films by this pre-development, means of collimated light, enables one to
extra exposure it is not the same as “pre-fogging” choose an image which is the sum of multiple
which merely lowers the inherent” contrast range passes through the original film, thereby raising
of films. The difference is in the “employment of the information signal level substantially. This
5 to 30 minutes pre-development exposure .to permits either direct observation or photo
weak green light, rather than an instantaneous reproduction
flash exposure to low level white light. It is image intensifier systems have developed
particularly useful with fast Polaroid photographic from the first electronic image converters that
material were used as fast-acting camera shutters (Ref
In many instances image rescue can be accomp- 3a). Multi-stage image-intensifying circuitry now
lished after the act, eg in case of extreme over- permits extremely high gain (Ref 5a). Signals
exposure. This can be corrected easily by reprinting due to individual photoelectrons leaving the
the film original on to highspeed reversal or photocathode of the intensifier have been
negative film stock using an intense print light photographed. Nearly all the information
source. Little or no detail loss will result. An available in low-density electron images can be
alternate procedure, having some minimal risk to recorded. In recent years multistage electronic
the original film, would be to employ photographic image converters have been developed that
chemical reduction. Standard photographic dark- produce a light gain from 8000 to -50,000X
room technique (Ref 1a) handbooks describe (Ref 4a). Film exposure times can be as large
this technique and include recommendations for as the interframe times, or as short as 5 x 10-9
proportional reducers sec. Picture taking rates from 1 to 100 million
pps a~e easily achieved
 HI08

Streak Cameras
Also known as “smear” cameras and con-
SLIT
IA
tinuously-writing cameras, they’ generally serve %
8 4’
to record movement velocities (Ref 26). Two
basic principles are applied t; the camera de-
sign in order to record a continuous section
I
of a moving image. Either the image is opti- LENS
C2a
cally “wiped” along a strip of photographic I
film lining a drum by a rotating mirror or
prism system or the film itself is moved at
a known rate past the image. Since only a
point of light is necessary to be observed as
it is displaced or moved normal to the film’s
directional axis, the real image of the sub-
ject is focused on to a slit nearly in contact
with the film. As the image of the action
being observed travels along the slit, this
multiplicity of points photographically are
“streaked” on to, the fdm at a known rate.
Frequently two or more slits are used when
more than one action is to be observed.
Spatial resolution is determined by the narrow- Diagram of a simple drum camera. From mea-
ness of the slit, the velocity of the image/fdm surements of the streak record, velocities of
travel rate, and the optical resolution of the movement of the object can be determined
lens system relative to the speed of movement of the film
As shown in the table below (from Ref 26), The” image-illuminated slit recorded when a steady
there has been a considerable improvement in rate of fdm movement was achieved. “Motion
the time-resolution capability of streak cameras picture fdms were used in the 35mm and 70mm
in the last two decades sizes in somewhat similar arrangements. Most of
the more recent designs of streak cameras sub-
Characteristics of Streak Cameras. stitute rotating mirrors for the moving film and
Time resolutions can give a time resolution at least an order of
Streak cameras <1972 <1957 , magnitude greater than the moving film type
5 x 109 10.7 (Ref 12)
Streak record, drum
camera . . . . . . . A somewhat unusual approach is encountered
Streak record, ro~ating when high-speed motion picture cameras of the
mirror, single rotor 2 x 10.9 10-8 Hycam type are used as a streak camera. This
is accomplished by filming through the camera’s
Streak record, rotating
viewfinder which bypasses the prism system
mirror, multiple
1().1o 0.25 x 10-9 that normally cuts up the scene inta frames or
reflection . . . . . .
0.25x 10-9 0.25 x 10-9 pictures. After nearly one-fourth of the film
“Schardin Limit”
Deflecting image has run through the camera the voltage-con-
converter tubes . . (20r 3) x 10-12 10-10.10.11 trolled rate of film travel is reasonably steady
and can be used for velocity measurements.
The format or film size, shape and dimen- Variations in film travel speed are easily ascer-
sion, runs the full range of photographic re- tained by the millisecond markings imprinted
cording. Early streak cameras consisted of a along the edge of the film as the camera’ runs.
large strip of film wrapped around a drum Two advantages are gdined by this technique:
electrically driven to rotate at a high speed. one, the camera can be set to initiate the
(See diagram taken from Ref 26) subject action at any pre-determined delay; and
two, since the film never is exposed again to
 H 109

the subject as with a rotating mirror syste”m,danger sources wa{ an electric spark discharged from
of re-writing is eliminated. Film lengths up to primitive capacitors of the Leyden jar type.
1000ft can be used in this manner. However, Thanks to General Liebessart and other’ early
most of the time, continuous-running cameras, experimenters (Ref 4), the spark evolved to
using short lengths of fdm, are used and double become a controlled, channeled efficient light
exposure caused by the over-run or rewriting source. However, at present it is more useful
is avoided by high-speed shattering in ballistic and wind tunnel studies of aero-
External Shattering dynamic phenomena than for studying
Frequently it is as necessary to cut off the explosives. Confined sparks are still used as a
illumination as quickly and precisely as it is to primary point source in Schlieren high-speed
turn it on. Internal electro-shattering, such as photography. This is particularly useful in
accomplished with the Faraday and Kerr’ cells, shockwave studies. Frequently, inexpensive
can be synchronized with the camera and event expendable fresnel lenses @astic) are used in
exactly as needed (Ref 17). However, as men- conjunction with spark light sources to redirect
tioned above, cameras such as the Beckman/ much of the spark light into a small lens aper-
~itley framing camera as well as most con- ture on the camera. Thk application of high-
tinuously writing “streak” cameras, run the speed photography, usually referred to as
risk of incurring double exposures (Ref 13). shadowgraphy ’ is useful in studying strong dis-
This is due to the image re-writing propensity turbances in a transparent medium such as air’,
of the rotating mirror and many drum-camera water and glass when a powerful shockwave
systems. Small auxiliary detonating charges or high temperature boundary is present
can be used in a number of ways to block Flash Lamp Light Sources
off light and image exactly when required. Electronic flash lamps are used when the
Some of the methods used are listed below: light duration has to extend into milliseconds
1. Explode a small charge in contact with rather than the microsecond range (Ref 7).
a block of glass in the image path. The in- Ultra high-speed cameras such as the Beckman/
ternal multiple cracking caused by the charge Whitley 189 framing camera can produce 25 or
makes the glass effectively opaque more sequential photographs during one flash
2. Blast a mirror out of the optical path of a small electronic flash, commonly, but
to terminate recording of the event incorrectly, called a “strobe” light. Repeating
3. Implode a ring-shaped explosive charge electronic flash units have been made in Germany
of Primacord wrapped around an aluminum that permit a picture taking rate up to 10,000
cylinder through which the light travels to pps at quite high intensities. However, in the
the film United States when a nondestructive extended
4. Wrap a coil of Primacord explosive, some- light source is required, conventional photo-
times covered with black grease, around the flash lamps are generally used to provide in-
camera observation port window safety glass tense illumination. Arranged in overlapping
outside the instrument shelter. Detonation of relay sets they supply light enough to cover
the explosive coil creates a dense black smoke a full length motion picture roll in a rotating
cloud. This method is usually called a smoke prism type of camera such as the regular high-
shutter speed cameras mentioned at the beginning of’
Illumination for High-Speed Photography this article
Despite the presence of brilliant li~t pro- Explosive Light Sources
duced by an explosion, additional high-intensity Still higher energy light sources can be fab-
illumination is often necessary to record high- ricated. These use blocks of high-explosive such
speed phenomena. Also, it is frequently required as Comp B detonated at one end of a tube or
to regulate the length of the picture taking funnel-shaped cone filled with argon, krypton
sequence by controlling the duration of a supple- or xenon (Ref 8). These ionizable gases serve
mentary light source as the light emitting source. Temperatures in
Spark Light Sources the vicinity of the shock wave in argon can
The original “instantaneous point” light exceed 28,000”K (Ref 15), but strangely enough
 H110

it affects’ color film much as a pulsed daylight rapid acceleration with no torn sprocket holes
quality source. The duration and luminosity of in all moving film type high-speed cameras.
this type of explosive “candle,” using free- One detriment with the new mylar type films
flowing argon, can range up to more than 500 is that conventional splicing can not be used–
microseconds at intensities much exceeding sun- pressure sensitive clear tapes seem to be the ,
light. Lining the light source tube with aluminum most practical approach to the joining of fdm
foil covered sheet explosive may help in achieving lengths
the longer duration (up to 500Ksec) luminosities. A still more useful improvement is in in-
Reflecting surfaces on the inside of the argon creased sensitivity. Exposure indices (EI) or
container have the effect of making the light fflm “speed” now easily attain the range of
source have an apparent radiating area greater 2000 to 5000, an increase of 10 fold over
than its actual cross-section. Thus, an”argon light former high-speed films. With vigorous film
source with a reflecting internal surface illuminates a processing at high temperatures, color and
target more effectively than an identical light black & white films have been successfully
source with matte surfaces. The length of. the exposed at an EI of 6400. The use of Polaroid
light path, is roughly proportionate to the film continues to expand with a soon-to-be-
duration of the luminosity. if rarefaction effects available fast film effectively equal in “speed”
can be minimized to 50,000
Laser Light High temperature film processing not only
New techniques in high-speed photography now permits film to be processed in the tropics
have been aided by recent developments in and in high temperature locations but allows
laser technology (Ref 19). In some instances the specially hardened emulsions to develop very
the monochromatic. nature of laser illumination rapidly with no detrimental changes in their
has been useful in replacing fast X-rays in characteristics
order to perceive important details in self- Cblor Photography
luminous events (Ref 18). The steady increase The use of color film in many instances ex-
in use of lasers permits simpler interferogram tends the usefulness of high-speed photography.
systems to be arranged. In addition, hologram When more than one explosive subject is being
techniques are now practical with sub-nanosecond studied simultaneously, it is convenient to ob-
exposures. This extends interferometric proce- serve each through complementary or contrasting
dures into a true 3rd-dimensional recording color filters. With streak cameras using more
system than one slit on the same experimental shot,
Nonexpendable light sources, such as a Q- the color contrasting hues can overlap and inter-
switched pulsed laser can be protected. from mingle and still be free of double exposure con-
destructive forces encountered in the photog- fusion. This is done simply by placing a clear
raphy of explosive material by piping the light bright-colored gelatin filter over each camera
through fiber optics. to the experimental zone. slit so that the resulting streaks are ~endered
Occasionally lens systems are used to relay the in the hue pertaining to a particular slit
light from mirrors located near a protective
barrier shielding the laser (Ref 16) Specially made color filters can be inserted
in place of the conventional knife-edges in
Photographic Films and l?ocessing Procedures Schlieren systems (Ref 20). Frequently this
High-speed photography benefits by certain produces higher resolution because of the avoid-
changes in modern films. Many of the newer ance of knife-edge diffraction., Restricting parts
film emulsions are now coated on polyester of the subject image to monochromatic record-
plastic bases. In addition to attaining dimen- ing also presents additional gains in sharpness.
sional stability approaching that of glass, these Composite color falters placed at field stops in
films are thinner and stronger than the conven- the optical system can add considerable infor-
tional acetate film supports hitherto used. This mation to the photo image when captured on
permits more film, thereby a longer run, on a color film
given motion picture size spool. The increased Special Color Films
‘strength and resistance to tear allows more A Kodak color film with the blue layer
.
 H111

quite sensitive to in fra-red radiation is now ton & D.A. Cahlander, HSP 5, 3-5 (1962) 8)
commonly available. This enables dynamic thermo- Z. Pressman, HSP 5, 56-60 (1962) ‘9) F.’J. ‘
graphy to be included in high-speed photographic Grundhauser et al, HSP 5, 149-153 (1962)
recording 10) A. Stenzei & G. Thomer, HSP 5, 173-175
The use of color film for high-speed photo- (1962) 11) G. Thomer & R. Schall, HSP 5,
graphic studies of explosions underwater has 176-178 (1962) 12) T.P. Liddiard, Jr. & B.E.
been made more feasible by GAF’s new Blue- Drimmer, HSP 5, 322-328 (1962) 13) S.J.
Insensitive Anscochrome Aerial Film which does Jacobs, HSP 5, 335-340 (1962) 14) L.E.
not have a blue-sensitive top layer (Ref 21). Davidson, HSP 5, 462 (1 962) 15) J. Roth,
This high-speed (EI nearly 1000) color film has JApplPhys 35 (5) 1429 (1964) 16) J.K. Cros-
high resolution and eliminates the need for a by & R.C. Honey, ApplOptics 2, No 12, 1339-
minus-blue falter on the camera. Schlieren and 1340 (Dee 1963) 17) M. Blanchet, HSP 6, 313-
photoelastic stress analysis can conceivably gain 320 (1964) 18) L.E. Hargrove & J.S. Courtney-
in contrast with this new film. In addition, it Pratt, J SMPTE 74, 1085-1095 (Dee 1965) 19)
should be less affected by smoke and other V.V. Korobkin et al, HSP 9, 232-236 (1970)
explosive debris which scatters the shorter wave- 20) J.R. Meyer-Arendt et al, J SPIE 9, 18-21
length light (blue) more than “red” light (Nov 1970) 21) W.G. Hyzer, PMI (Photo
Lastly, a somewhat unorthodox color film, Methods for Industry) 18-20 (Jan 1971 ) 22)
referred to as Extended Range (EG & G) film C. Wyckoff, PM1, p 20, (Jan 1971) 23) A.S.
permits photographing an explosive subject over Dubovik & N. M. Sitsinskaya, J SMPTE 80, 691-
an extremely wide exposure range. This mul- 698 (197 1) 24) W.G. Hyzer, Research/Develop-
tiple layer color negative fdm permits photog- ment, p 56 (Aug 1972) 25) V.A. Babits, Photo-
raphy requiring effective exposure ratings from graphic Appl in Sci, Tech & Meal, 22-28 (Jan
approximately .03 or slower-to a maximum 1972) 26) J.S. Courtney-Pratt, J SMPTE 82,
equal to El 400. Originally developed to 167-168 (Mar 1973)
photograph the sun’s corona, it has found use * J Soc Motion Picture & Television Engr
** Boc Intl Congress of High-Speed Photography
with high-speed photography when the correct
exposure is difficult to determine. Thk film, Refs: (for section on Electronic Amplification
however, produces colored images in blue, red, of Light Image & Techniques of Image Enhance-
and yellow that bear no relation to the subject’s ment): 1a) B. Dudley & K. Henney, Handbook
original colors of Photography, McGraw-Hill, NY, pp 547-561
An experimental new color film called XRC (1939) 2a) T.H. James &G.C. Higgins, Funda-
(for extended response color) has been intro- mentals of Photographic Theory, John Wiley, NY,
duced by Applied Photo Sciences Inc (Ref 22) p 57 (1948) 3a) A.E. Anderson et al, HSP
that is a “true” color film. It too has a re- 5,95 (1962), “The Astracon Tube and its
markably extended exposure range of responses Application in High-Speed Photography” 4a)
to scene brightness, said to “nearly match the M.L. Ped & L.W. Jones, I-ISP 5, 98 (1962) “Very-
human eye” High-Gain Image Intensifier Systems” 5a) R.A.
An excellent review of advances in high-speed Chippendale & J.R. Folkes, HSP 5, 104 (1962)
photography is presented by Courtney-Pratt in “Electronic Image Intensification” 6a) Z. Press-
Ref 22, listing 115 references. Additional source man, HSP 5, 80 (1962) “High-Speed Films with
material, taken from Courtney-Pratt’s article, is Vigorous Development” 7a) M. Clouppeau, HSP
listed at the end of the references to this article 5, 240 (1962) “Optical Contrasters”
Written by ZEV PRESSMAN Attention is drawn also to the following
Refs: 1) C. Cranz & H. Schardin, ZPhysik 56, books, etc which provide valuable source
147 (1929) 2) J.H. Waddell, JSocMotionPic- material:
tureEng 46, 87 (1946) 3) M. Sultanoff, J P. Fayolle & P. Naslin, Photographic Insian-
SMPTE* 55, 158-166 (Aug 1950) 4) J.S.T. tarr~e et Cin6matographie IJltrarapide, Editions
Looms & R.J. North, HSP** 3, 62-66(1 956) 5) de la Revue d’Optique, Paris, 1950
G.H. Lunn, HSP 3, 102-107 (1956) 6) R. W.D. Chesterman, The Photographic Study
Schall, HSP 3, 228-237 (1956) 7) H.E. Edger- of Rapid Events, Clarendon Press, Oxford, 1951
 H112

G.A. Jones, High-Speed Photography, Chap- High-Speed Processes, Pergamon Press, London,
man & Hall, London, 1952 1968
H. E.. Edgerton & J.R. Killian, Flash!, Charles K.S. Karsten, Science of Electronic Flash
T. Branford, Boston, 1939 & 1954 Photography, Chilton, NY, 1968
A.A. Sakharov, High-Speed Photography in H.E. Edgerton, Electronic Flash, Strobe,
Science & Technology, Publishing House of McGraw-Hill, NY, 1970
Foreign Literature, Moscow, 1955 The bibliography on high-speed photography
J.H. Waddell, Photographic Motion Analysis, (to 1960) compiled by Elsie Garvin, Eastman
Industrial Laboratories Publishing Co, Chicago, Kodak, Rochester, NY (Distributed at HSP 5)
1955 Bibliography on High-Speed Photography
W.G. Chace & H.K. Moore, Exploding Wires, 1960-1964 (Kodak Pamphlet P-27) compiled
Plenum Press, NY, 1959; ibid, Vol 2, 1962 by Elizabeth W. Tapia, Eastman Kodak Co,
R.L, Aspden, Electronic Flash Photography, Rochester, NY, 1965 (Distributed at HSP 7)
Macmillan Co, NY, 1960 The bibliography on high-speed photography
C.H. Greenewalt, Hummingbirds, Doubleday, 1964-1970 compiled by Elizabeth W. Kraus,
NY, 1960 ed W.F. Walker, Eastman Kodak, Rochester,
W.G. Hyzer, Engineering & Scientific High- NY (Reprinted HSP 9, 548-595)
Speed Photography, Macmillan Co, NY, 1962 The volumes comprising the Proceedings of
K.R. Coleman, “Ultrahigh Speed Photog- the International Congresseson High-Speed
raphy,” Reports on Progress in Physics, 26, Photography, as described above
269-305, 1963
P.W. Holder & R. J. North, “Schlieren High Temperature Behavior of Explosives. See
Methods,” Natl Physical Laboratory Notes on Wenograd Test
Appl Science, No 31, HMSO, London, 1963
The bibliography on image dissection in High Velocity Test Gun. A high-velocity gun
high-speed photography by J..S. Courtney- facility, 87 feet long and with a .3.5-inch bore,
Pratt is being used to study material behavior under
W.G. Hyzer, “Photographic Instrumentation extreme impact conditions. Impact velocity will
Science & Engineering,” Superintendent of reach a maximum of 8000 to 10,000 fps and
Documents, US Govt Printing Office, Washing- will exert pressures of several million pounds
ton, DC, 1965 per square inch upon experimental materials
F. Friinpjel, High-Speed Pulse Technology{ Studies of the reaction of materials to
Vol 1 & 11, Acqdemic Press, NY, 1965 extreme mechanical shocks are important in
J. Rutkowski, Stroboscopes for Industry the design of components and systems which
and Research, Pergamon Press, London, 1966 may experience severe impact. Experiments with
F. Van Veen, Handbook of Stroboscope, different metals, alloys, ceramics, plastics and
General Radio Co, W Concord, Mass, 1966 composites help engineers choose the ideal
The bibliography on Holography compiled material for different applications under shock
by R.P. Chambers & J.S. Courtney-Pratt loading. They also provide the scientist with
R. F. Saxe, High-Speed Photography, The a more fundamental understanding of the
Focal Press, London, 1966 materials themselves
C.E. Miller, Handbook of High-Speed Photog- The gun will be fired by igniting a charge
raphy, 2nd ed, General Radio Co, W Concord, of conventional artillery propellant weighing
Mass, 1967 up to 20 pourids. The explosion propels a two-
K. Vollrath & G. Thomer, High-Speed pound projectile (Sabot) and impactor through
Physics, Springer, Vienna, 1967 the barrel to the target. Since the experiments
E.C. Cassidy et al, Investigations of the require precisely controlled impact conditions,
Exploding Wire Process as a Source for High the ba~el must be honed to a tolerance of
Temperature Studies, (NBS Monograph 109), 0.0001 inch and aligned to 0.020 inch along
US Govt Printing Office, Washington, DC, 1968 its entire length before each test. As in similar
A.S. Dubovik, Photographic Recording of guns, the bore is evacudted to about one micron
 H113

of mercury to prevent undesirable effects (1955-60), in 1926 published “Kinetics of Chem-

during impact ical Change,,” a sr.ibject in which he was already
The test material rmy be mounted either on world-renowned. Continuation of his research
the Sabot or placed as a target at the muzzle. into chemical kinetics later earned him the Nobel
Instrumentation which will record data on Prize in Chemistry (1956), along with N. N.
material deformation will provide a resolution Semenov of Russia. Sir Cyril was also noted for
of a few billionths of a’second in time and a his breadth in fields other than science. He spoke
few millionths of an inch in displacement six languages, including Chinese, and was a
Refs: 1) Sandia Science News, Vol 2, No 4 serious, student of the literature of many coun-
(March 1969), Sandia Corp, PO Box 5800, tries, as well as being a painter. He served on
Albuquerque, New Mexico 87115 2) G. Cohn, many government advisory bodies and boards
Edit, Expls & Pyrots 2 (1 1), 1969 and was, for these contributions, knighted by
King George VI in 1948. He was president of
Highways and Byways in Combustion. Title of the Chemical Society (London) in 1946
a paper by D.T.A. Townsend, JlnstFuel 27, Ref C&EN 45, No 46, 63 (1967)
534-44 (1954) & CA 49, 2057 (1955). [n this
paper investigations of high-pressure explosions, Hippuric Acid and Derivatives
flame propagation and combustion of higher- Hippuric Acid, also called Benzoylaminoacetic
mol-wt hydrocarbons are reviewed acid, Benzoylglycine, Benzaminoacetic acid,
Cc Hs CONHCH2 COOH, mw 179.19; colorless
Hill Powder. Has been used for loading shells: crystals, mp 188° (decomposes on further
NHq Picrate 43.0, K Picrate 53.5 & charcoal heating),d 1.371, sol in hotwater, alc & eth.
3.5 Used in org “synthesis& medicine
Refi Daniel (1902) 375 Refs: 1) Beil 9, 225, (107), [174] & {1 123}
2) CondChemDict (1971), p 446
Himalaya’s Explosives KC103
(Portugal).
Hippuric A cid Azide or Hippuroyl Azide,
60-80, starch, charcoal etc 10-25, oil 4-10, C6 H,5 .C0.NH.CH2 .C0.N3 ; mw 204.19, N
metallic dust or powder 2-10, metallic oxides, 27.44%; ndls (from benz or eth), mp 98°; sol
or dehydrated CuSOq 2-5T0 in ale, chlf & glac acet acid; S1sol in eth & cold
Ref M.,A.G. Himalaya, BritP 22030 (1910) & benz; insol in w; was prepd by the action of Na
CA 5, 3158 (1911) nitrite on hippuryl hydrazine in warm water
Refs: 1) Beil 9,247 2) T. Curtius, Ber 23,
Himley Explosive. KC103 45, KN03 35 & 3031 (1890)
coal tar 20 Mononitrohippuric Acid,
Note: This explosive was prepared by impreg- 02 N.C6H4.C0.NH.CH2 .COOH; mw 224.17, N
nating the first two ingredients with tar 12.50%. Three isomers are known:
dissolved in petroleum ether and allowing the 2-Ni[rohippuric Acid, trysts (from w), mp 190°
ether to evaporate (Ref 1)
Refs: 1), Daniel (1902).375 2) Pfrez Ara 3-Nitrohippuric Acid, ndls (from w), mp 166°
(1945) 216 3) Giua, Trattato 6, 400 (1959) (Ref 2)
4-Nitrohippuric A cid, colorless prisms (from w),
Hinde Explosive. NC 64.0, pulverized coal 23.0, mp 129–30° (Ref 3)
Arnm citrate 12.0, ethyl palmitate 0.25, Ca car- Other props & methods of prepn are given in
bonate 0.2.5 & Na carbonate 0.50% the Refs
Refs: 1) Daniel (1902) 375 2) Giua, Trattato Refs: 1) Beil 9,374, [246] & {1478} 2) Beil
VI (1) (1959), 344 9,383, [252] & {1517} 3) Beil 9,395, [272]
& {1726}
Hinshelwood, Sir Cyril, 70, retired since 1965 as Mononitrohippuric Acid Azide,
professor of chemistry at Oxford University, 02 N.C6H4.C0.NH.CH2 .C0.N3; mw 249.21, N
died Ott 9; 1967”in London. Sir Cyril, who was 28.1 l%. Two isomers are known:
a fellow of the Royal Society and its president 3-Nitrohippuric Acid Azide, yel powd, very un-
 HI14

stable especially in daylight, decomp explosively HISTORY OF EXPLOSIVES, AMMUNITION

above 74° if heated rapidly. Moderately sol in . AND WEAPONS
eth; S1sol in ale, chlf & benz; insol in w; prepd Introduction
from 3-nitrohippuric hydrazide & Na nitrite in Prior to describing history of explosives, it is
glac acetic acid (Refs 1 &3) desirable to &y a few words about cold weapons
4-Nitrohippuric Acid Azide, yel powd, mp 70–72° which were used in wars many centuries before
(dec), deflgr on heating & explodes on heating in explosives or incendiaries were invented
light; sol in eth; S1sol in alc & benz; insol in w; Greener (Ref 7, pp 1-12) described such
can be prepd from 4-nitrohippuric hydrazide & weapons and gave many illustrations as did
Na nitrite in HC1 (Refs 2 & 4) Dupuy & Dupuy (Ref 69, pp 2ff)
Refs: 1) Bei19, (156) 2) Beil 9, (164) Primitive cold weapons can be subdivided
3) T. Curtius, JPraktChem [2] 89,490 (1914) into two major categories: shock and missile,
4) T. Curtius, JPraktChem [2] 84,131 (1 916) of which missiles could be operated by hand
3,5-Dinitrohippuric Acid, or mechanically. The earliest shock weapon
(02 N)2C6H3 .CO.NH.CH, .COOH; mw 269.17, was a heavy club, while the first missile was
N 15.61 %;nd1s (from w) + H20, mp 181.4°; a stone or other heavy object hurled by hand.
was prepd by treating glycine in a NaOH soln The next development in missiles was a sling
with 3 ,5-dinitrobenzoyl chloride (leather or string) which could be used for
Refs: 1) Beil 9, <1937> 2) B.C. Saunders et hurling smooth stones at longer distances than
al, BiochemJ 36,368, 371 (1942) by hand. The stones were later replaced by
4-Nitrohippuryl-aminoacetyl Azide, lead balls. This weapon was used as late as
02 N.C6H4.C0.NH.CH2 .C0.NH.CH2.C0.N3 ; AD 1572 and is still used by some savage
mw 306.24, N 27.45%; yel powd, mp 91–92° tribes (Ref 69, p 2). In some weapons a stick
(dec), explodes on heating in the light; sol in was hurled and this, in turn, evolved into darts
NaOH; v S1sol in eth; was prepd by treating 4- and javelins. In Australia appeared the boomerang
nitrohippuryl-aminoacet yl-hydrazide, Na nitrite which is still used for hunting. The club was
& HC1 modified by a number of ways, one of them
Refs: 1)Beil9,(163) 2) T. Curtius, JPrakt- was to attach a heavy stone or metal piece at
Chem [2] 94, 134(1916) its end. One such weapon was the Russian
palitsa. The club with a sharp ax-like end was
Hirschfelder-Sherman Calculation of Thermo- the tomahawk of the American Indians. The
chemical Constants for See A.M.
Propellants. shock action counterpart of the javelin was the
Ball, “Solid Propellants Part One,” Army Materiel heavy pike or thrust spear. The spear with an
Command Pamphlet AMCP 706-175, ‘Washington, ax-like end was halberd invented in 15th century
DC (1964), pp 7, 9, 10 & 53 and used since then by Vatican Guards
The bow and arrow, invented late in the
Hispano-Suiza Gun. A 20mm aircraft gun used Stone Age (ca 3500 BC), became an invaluable
by the British during WWII and which proved to weapon for many centuries (See Vol 1 of Encycl,
be a successful weapon. It was mounted either for p A488-R) (Illustrated in Ref 7, p 3)
firing thru the propeller hubs or from f~ed mounts At the Bronze Age (sometime before 2000 BC),
in the wings of an airplane which followed the Stone Age and then later at
It was capable of delivering fwe at the rate of the Iron Age (ca 1000 BC), the most important
600-700 rounds per minute contribution was the adoption of metal for points
Refs: 1) War Dept Tech Manual, TM 9-1901, of arrows & spears and also for edges and smash-
p 323 2) J.A. Solomon, PATR 949 (1939) ing surfaces of other weapons. The new weapons
(20mm CRA for Hispano-Suiza gun) 3) M.L. of metallic era were the dagger and the sword.
Mathesen, PATR 984 (1939) (20mm CRA for They were propably first made by Assyrians
Hispano-Suiza gun) 4) M.L. Mathesen, PATR (Ref 69, pp 2 & 8). Their chariots also were
1025 (1940) [20mm CRA for Hispano-Suiza made of iron
(Birkigt) gun] 5) A.B. Schilling, PATR 1627 The most important protective armor deve-
(1946) (20mm HE CRA for Hispano-Suiza gun) loped in ancient time was the shield, which was
6) A:B. Schilling, PATR 1628 (1946) (20mm
AP CRA for Hispano-Suiza gun)
 H 115

\
usually held in the left hand or on the left arm, It is illustrated on p 7 of Ref 7 and p 279 of
leaving the right arm free to wield a weapon Ref 69. It was used successfully by the Normans
Emergence of historical China, as a small in invasion of England and one of the crossbow’s
country around Yellow River Valley was around arrows killed King Harold
1600 BC and the first known ruler was the In siege operations, one new weapon was in-
Shung Dynasty (1 523 to 1024 BC), which was troduced. This was the trebuchet or mangonel,
followed by the Chou Dynasty (1027 to 500 BC). a missilehurling machine for battering fortifi-
Their weapons were metallic but not as good as cations or for throwing rocks or other objects
those of the Middle East. The same may be over walls. Unlike the ballista and catapult,
said about early Hindu weapons (Ref 69, pp 14–1 5). which obtd their power from tension or torsion,
More about China is below the propelling force of the trebuchet was provided
Substantial advances in tactics and doctrine by a counterweight (up to 10 tons) (Ref 69,
of land warfare were made in the middle of the p 281 and Fig on p 280)
6th Century BC by Cyrus the Great of Persia, One very important cold weapon appeared
but he used the same cold weapons as listed shortly before the introduction of Gunpowder
above with only slight modifications (Ref 69, p 16). (ca 1200 AD): the so-called English longbow,
The Greeks at that time developed an Army which was originally a Welsh weapon. It was
outfit consisting of well trained soldiers known claimed to have a range of up to 400 yards,
as hoplites. They carried a pike, a short sword maximum, and effective range ca 250 yards.
and a shield (See Fig on p 17 of Ref 69) It is described and illustrated on pp 5 & 12
A very important improvement in hurling of Ref 7 and on p 332 of Ref 69
missiles took place ca 400 BC when ballista Crossbow and longbow continued to be in
(See Vol 2 of Encycl, p B5-L) and catapult service up to ca 15th century, competing with
(Vol 2, p C9 l-L) were invented. They are il- early firearms such as handgun (Ref 7, p 4]
lustrated in Ref 7, p 6 and Ref 69, p 38). History of Incendiaries, Fireworks and Black
They hurled missiles up to 500 yards Powder up to the Middle of 19th Century.
In siege warfare invented “after 350 BC by In addition to a brief history of Black Powder
engineers of Alexander the Great of Macedonia (also known as Gunpowder) given in Vol 2 of
were the battering ram and the famous movable Encycl, pp B165-R to B168-L, we are giving
tower (turns on wheel) (See Fig on p 39 of here chronological listing in the manner done
Ref 69). Other inventions were mantelet, in a Japanese article by Dr Heizo Nambo (Ref
telenon and mural hook (See Figs on p 40 of 66). Its English translation was obtd thru the
Ref 69) courtesy of Mr Gunther Cohn of the Franklin
The above described weapons were also used Institute, Philadelphia, Pa, 19103
by Macedonians under Alexander the Great We also used the following books, full titles
(b356, d323 BC) during’ their conquest of Europe of which afe given in the list of Refs, which
and half of Asia. No new weapons were used, follows the description: Daniel (1902) (Ref 3,
but they encountered in India a new weapon pp I to X, written by M Berthelot); Greener
which will be described” below (1910) (Ref 7, pp 13–17); Marshall 1 (Ref 11,
Next to Alexander, Julius Caesar (100– pp 11–50); Colver (1918) (Ref 12, pp 1–29,
40 BC) was the outstanding director of siege 496–505 & 563–64); Marshall 3 (1932) (Ref
operations, bringing systematic procedures to 20, pp 1–2); Stettbacher (1933) (Ref 21, pp
operations. Fig on p 83 of Ref 69 shows fort, 3–1 8); Newman (1943) (Ref 33); Dutton (1960)
tower, mound and mantelets designed by him, (.Ref 58, pp 5 to 174); Dupuy & Dupuy (1970)
while on p 84 is shown testudo, which consisted (Ref 69, pp 332–33 and other pp listed in
of long shield raised and interlocked over the General Index on p 1322-R, under Gunpowder);
soldiers’ heads and backs Gorst (1972) (Ref 71, pp 5–12)
One important cold weapon, the crossbow or We are referring also to historical information
arbalist, appeared in the 11th century (See Vol 1 given under individual items in Vols 1, 2, 3, 4,
of Encycl, p A477-L, where it is erroneously 5 and 6
shown that it was invented in the 4th century). Accdg to Greener (Ref 7, pp 13 & 14):
 HI16

“There seems little doubt that the composition Delium. Another use of poisonous gaseswas
of gunpowder has been known in East from times recorded in 187 BC when the Remans were
of dimmest antiquity. The Chinese and Hindus driven from the town they besieged by means
contemporary with Moses are thought to have of fumes produced by burning feathers and coal.
known of even the more recondite properties Poisonous fumes produced by burning green
of the compound. It is very possible that wood were used during France-Algerian War.
Alexander the Great did absolutely meet with More effective chemical agents were proposed
fire-weapons in India, which a passagein Quintus during Crimean War ( 1853–56) and American
Curtius seems to indicate”. Civil War (1861 –65), but the real chemical
The introduction of explosives into Europe warfare began in 1915 (qv) (See Vol 2 of
followed the Mohammedan invasion. Greek fire, Encycl, p C 166 and also next item)
into the composition of which nitre and sulfur 400 BC. Accdg to Dutton (Ref 58, pp 13–14),
entered, was used prior to the fall of the Western Spartans soaked blocks of wood in hot pitch &
Roman Empire (prior to AD 284) sulfur, piled them against the walls of enemy’s
It is known that prior to invention of explo- fortresses, and applied the flame of a torch. As
sives, incendiaries and fireworks were known, the walls were then built of wood the device
especially to Chinese and Hindus and later to was very effective. This served as a prototype
Arabs and Greeks. That is why the chronolo- of wild fire used much later. It seems that
gical list given below starts with them: Spartans also invented a prototype of flame
1190 BC. This is the earliest date for incen- throwers. The original device was in the form
diaries used in warfare listed in Ref 66, p 10. of a huge iron caldron fdled with burning pitch,
It concerns Trojan troops attacking Greek Navy sulfur & charcoal. This was mounted on top a
with incendiaries high movable platform which the attackers
fvote.’ The siege of Troy is listed in Ref 69, moved up to the defenders’ walls. The hollow
p 11-R as taking place ca 1184 BC trunk of a tree was then tilted to the edge of
850 BC. In this year incendiaries were used in caldron, and air was pumped thru the trunk with
the battle of Mesopotamia, Irak (Ref 66, p 11) a big bellows. Thus tarry-sulfurous smoke and
Note: This battle is not listed in the book of tongues of fire were air-blasted upon the enemy
Dupuy & Dupuy (Ref 69) to suffocate them. It is probable that fire pots
500 BC. Accdg to Dupuy & Dupuy (Ref 69, were invented as early as that. They were
p 36-L), Sun Tzu, a native of the state of Ch’i earthenware jugs of various sizes, some thrown
(Modern Shantung) wrote the “Art of War”, by hand, others for hurling by ballista or
the first known military treatise, which provided catapult. Filled with burning brews and acids,
valuable lessons for military men even today the jugs broke upon striking and showered
500–470 BC. In the military tactics of Fan Li their contents on the enemy. The most fiendish
of Yuen (Che Chiang province), ballista of stone and destructive of the fire weapons was the
(Pao of stone) was described (Ref 66, p 11). Greek Fire, invented in the 7th Century AD
There were several ballistas of stone listed on 410–304 BC. Allied Navy of Sparta threw
p 25 of Ref 66. All of their names contained shells of sulfur, pitch and pine rosin by means
the word Pao, such as “Pao Che’ “, “Tan Shao of ballista to fire the Athenian Navy (Ref 66, p 11)
Pao”, “Suang Fen Pao” and “HU Tung Pao” 325 BC. Alexander the Great’s troops which in-
(See Fig on the left side of p 38, Ref 69) vaded India were defeated by means of “thunder
500–450 BC. In the military tactics of Sung bolts” thrown from the castle wall in Lahore by
Si in Wu of Kiang Su, soldiers used “pile of its ,inhabitants called Oxydarace (Ref 66, pp 4 & 11)
fire” and fireworks in the attack (Ref 66, p 11) AIote.’ Accdg to Greener (Ref 7, p 13), Alexander
431–404 BC. Chemical Warfare. The earliest met with real “fire-arms” in India
recorded use of chemical gas during the Pelo- 249 BC. Spartans used incendiaries, consisting
ponesian War (431 –404 BC) when Spartans of small wood pieces impregnated with sulfur
directed the fumes produced on burning of and pitch, in the battle of Plataena (Ref 66, p 11)
green wood mixed with tar and arsenic towards 160–122 BC. Three components of Black Powder
the besieged Athenians in towns of Plathaea and nitre (saltpeter), charcoal and sulfur were de-
 H117

scribed by Chinese alchemists in the Chuan Nan enemy. Marshall prepd a similar mixture but
‘Tsu of Liu An (Ref 66, p 3) was not able to ignite sulfur. He thought that
220 BC & 160-122 BC. When several Chinese the naphtha was ignited by a flame located at
alchemists were separating gold from silver at the orifice of the discharge tube (Ref 11, p 13)
low-temp reaction adding saltpeter and sulfur Later the name “Greek Fire” was given also
to the gold ore in the alchemist’s furnace, they to combustible materials which were ignited
forgot to add charcoal in the first step. Trying and then thrown by ballista or other machines.
to rectify their error they added charcoal in These compns were solid massesof sulfur, pitch,
o the last step. This resulted in tremendous ex- naphtha, and other combustibles, and when
plosion. This accident indicates that the mixture saltpeter was discovered it also was included.
of saltpeter, sulfur & charcoal, exploded at that Such mixtures may more correctly be called
time, was similar to present Black Powder. No Wild Fire. Such mixts were used by Moslems
advantage of this accident was taken at that in the Crusades (See under year 1250 AD)
time (Ref 66, pp 3 & 29–31) (Ref 11, p 13)
141–87 BC. In Robert Norton’s “Gunner” 673–678. Moslem Arabs (of Caliphate) were
published in 1628, it was reported that BkPdr defeated at the walls of Constantinople by de-
was invented at the time of King Vitey (Wu Ti) fenders using Greek Fire (Ref 58, p 14)
of China and used in battles (Ref 66, p 11) 683. In the battle of Mecca (Saudi Arabia),
Note: More detailed description of this subject Kaiaba was fired by the incendiary missiles of
is given in Greener (Ref 7, p 17) Syrian Army (Ref 66, p 13)
200 AD. Tseng Tsao of Wei at the San Quo 690. Accdg to Greener (Ref 7, p 14), the Arabs
Dynasty threw stones in the battle of Kuan Tu or Saracens are reputed to have used Gunpowder
by means of the “thunder vehicle” (Ref 66, p 12), at the siege of Mecca; some writers even affirm
which was actually stone ballista (Ref 66, p 24) that it was known to Mahomet. Marcus Graecus
222-235 AD. Alexander VI of Roman Empiie described in “Liber ignium” an explosive com-
called the “automatic fire” a ball (consisting of posed of 6 parts saltpeter and 2 parts each of
quicklime and asphalt) which spontaneously charcoal and sulfur
ignited on coming in contact with water (Ref 716–718. The Arabs of Caliphate again ap
66, pp 6&12) peared before Constantinople with 1800 ships,
275 AD. Accdg to Greener (Ref 7, p 14), but again were defeated by Greek Fire (Ref 11, p 12)
Julius Africanus mentioned “shooting Powder”, 904. Accdg to Greener (Ref 7, p 14), it was
but its compn was not given recorded that Gunpowder was used by the Sara-
350 AD. Aeneus of Rome put sulfur, pitch, cens at Thessalonica
incense, pine-rosin, and tow (crude flax fibers) 904. The Caliphate troops (Baghdad, Irak), when
into an oval wooden container, ignited the attacking Salonica (Greece), threw ceramic pots
mixture and threw it on the decks of enemy charged with a mixture of pitch, pine rosin, and
ships (Ref 66, p 12) quicklime over the heads of enemy troops to
668 AD, On the basis of advice given by suffocate them (Ref 66, p 13)
Kallinikos of Heliopolis in Syria, an incendiary 904. Before the end of Tang’s rule, Cheng Fan
of secret formula kriown now as Greek Fire or attacked Yu Chang by means of “flying fire”
Sea Fire. Fire was used by the Byzantine fleet to hurled by ballista (Ref 66, p 13)
amihilate the Caliphate Navy (Ref 11, p 12) 940. The Chinese device, called “fire pao”,
Note: Accdg to Marshall 1 (Ref 11, p 12), Col consisted of ballista throwing a “fire ball”, made
Hime in his book listed here as Ref 4, came to of explosive similar to BkPdr, tied to the top of
the conclusion that , besides naphtha, sulfur and an arrow (Ref 66, p 13)
pitch, there must have been quicklime in mixture, 941. The East Roman (Byzantine) Navy poured
which on coming in contact with sea water turned from the tube or syphon located at the” boat’s
into slaked lime whilst raising the temperature stern a liquid (“sea fire”) made from naphtha,
to the point of ignition of sulfur. Greek Fire quicklime and sulfur, over the Russian ships
mixture was discharged from tubes or siphons attacking Constantinople (Ref 66, p 14)
located in the bows of the ships, against the 1000. Tung Fu of Sung Dynasty invented “fire
arrow”, “fire bal~’ and “fire dart rocket”
 HI18

(Ref 66, p 14) and then by others. The devices included: flue
Note: In the book of Dutton (Ref 58, p 5), it arrow, radiation firearm, fire burst er, fire lance,
is stated that during Sung Dymsty (960– 1280) fire ball, thunder ball, etc. They are described
some unknown man described the invention of in the paper of Nambo (Ref 66, p 14)
To-lo-tsi-ang which consisted of a long bamboo 1129. It was suggested equipping, Chinese fleet
tube in which a handful of explosive similar to with weapons such as ballista, fire arrow, etc
BkPdr was placed. When set on flue a strong (Ref 66, p 15)
flame came out accompanied by ejection of 1132. Li Heng besieged Te An using long
some grains of pdr (to a distance up to 150 paces) ladders. The General of Defense Army used
and creating thunderous noise similar to that of 20 fire lances, long bamboo tubes charged with
“paos” Gunpowder (Ref 66, p 15)
1002. In the reign of Chen Tsung of Sung, Lo 1135. During Chinese Civil War, Kin’s fleet
Yung Si invented a “portable ballista” (Ref 66, used thin, brittle pottery bottles charged with
p 14) quicklime, poison and iron pickles (?). The
1040. At the time of Chen Tsung of Sung, Pe resulting smoke injured the eyes of enemy
Sung built a Gunpowder Plant in Pien King (Ref 66, p 15)
(Haifeng, Honan) (Ref 66, p 14) 1147. Accdg to Greener (Ref 7, p 14), Arabs
1043. Russian fleet was defeated at the siege used firearms against the Iberians (Spanish)
of Constantinople by means of Greek Fire 1169-1189. In the reign of Haiao Tsung of
(Ref 11, p 12) - Nan Sung, true fireworks, Yan Hue, made
1045. Pe Sung, Govt issued permit to Wu Ching their debut. They were similar to those used
Tsung Yao for manuf of “firing arrow”, “thorn today (Ref 66, p 16)
fire ball”, and “poisonous smoke ball” (Ref 66, 1214. When the Mongols captured Chung
p 14) Ching, Kin moved his capital to Pien Ching
Note: Brief description of these and other Chinese and the Mongols came into possession of tech-
devices is given in Ref 66, pp 32–35 & 41) niques for manuf of Gunpowder and firearms
1045. Accdg to Nambo (Ref 66, p 38), the (Ref 66, p 16)
compn of powder for “fireballs’?, as described 1218. Accdg to Greener (Ref 7, p 14), there
by Wu Ching of Sung, was: saltpeter 48.5, was artillery at that time in Toulouse
sulfur 25.5 & other ingredients 26.07~ 1218-1258. In the reign of Nan Sung, Gun-
1045. Accdg to Nambo (Ref 66, p 38), the compn powder and fireworks were manufd in quantity
of powder for “thorny flue balls”, as described sufficient not only for local consumption but
by Tsung Yao of Sung, was saltpeter 50.0, sulfur also for export, mostly to Caliphate country
25.0, charcoal 6.25 & other ingredients 18.75%, (Irak) (Ref 66, p 19)
while the compn of powder for “poisonous fire 1220. Accdg to Sancho (Ref 30, p 254), Moors
balls” was saltpeter 38.5, sulfur 19..25, charcoal used machines for hurling stones
6.4 & other ingredients 35.85% 1221. During the siege of Chin Chou, Kin ar-
1073. Accdg to Greener (Ref 7, p 14), Gun- ranged 13 sets of ballistas to shoot “iron bombs”
powder was used by King Salomon of Hungary into the castle. The iron bomb (Tie huo pao),
at the siege of Belgrade was cast, hollow ball, 6cm in diam, filled with
1098. Accdg to Greener (Ref 7, p 14), in a sea Gunpowder and equipped with a fuse cut to
conflict betw the Greeks and Pisanians, the for- the desired length and ignited before launching
mer had flue-tubes f~ed at the prows of their the bomb (Ref 66, p 16)
ships 1221. When Chingis (Chenghiz) Khan and his
1096–1099. In the battle of Nice of the 1st Mongolian troops invaded Europe and Rfissia,
Crusade, the Caliphate troops threw burning they threw stones by crossbow ballistas to break
pitch and fatty, balls. They also shot fire arrows fortification walls; also used poisonous powder
with pitch, sulfur and tow from the walls of flasks (Du huo fou), fire arrows (Huo jian)
Jerusalem (Ref 66, p 14) and fire stone balls (Hua pao). Such weapons
1126. In a triple war among the Sung, Kin and were used at the battle at Amu Dariya river
Mongols, explosive arms were used, first by Sung against Khorasan Empire (present Russian
 HI19

Turkestan) and in other battles (Ref 66, p 18) above Chinese devices could hardly have been
1225. Saltpeter became known in Europe produced without the use of saltpeter, nor the
(Ref 11, p 21) great noise without an explosive (Ref 11, p 15)
1231. When Mongolian general Touloui captured 1233. In the battle of Nan Ching, Kin defeated
Hochung Fu, the Chinese garrison escaped by the Mongols by means of “flying fire lances”
crossing the channel on old ships; then they (Huo quiang), which were tubes, 0.8m long
destroyed the ships by iron bombs (Chen tien made of 16 piled sheets of strong paper charged
lei) (Ref 66, p 16) with an incendiary mixture and porcelain frag-
1232. During the 2nd attack by Mongols on ments. On ignition the flame shot no less than
Nan Ching, Kin used iron bombs (Chen tien lai) 3 meters (Ref 66, p 17)
charged with powder and provided with a fuse. 1234. Allied Army of Mongols and Sung
They flew off a long way to burst. He also against Kin used stone fire brdls, called “HUO
used flying fire lances (Fei huo quiang) (Ref pao”. Kin was defeated and committed suicide
66, p ,16) (Ref 66, p 17)
1232. Accdg to Marshall 1 (Ref 11, pp 14–1 S), 1241. When the Mongolian Khan Bhatu (Batyi)
in the Chinese chronicle “Tun Klang Kang-mu”, invaded Russia and Western Europe, and went
translated into French in the Journal Asiatique as far as Nahlstadt near Lignitz, his troops used
for Ott 1849, there was a description of a poisonous smoke bombs (Ref 66, p 18)
weapon used at the siege‘of Pien King (now 1241. When Bhatu troops besieged castle
Kai-fung-fu). It was “Ho-pao” or “Fire-pao”, Olmiitz in Moravia (present Slovakia), they used
called “Tchin-tien-loui”, translated as “thunder fire arrows to burn the temple (Ref 66, p 19)
that shakes the sky”. The device consisted of 1247. Accdg to Greener (Ref 7, p 18), Seville
an iron pot filled with “ye” (medicine). As had been defended by a “cannon throwing stones”
sopn as light was applied the “pao” rose and 1249. English Monk Roger Bacon (1 214–1292
fire spread in every direction. Its noise re- or 1294) gave in his book “Operibus Artis et
sembled that of thunder and could be heard Magic” the compn of Gunpowder as saltpeter
more than 100 lis (33 Engl miles). It could 7, sulfur 5 and charcoal 5 parts (Ref 66, p 17)
spread fire over more than a third of an acre. Note 1: Accdg to Greener (Ref 7, p 14), it
This fire even penetrated the breast plates on is presumed that Bacon obtd his knowledge
which it fell. These “bombs” were probably about BkPdr from the Treatise found in the
thrown by ballista o Escorial (Spain) Library collection
Note: This item described in Marshall (Ref 11) Note 2: Accdg to Marshall (Ref 11, p 17), Bacon
is identical with that described by Nambo (Ref published ca 1250 his “Opus Tertium” and a
66, p 16) part of its translation (from Latin) was published
1232. Mongolian soldiers constructed with ox- by Col Hime in the Journal of the Royal Artil-
hides a passageto the ramparts of Nan Ching lery, July 1911
castle. They commenced to sap the walls and 1250. Compn of Roger Bacon’s Gunpowder is
made holes in them in which they could remain given in Ref 11, p 26 as: saltpeter 41.2, char-
sheltered from the besieged men above.. Then COd 29.4 & sulfui 29.4%
the besieged Chinese hung “fire paos” on the 1250. ‘It was mentioned under the year 668 AD
chains down the face of the wall. When the as the incendiary which Marshall proposed to
“paos” reached the levels of hidden Mongols, name Wik# Ftie. Such incendiaries were used
they were ignited to explode, thus killing the by Arabs against the Crusaders. Thus Joinville,
invaders. In addn the besieged used “Fei ho participating under St Louis in the disastrous
tiang” (arrows of flying fire), which consisted Sixth Crusade wrote that this, incendiary device
of arrows with attached substance which was came flying thru the air like a’ winged long-tailed
susceptible to taking fire in flight. While flying, dragon, about the thickness of a hoghead, with
such arrows spread flames over a width of 10 the report of thunder and velocity of lightning;
paces. These Chinese devices were much feared and the darkness of the night was dispelled by
by Mongols (Ref 11, p 15 & Ref 66, p 17) this deadly illumination. These devices terrified
Note: Marshall thought that the effects of the the crusaders, because they believed them to be
1
!
I
 H 120

the products of Devil: Fortunately the damage were sent on 100 boats and they routed the
was only slight (Ref 11, p 13) Mongols by means of fire lances and other fire
1257. In the reign of Li Tsung of Sung, the arms (Ref 66, p 18)
invading Mongolian troops were held back by 1273. Accdg to Greener (Ref 7, p 18), Abou
means of big supply (found in Chinese Arsenals) Yuesof used cannon firing stone shots at the
of iron bombs (Tie huo pao) and flying fire siege of Sidgil-messa
lances (Huo quiang) (Ref 66, p 17) 1274. When Chinese troops under Yuang
1259. In the battle of Niebla, Spain the Moors landed at the Hakata Bay (Japan) they shot iron
(Arabs) threw (by means of ballista) stones and bombs (Tie pao), which surprised and defeated
fdth and also “missiles with thunder” (Ref 66, Japanese troops. They called the bombs “teppo”
p 19) (Ref 66, p 20)
1259. In the battle of Melilla, Morocco, the 1277. When Ching Chiang fell, the defending
Moors used cannons and firearms (Ref 66, p 19) general of Sung fired a large cannon (Huo pao).
Note.’ It is more probable that they threw “Wild This destroyed the castle walls and burned to
Fire” missiles by means of ballistas death a 200-man garrison (Ref 66,, p 18)
Note: In the opinion of Marshall 1 (Ref 11, 1279. In the Naval battle near Asmen (Huan
p 13), it is probable that the “missiles with Tang), betw Chang Shih Chieh of Sung and
thunder” used by Moors in Spain and Morocco Chang Hung Fan of Yuan large cannons (Huo
were the same as used in 1250 AD by Arabs pao) were used by both sides. The Navy of
against the Crusaders of Saint Louis (See above Sung was defeated (Ref 66, p 18)
under the year 1250 AD) Note 1: Chronological list given in the article
1259. Accdg to Marshall 1 (Ref 11, p 15) and of Nambo (Ref 68) does not go later than
Dutton (Ref 58, p 5), it was stated in Chinese 1279 AD
annals that in the 1st year of Kai-King was Note 2: Accdg to Marshall 1 (Ref 11, p 18),
made an appliance called “fro-ho-tsiang”, the Chinese do not appear to have developed
meaning “lance with violent fire”. A nest of expls beyond this point, or to have made the
grains of powder was introduced into a long next step, namely of causing the pdr to throw a
bamboo tube, and when the pdr was lit the heavy metal projectile instead of a ball of fire.
flame shot forth from the tube with a noise This step could only be taken by a nation which
like that of a “pao”, which could be heard at was at once progressive and well acquanted with
a distance of about 500 paces (Dutton gives the working of metals
150 paces). It was a device resembling current Note 3: Marshall forgot to mention that progress
Roman candle in China was impeded by Chinese Civil Wars and
1259. In the reign of Li Tsung of Sung Dynasty Mongolian invasion
was invented “fire lance with projectile” (Shi Prior to 1300. The Arabs introduced saltpeter
huo quiang). It consisted of a bamboo tube in their Greek Fire and other incendiaries. In
charged with powder and contg on top of it a Europe saltpeter was more scarce than in Africa
ball serving as a projectile. When the powder was and Asia (Ref 11, p 17)
ignited the flame came out and the ball flew 1300. In the “Liber Ignium” of Marcus Graecus,
away. It was accompanied by a loud noise which which was probably translated into Latin from
was heard at a distance of 270 meters (Ref 66, p 17) an Arabic source ca 1300, were several references
Note: It is not stated whether the lower end of to incendiaries used by Arabs. One of them “ignis
bamboo tube was open or closed. In case of volatilis” (flying fue) consisted of resin 1, sulfur
closed tube it was necessary to attach it to some 1 and saltpeter 2 parts, dissolved into a hollow
firm object because the recoil will kick it in reed or wood. This was in the opinion of Marshall
reverse direction, and in this case it could be 1 (Ref 11, p 17) an incendiary (“wild fire”)
considered as a prototype of modern rocket. The compn listed on p 18 of Ref 11 consisted
Similar bamboo weapons were used by Arabs of sulfur 1, vine or willow charcoal 2 & saltpeter
(Ref 58, p 9) 6 parts. The ingredients were rubbed down to-
1268. In order to relieve the 5-year siege of gether on a marble slab and put into a case, which
Sing Yang by Mongolian troops, 3000 Chinese was short & strong and filled only half-full
 H121

when it was desired to make a loud noise. C)n at Petrograd probably compiled by Shems ed Din
the other hand, a thin, long container, known Mohammed about 1320, which shows tubes for
as “tunics” was completely filled with the above firing off both arrows and balls by means of
powder and flew on being lit. This “flying powder”
tunic” was an imperfect rocket (Ref 11, p 18) Note: It seems th’at the manuscript listed by
14th Century, Early. Accdg to Greener (Ref Marshall as of 1320 is the same as described by
7, Chap IV, “Early Hand Fire Arms”, pp 44– Fuller and Dutton as of 1304. It is also probably
51): ‘No distinction can be drawn between the the same manuscript as listed by Sancho (Ref
small cannon or “crush-gun” of the fourteenth 30, pp 253–54), saying that the manuscript written
century and the earlier fire-arms. A pyrotech- in 1304 in Arabic, discovered by Reinaud & Fave
nical piece developed into a variety hand weapon in a library at StPetersbourg, contd the following
and used for military purposes, especially for compn: saltpeter 10 drachmas, charcoal 2 &
causing disturbances among troops, frightening sulfur 1.5, called Medfraa
horses and stampeding cattle, was employed by Note: Historical description of development of
Eastern nations and by Arabs in Northern Africa”. cannons is given in Vol 2 of Encycl, pp C26 to C29
Such a device which was also used by incendiaries, 1308. Accdg to Greener (Ref 7, p 18), Ferdinand
pillagers, and outlaws is shown in Fig on p 44 of IV of Castille employed guns (marquenas de truefias)
Ref. The gun consisted of an iron tube ca 6 ft in the siege of Gibraltar
long, covered with two hollowed pieces of wood, 1308. A cannon was used for defense of the
and bound round with hemp, hair or leather. castle of Heyer on the Rhein. The castle was
“The tube was fastened to a stick, which could destroyed and the cannon remained in its ruins
be held under arm or placed on a shoulder. The until it was found in 1560 (Ref 7, p 18)
compn of the charge resembled a Roman candle 1310. Accdg to Greener (Ref 7, p 18), firearms
14th Century. Accdg to Marshall 1 (Ref 11, were used by the English at the siege of D’Eu
p 25), some early powder makers added camphor, 1311. Accdg to Greener (Ref .7, p 18), Ismail
sal ammoniac and gum to their Gunpowder to attacked Bazas in Granada, Spain, with “machines
prevent its crumbling. In the “Codex Ger- throwing balls of fire, with noise like thunder”
manicus” of the 14th Century, the following 1313. Accdg to Col Hime (Ref 10, p 2), a
recipe is given: If you want to make a good, weapon resembling cannon was invented by an
strong powder, take 4 lbs of saltpeter, 1 lb unknown German monk. The weapon was used
of sulfur, 1 lb of charcoal, 1 lb of “salpratica” in 1314 at the battle of Bannockburn [Quoted
(mixt of saltpeter, camphor& ammonia dissolved from Marshall 3 (Ref 20, p 1)] (See also Vol 2
in alcohol), 1 CMof sal ammoniac and one twelfth of Encycl, p C26)
part of camphor. Pound it all together with some 1313. Accdg to Greener (Ref 7, p 18), the city
alc untd well mixed and then dry in the sun. archives of Ghent (Belgium) stated that the city
When “coming” of powder was invented in 1425, was in possession of a small cannon
there was no necessity to incorporate camphor 1313 (About). Accdg to Newman (Ref 33, pp
1304. Accdg to General Fuller (Ref 50), this 71 & 75), the gunmakers of Flanders constructed
is the earliest year when a weapon resembling (no year is given) the famous Griznt Bombard of
a cannon was documented. It was in an Arabic G/rent, also known as “Dune Griete”. Its caliber
manuscript. Accdg to Dutton (Ref 58, p 6), it was 25 inches, while its length was 40 feet
was preserved in the Asiatic Museum at StPeters- Note: Accdg to Greener (Ref 7, p 27), Sir John
bourg, Russia, a fragile and faded Arabic parch- Froissart stated that this gun was used by
ment, which presents a sketch drawn by Shems D’Ardevelde at the siege of Oudenarde (no date
Eddin Mohammed in 1304 of a new weapon. It is given)
is described as a “spear that hurls arrows at the 1320. Accdg to Greener (Ref 7, p 17), Berthold
enemy. The spear was a bamboo tube which Schwartz, a monk of Friburg in Germany, studied
had been reinforced by metal bands. Among the writings of Bacon regarding explosives, and
flame and smoke, an arrow is shown on the sketch manufactured gunpowder while experimenting.
flying from the muzzle. Marshall 1 (Ref 11, p 19) He has commonly been credited as an inventor,
said: “There is a manuscript in Asiatic Museum and at any rate the honor is due to him for
 H 122

making known some properties of gunpowder; 1326. Accdg to Sancho, the French attacked
its adoption in “Central Europe quickly followed Gravelines using camons & bombards (Ref 30,
his announcement, which is supposed to have p 255)
taken place about 1320. It is probable that gun- 1326. Accdg to Marshall 1 (Ref 11, p 19), the
powder was well knoin in Spain and Greece Republic of Venice ordered the provision of metal
many years prior to its being used in Central cannons and iron bullets for the protection of
Europe castles and villages. Accdg to Sancho (Ref 30,
1323. Accdg to Sancho (Ref 30, p 254), “balls p 255), the Venetians took Guera employing
of fire with noise” were used at the siege of cannons
Baeza (or Baza), Spain Note: Definition of term “cannon” is given in
1324. Accdg to Marshall 3 (Ref 20, p 1), the Vol 6 of Encycl, under GUN. It is preferred to
town of Metz, France appears to have cannons that given in Vol 2 under CANNON. We are
at that time using the word “cannons” for plural in order to
1325. ‘Accdg to Greener (Ref 7, p 18), in the avoid confusion
records of Florentine Republic was stated “that 1327. Accdg to Greener (Ref 7, p 19), John
two officers were ordered to manuf cannons and Barbour wrote in 1372 that in 1327 at the
iron balls for the defense of castles and villages battle of Warewater, the Scotch first saw the
1326. Accdg to Sancho (Ref 30, pp 254–55) in firearms
Florence there were used cannons of bronze to 1330. Accdg to Sancho (Ref 30, p 254), the
shoot iron balls and the existence of plant manufg first firearms appeared in France during the
cannons is mentioned in chronicles reign of Philippe de Valois ( 1293–1 350)
1326. Accdg to Marshall 1 (Ref 11, p 19), in an 1331. Cannons were used by Moors at the siege
illuminated manuscript entitled De Officiis Regum, of Alicante (Spain) to open a breach in the wall
written in Latin by Walter de Millemette and (Ref 11, p 19& Ref 30, p 254)
preserved in Christ Church Library, Oxford, Eng- 1338. Accdg to Greener (Ref 7, p 18), the
land, there is a drawing reproduced here of a ‘ English contemporary record mentions that
rudimentary gun shaped like a bottle, showing a King’s ships “Bernard de la Tour” and “X’ofre
dart used as a missile and a man applying a fire de la Tour” were equipped with cannons and
to a touch hole. The same illustration is repro- handguns
duced in the book of Dupuy & Dupuy (Ref 69, 1338. Accdg to Nambo (Ref 66, p 39), the
p 333). The beautiful manuscript (in color) was compn of French powder of unknown use was:
seen by the senior author of this Encycl during saltpeter 50, sulfur 25 & charcoal 2570
his trip to England 1338. Accdg to Greener (Ref 7, p 19), powder
Note: Accdg to Dutton (Ref 58, p 32) this type and cannons were provided for the protection
of weapon was made of brass of the ports Harfleur and l’Heure (France)
against Edward 111
1339. Accdg to Marshall 3 (Ref 20, p 1), there
was mention of six brass “gonnes” in the London
Guildhall, together with “peletae” weighing
4.5 lbs and 32 lbs of powder, showing that the
darts used in the very earliest guns were replaced
by small balls
1340. Sir John Froissart in “Chronicles of
England, France and Spain”, Bk I, Chap 72,
stated that Scots used cannons in the siege and
capture of Stirling and in 1340 or 1341 Gedymin,
Grand Duke of Lithuania was killed by a cannon
ball at the fortress of Walona, which was being
besieged by the Germans. It is evident that at
Early cannon that time the guns were in use for siege warfare
but they were not sufficiently mobile for the
field (Ref 20, pp 1–2)
 H 123

14th Century. Accdg to Nambo (Ref 66, p 39), Calais, he obtained a further supply. That fue-
the compn of German powder of unknown use arms were used by the English at Crt?cy in 1346
was: saltpeter 66.7, sulfur 22.2 & charcoal 1~. 1%. is a well ascertained fact
A sfightly different compn is given in Marshall 1 Note 2: Accdg to Marshall 3 (Ref 20, p 2), it
(Ref 11, p 31). It was: saltpeter 66.6, charcoal was improbable that cannons were used at the
16.6 & sulfur 16.6% battle of Cr6cy, because at that t~e no light
1340. Accdg to Colver (Ref 12, p 496),’ solid weapons existed but there were only heavy siege
spherical projectiles for cannons started to re- cannons
place the arrow-shaped projs. The material was Note 3: Gen Fuller stated in Vol 1 of his book
stone, bronze or iron ‘ (Ref 50) that accdg to Sir Charles Oman the
1340. In two frescoes in the church of former weapons used at Cr6cy were .ribaudequins, which
monastery of San Leonardo in Leccetto, near were invented in 1339 and may be considered
Siena, painted by Paolo del Maestro Neri, are as ancient machine guns. They consisted of
shown: a large cylindricrd cannon discharging a several iron tubes ck-imped together to form a
spherical ball, and several hand guns (Ref 11, p 19) device resembling a multiperforated cylinder. The
1341. Accdg to Sancho, the Scots took from the tubes could be fued separately or simultaneously
English the town of Stirling employing artillery 1347. Accdg to Dutton (Ref 58, p 39), cannons
(Ref 30, p 254) were definitely used by the British at the siege
1342. Cannons were used by Moors in the de- of Calais, France. They also had ribaudequins,
fense of Algeciras (Spain) against Don Alfonso XI mentioned above under Note 3
de Castilla (Ref 11, p 19 & Ref 30, p 254) 14th Century, 2nd Half. A brief description and
1342. Accdg to Marshall 1 (Ref 11, p 19), illustrations of 14th century cannons are given
Counts of Derby and Salisbury, who were present in G“reener (Ref 7, pp 20–5). The illustrations
at the above battle of Algeciras, supposedly in- include: p 21 — Early breech-loading cannons;
troduced guns and gunpowder into England. In p 22 – Iron breech-loading cannon, Cast breech-
the following years there are several refs in the loading cannon, Italian bombard, and Early
accounts of the Wardrobe of Edward III of English breechioader; p 23 – Italian muzzle-
payments for saltpeter for manuf of Gunpowder loading cannon called “Cerbotain”; p 24 –
Note: Accdg to Greener (Ref 7, p 15), ingre- German Artillery; p 25 – Elbow-joint bombard
dients for Gunpowder manufd in England were 1350. Bullets. The primitive bullets, which were
usually separately purchased abroad and mixed either stones or metallic slugs of irregular shape
when required. Mr Oliver of Boklesberry ap- were gradually replaced by cast spherical lead
pears to have been one of the first dealers in slugs (balls) which were smaller in diam than the
Gunpowder (Ref 7, P17) bores of the guns “which at that time had irregu-
1344. Accdg to Dutton (Ref 58, p 32), Edward lar calibers. When the calibers were standardized
111of England was the first to add cannons to the bullets were made of the same caliber as the
his Army. There were at least two clumsy barrel. All early bullets were loaded thru the
bronze camons with him when he crossed the muzzle on top of a wad previously placed on
channel to France in the War against Philippe top of a charge of BkPdr. There were no car-
de Valois tridges until the time of Gustavus Adolphus,
1346. Accdg to Dutton (Ref 58, p 34), the born in 1594, King of Sweden, 1611 to 1632,
battle of Cr6cy, fought on August 26, 1346 was when a successful paper cartridge was invented.
won by English kmgbows, but it is not known The first elongated bullet was invented in 1823
if the cannons took action, because some ac- by the British Officer Norton. The other elon-
counts do not mention them ,at ail gated bullet was invented in 1836 by W. Greener,
Note 1: Accdg to Greener (Ref 7, p 18), John the famous Brit gunmaker. More detailed de-
Cook, a clerk of the King’s wardrobe, to which scription of historical development of Bullets
department the arms and munitions of war be- is given in Vol 2 of Encycl, pp B324 to B331
longed, stated that 912 lbs of saltpetre and 1350. Accdg to Nambo (Ref 66, p 39), the
846 lbs of sulfur were provided for the use of compn of British Gunpowder “Arderne”, used
the army in France; later in the year, before at that time was saltpeter 66.7, sulfur 11.1 &
 H 124

charcoal 22.2% (See also Ref 11, p 26) 1391. Accdg to Fuller, Vol 1 (Ref 50), solid
1360. Accdg to Marshall 1 (Ref 11, p 23), as iron balls partly replaced stones as cannon missiles,
quoted from paper of F.M. Feldhaus in SS 4, but hollow iron projs filled with Gunpowder (to
p 275 (1909), the Rathaus at Liibeck was de- act as an explosive) were not invented (in Holland)
stroyed by fire thru the carelessnessof Gunpowder until the 16th century (Greener, 1st edn, Ref 2,
makers p 27)
1372. Accdg to Feldhaus (see above) there was 14th Century, Late. The smallest among the early
no mention of Gunpowder or firearms in the fire-arms were the Italian bombards, one of which
archives of Augsburg before this year, although is shown in Fig on p 23 of Ref 7. The bombards
Berthelot claimed that a powder mill existed were muzzle-loading, and had the powder chamber
there since 1340 and that a mill was at. Spandau of much smaller caliber than the forward portion.
in 1344 and at Liegnitz in 1348 (Ref 11, p 23) This fore part was usually more or less tapered so
1378. Accdg to Greener (Ref 7, p 22), the that shot of different diameter might be fired
earliest cast cannons made of copper and tin Another early weapon was the “bombardo
were produced by a founder named Aran at cubito” or “elbow-joint gun” which is described
Augsburg, Germany. They were primitive and illustrated on p 25 of Ref 7
breech-loaders, built up of iron strips surrounded Large cannons were made at a very early date,
by iron rings – a method which continued for even if they were never used. The fact that such
several centuries (See illustrations on p 22 of a weapon was possessedby a town, possibly
Ref 7) terrorized opponents. One of such huge weapons
1379. Cannons and bombards were employed was the “Faust Bucleae” of Frankfurt, made in
at the siege of Puy de Guillen in Perigord 1399 and used at the siege of Tannenburg Castle
(Ref 30, p 254) (Ref 7, p 27). Method of manuf of Gunpowder
1379. The French possessedat Cambray 5 iron at the end of 14th century is shown in illustra-
cannons & 5 of other metal (Ref 30, p 254) tions on p 16 of Ref 7. It is briefly described
1361. Accdg to Greener (Ref 7, p 45), the first on p 24 of Marshall 1 (Ref 11)
account of hand-cannon being used in Germany 1399. Accdg to Sancho (Ref 30, p 255), the
was in 1381, when the town of Augsburg English used 10 cannons during the siege of
supplied thirty men armed with them to the St Malo (France)
contingent of the Swabian towns in theii war 1400. Cristina de Pizana employed “balls of
against the South German nobles fire” and other incendiary projectiles (Ref 30,
Note: In the same book it is stated that hand p 255)
guns were used in the 14th century by French, 15th Century, Early. Accdg to Dutton (Ref 58,
Italians and Netherlanders (See also Vol 2 of pp 39–40), by 1400 iron cannons, bound by
Encycl, pp B324–B325) iron hoops to keep them from bursting, and iron
1382. Accdg to Gorst (Ref 71, p 6), the first cannon balls were coming into use. At the end
recorded use of Gunpowder and artillery in of the 14th century a handgun was invented”
Russia was in 1382 at the defense of Moscow which weighed 10 lbs and fired lead shots. One
against the invading Mongols (Tartars) (called man carried it mounted on the stand and aimed
by Russians Tatary), under the Khan Takhtamysh at the enemy. A similar gun but of 16th century
1386. Accdg to Greener (Ref 7, p 49), handguns is shown in Fig on p 54 of Greener (Ref 7). A
were used in Padua, Italy cavalry handgun, called petronel is shown on
1388. The fire-arm of Rouen was, accdg to p 46 of Greener and a larger semi-portable gun
Greener (Ref 7, p 20), a small iron-forged weapon. on p 42. Some lighter hand guns did not need
It was shooting feathered iron arrows, loaded any stand – they could be fired from the shoulder,
from muzzle, propelled by a charge of Gunpowder, as shown in Figs on pp 45 & 51 of Greener. A
which was put in a separate movable breechblock simpler hand gun is shown and briefly described
or chamber (See illustrations on pp 21 & 22 of in Vol 4 of Encycl, p D755-R with Fig on p D755.
Ref 7) Its stock was a long piece of wood held under, the
1389. Accdg to Sancho (Ref 30, p 255), the arm of the soldier. The first improvement of
manuf of firearms and Gunpowder started in Russia hand gun was the introduction of bent stock and
 H125

,-
the resulting gun was known as arquebus. It is be considered as a predecessor of present “armor-
briefly described in Vol 1 of Encycl, p A488-L ed vehicles” and of tanks. With the help of
and illustrated on p 54 of Greener (Ref 7). This waggon-forts, Zhiska won many battles against
weapon was known accdg to Newan (Ref 33, the Germans until his death which took place
p 33) before 1503, although Dutton (Ref 58, in 1324. This insurrection is known as Hussite
p 60) claimed that it was invented in 1521 War and it lasted fourteen years
Each hand gun or arquebus was provided at Accdg to Greener (Ref 7, p 49), handguns
the rear, closed end (breech) with a touch hole figured conspicuously during Hussite War
serving for igniting by means of a match of BkPdr fvote: Previous to this war the “wheeled forts”
proplnt located in the barrel (See Vol 2 of Encycl, were used by the Tartars against the Russians,
p C73, and Vol 4, p D753-R). When the match but they were manned by bowman instead of
was mounted later (after 1460) on a S-shaped gunmen. The idea was resurrect ed in 1919
lever, called “cock”, the device became known as during Russian Civil War (19 19–1 920) when
matchlock (See also under years 1460– 1480) the two-wheeled carts (known under the name
1410. Accdg to Gen Fuller 2 (Ref 50), canister of tachanka) were equipped with light guns and
or case-shot was invented in 1410 and although machine guns
it was partly replaced by shrapnel (See Ref 11, 1425. In this year is the earliest known re-
p 30), it is still used (See Vol 2 of Encycl, pp ference to corned powder. It was in the
C24-R & C25-L) “Firebook” of Conrad von Schongau and listed
1413. Accdg to Greener (Ref 7, p 27), in Marshall 1 (Ref 11, p 25). “Corning” means
Mahomet 11,of Ottoman Empire used at that the BkPdr cake was broken into small
the’ siege of Constantinople a giant cannon grains instead of preparing it in fine powder,
which was 48 inches in diameter and fired known as “serpentine”. The process was es-
stones weighing 600 lbs sentially the same as described in Vol 2 of
1415. Accdg to Marshall 1 (Ref 11, p 33), the Encycl, p B1 69-L
English used at the siege of Honfleur, France, Note: Apparently, corned powder came gra-
mines charged with Gunpowder for blowing up dually into use for small arms and hand grenades
the walls of fortifications during the 15th century and for big guns in the
1418. Accdg to Greener (Ref 7, p 33), this 16th; the construction of these being sufficiently
seems to be the first year when mortars were improved by that time (Ref 11, p 26)
used. It was in defense of Cherbourg, that 1425. French Gunpowder mills began to grain
these weapons hurled red-hot shot. Three il- and classify their pdr by passing thru. sieves
lustrations of mortars are on pp 35, 36 & 37 (Ref 11, p 26)
of Greener. Current mortars a,re briefly de- 1453. Accdg to Dutton (Ref 58, pp 49–55),
scribed in Vol 2 of Encycl, p C27-R, under the next important step in the use of firearms
CANNON. Mortars were also used at the siege came during the siege of Constantinople by
of LaF2re in 1580 and at Gibraltar in 1780 Ottoman Turks. In 1453 the big Army led by
1419. Accdg to Dutton (Ref 58, pp 41 & 46), Sultan Mahomet 11, lined up against the walls
the earliest cannons were not mounted on wheels of Constantinople, fourteen batteries, totaling
but were just dragged by beasts or men over the 69 cannons. Thirteen of the cannons were of
roads or fields. For the 1st time in history gigantic size and could project stone balls
cannons were not put on wheeled gun carriages, weighing more than ‘% ton each. Two of such
but on stout four-wheeled farm carts. This was stones measuring 46 inches in diameter may be
done by Jan ~iska (pronounced Zhiska) in 1419 seen now at the Turkish Museum at Istanbul.
during the insurrection of Czechs against Sigis- The biggest of these cannons was the Basilica.
mund of Germany who was the ruler of country It required 60 oxen for dragging it on a sled.
known as Bohemia at that time. Zhiska’s After two months of constant bombardment of
supreme stroke was a big “waggon-fort”, called all 69 cannons aimed at one section of the wall,
Wagenburg. Zhiska armorplated his forts, a big gap was made and this allowed the Turkish
pierced iron sides with loop-holes and put at Army to pour thru
each hole a soldier with a handgun. This may Note: Mahomet’s great cannons were cast
 H 126

bya Hungarian named Urban, because such, arquebus was replaced by musket about 1600
industry did not exist outside of Europe and at about the same time crossbowmen
15th Century, Middle. Accdg to Greener (Ref 7, and longbowmen were finished, while the
p 27), the production of large muzzle-loading number of pikemen was reduced to six for
cannons became quite cohon in Germany and every four arquebusiers or musketeers. Some
several of these huge weapons were often re- pikemen were necessary to protect musketeers
ferred to by name, such as “Foulenette” and from heavy-armored cavalry. The pistol was
“Helfant”. Of these, the most known was developed so that armored cavalry could ride into
lforrs A4eg constructed in city of Mons, Belgium. the thick of the pikemen and shoot them down.
It weighed nearly 4 tons and threw stones ,. The cavalry pistol was at first half size arquebus
weighing over 350 lbs. It was installed at or dem;bague and because they were held
Edinburgh Castle and was supposed to have against the chest, they were called poitrirurles
been of the same general construction as the In the book of Greener (Ref 7, pp 48–9)
cannon which in 1460 killed King James II. are given illustrations of the following early
Its illustrations are on p 26 of Ref 7, together pistols: “Iron Club Pistol of 15th Century”
with illustration of large German cast gun. and “Pistol Battle-Axe”
Another huge camon was “Endorfferen” made 1480. Accdg to Nambo (Ref 66, p 39), compn
in 1487 for Sigismund of Tyrol. It was a pair of Swedish Gunpowder for common use was:
with “Bassina” at the Paris Museum (Ref 7, saltpeter 57.0, sulfur 21.5 & charcoal 21.5%
p 27). Illustration of French “Orgue des 1492. Accdg to Dutton (Ref 58, p 57), the
Bombardes” is on p 27 of Ref 7 success of firearms at Constantinople created
During the reign of Henry VI, who lived big demand for them and European producers
betw 1421 & 1471, English artillery was’ in- of Gunpowder and camons became very busy.
ferior to that of France, and many French This required money to pay for them, and
towns previously occupied by English fell fortunately for Europe newly discovered America
back to French. This situation was remedied started to supply gold
later by Henry VIII (1491–1 547) (Ref 7, p 30) 1497. The first successful attempt to use any-
Accdg to Fuller 2 (Ref 50, p 12), a light, thing but simple, solid, spherical projectiles (See
long muzzle-loaded artillery weapon, called year 1340) seems to have been made at the siege
Culverin was developed in the 15th century of Weissenburg. There, use was made of stone
(See Vol 3 of Encycl, p C573-L). Culverin balls of slightly smaller diam than the bore of
fired iron balls weighing 17 lbs each, while the cannon, but coated with an incendiary
its lighter model, demiculverin,’ was 9–1 O material and wrapped in a cloth soaked in
pounder. Still lighter were saker, minion, the same material. The proj was placed thru
falcon and falconet (See Vol 6, p F5-L) the muzzle on top of Gunpowder and on firing
In the book of Greener (Ref 7, pp 48–9) the wrapping ignited and the flame did not ex-
are given illustration of: “Early Culverin”, tinguish until the target was reached. This was
“Hand Culverin with Bent Stock” and two the first successful incendiary projectile (Ref
“Culverins with Side Flash Pans” 12, p 497)
1460–1480. Matchlock was developed sometime 15th to 20th Centuries. Hand Grenades pro-
in the 15th century and Greener (Ref 7, pp bably existed as early as 15th century (See Vol
51 ff) gives a brief description and illustrations 6 of Encycl, p G134-R, under GRENADES).
taken from German MMS of 1460–80 which Accdg to Marshall 1 (Ref 11, p 32), the early
were located in the University Library at grenades, probably made of earthenware, were
Erlangen. On p 52 are four figs showing the used at the siege of Aries in 1536. Whitehorne,
development of matchlock; on p 54 the mechanism writing in 1560, recommended replacing earthen-
of matchlock and on p 68, German Matchlock ware grenades by hollow balls, cast from molten
Gun. The guns equipped with matchlocks were mixture of brass 3 parts and tin 1 part and
known as muskets and the soldiers using them loading them with serpentine powder 3 parts,
as “musketeers” (See Vol 4 of Encycl, p D753) fine corned pdr 3 parts and rosin 1 part. A ,
I
fvote: Accdg to Newman (Ref 30, pp 36–7), small quantity of fine corned pdr was used for 1
priming I
 H 127

The term “grenades” was coined on account very fond of shooting. The firearms were of
of their resemblance to pomegranate. By the smooth-bore (Ref 11, p 28)
middle of the 17th century, special military 1515–1547 are the years of rule of French King
units were organized consisting of tall, strong Fran~ois (Francis) I, born in 1494. He created
soldiers called “Grenadiers”. Grenades thrown permanent Army and equipped it with various
by them consisted of hollow, cast iron balls cannons and small arms. Illustrations on p 32
(spheres) ca 2?4 inches in diam, contg chge of of Greener (Ref 7) include: Cannon, Great
BkPdr and provided with a fuse. Before throwing Culverin, Bastard Culverin, Culverin and two
the grenade, the fuse was ignited. The hand Falcons. On p 33 is shown a cannon mounted
grenades practically disappeared beginning with on wheels
the middle of the 1llth century. However, their 1517. Accdg to Marshall 1 (Ref 11, p 30), the
modified versions, revived during Russo-Japanese doubtful honor of having invented infernal
War (1 904– 1905) and during WWI. As the machine was ascribed to a ITtirenberg citizen
range of grenades thrown by hand was rather in 1517, but there is a drawing of one by
short (max ca 35 yards), attempts were made to Leonardo da Vinci who lived from 1452 to
increase it by using a sling or catapult, but by 1519. In 1645 attempts were made to blow
throwing hand grenades by means of rifles (or up Swedish ships in Wismar harbor by means
using specially designed rifle grenades), ranges of clock-work bombs. In them the clock-work
up to several hundred yards were achieved. More actuated a flint lock with a revolving steel wheel.
detailed information on this subject is given ~ Clock-work infernal machines contg a NG ew
Vol 6 of Encycl, pp G 134-R to G 139-R. De- plosive were used also by the Irish-American
scription of “Grenade Launcher” is on pp Fenians in 1882 and 1884
G139-R & G140-L of Vol 6 Note: Daniel (Ref 3, pp 268–83), under the title
15th Century, Late. Accdg to Dutton (Ref “Engins Criminals”, described them as “devices
58, p 8), Leonardo da Vinci (1452–1519) intended for committing criminal attempts
invented a steam cannon. Such a cannon was against persons or property”. The following
actually built and tested during American Civil attempts against important persons are de-
War (1861–1865) but rejected as being too scribed by Daniel: 1) Dec 24, 1800 an attempt
cumbersome. He also invented multibarreled in Paris against Bonaparte, while he was First
machine-guns, three types of them are shown Consul resulted in death of many persons, but
on plate VI, opposite p 51 of Newnan (Ref 33) Bonaparte was just shaken 2) July 28, 1835
16th Century, Early. Henry VIII improved the an attempt in Paris against King Louis Philippe
armament situation in England, and by 1515 resulted in death of many persons but left the
there were assembled in Tower of London 400 King ufiurt 3) Jan 18, 1858 an attempt by
cannons, most of them mounted on wheels. Ital patriot Count Orsini against Napoleon 111
Further enlargement of supply came when left Emperor unhurt but killed and wounded
Henry VIII seized in 1522 some firearms from many of the escort 4) March 13, 1881 an “
Venetian galleys trading them to Flanders (Ref attempt against Czar Alexander 11 of Russia
7, p 30) resulted in his death. Two bombs were thrown,
Accdg to Greener (Ref 7; pp 39–40), the each of thick glass loaded with Dynamite and
war vessels of the early 16th century were initiated by Ag azide. The 1st bomb wounded
furnished with small cannons which were fired some of the soldiers escorting the Czar. Then
from taffrail, and others which were f~ed to he ordered the carriage to stop and went to see
the decks and fired thru portholes, as may be the wounded in order to comfort them. Just
seen from illustration on p 39, showing the deck before he intended to remount the carriage,
of Mary Rose (sunk by French in 1545) with the 2nd bomb hit at his feet causing most
big breech-loading cannons serious and painful wounds which resulted in
1500 is the date of birth of Benvenuto Cellini great suffering and death. He was the best Ruler
(who died in 1571). It is given to indicate that in the more than 1000-year history of Russia
at that time sporting firearms were already Stettbacher (Ref 21 j pp 41 7–19) described
known. Cellini, when a very young man, was under the title “Anarchistenbomben und Hol-
 H128

lenmaschinen”, construction of anarchist’s aid of these ships, Spanish galleons were at-
bombs and infernal machines and mentioned tacked and their gold seized. This created bad
attempts against Napoleon III and Alexander II relations with Spain (Ref 58, p 61)
In his later work, Stettbacher (Ref 41, pp 1543. Japanese Gunpowder “Tanegashima”,
130–32) described under the title “Sabotage- early period was, accdg to Nambo (Ref 66, p 38):
zunder”; chemical igniters used in anarchists’ saltpeter 75.0, sulfur 8.3 & charcoal 16.7%
bombs and other devices 1548. Chinese Gunpowder of Ming Dymsty
The same,information is given in Spanish was accdg to Nambo (Ref 66, p 38): saltpeter
version of his book published in Argentina 75.75, sulfur 10.6 & charcoal 13.65%
(Ref 46, pp 164–66), under the title “Bombas 16th Century, Middle. In addition to early
de Sabotaje” breech-loading cannons in which the charge of
1520. Rifled Small Arms are said to have powder was loaded into a separate breech (See
been invented by Augustus Kotter of IVtirenberg, illustrations on pp 21 –22 of Ref 7) and
but for a long time they were used for sporting wedged into the cannon, there were numerous
purposes, because the necessity of ramming the methods employed for closing the breech after
bullet down the barrel with the spiral grooving inserting the charge. One of these is shown in
made the loading very slow. Moreover; the illustration on p 37 of Greener which is not
powder left much fouling in the grooves, and reproduced here
consequently it was necessary to clean ‘the gun 16th Century, Middle. Up to that time, no car-
after a few rounds. With the old musket which tridges of any kind existed for propelling a
was smooth-bore, the bullet was smaller than the charge of BkPdr and it was loaded loose thru
bore and there was no difficulty in loading, but the muzzle. Then the paper’ cartridges started
it was not as accurate as rifles. As for sporting to be invented and by about 1590, three types
purposes, accuracy was more important than were known. They are shown in Fig 17 of
rapidity of fire, therefore the rifle was able to Vol 4 of Encycl, p D754-R. The really successful
hold its own. Sporting rifles were successfully paper cartridge was adopted by King Gustavus-
used by American colonists during the War of Adolphus of Sweden (1 594–1 632) for his Army
Independence. Then the English created the “Rifle (See Fig 18 on p D755). None of the paper
Brigade” to fight the American marksmen (Ref cartridges contained primers as we know them
1 l:pp 28–9) now (See under year 1805)
Abte: In the Crimean War (1 854–1856), rifles Paper cartridges were not replaced by me-
used by the English and French (called Stutzers tallic cartridges provided with caps until the
by Russians) against Russian smooth-bore arms, beginning of the middle of the 19th century
contributed greatly to defeat of Russian’s (See under year 1805)
1525. Beginning with this year, bronze cannons The historical development of cartridges
were cast in England by Peter Bawde, French from paper to metallic is also described
artificier. Later, in 1535, John O’Ewen was in Vol 2 of Encycl, p C73-R
engaged in the work, and by 1543 the cannon 1554. Accdg to Marshall 1 (Ref 11, p 23), a
industry was established in Uckfield, Sussex, Gunpowder mill was erected at Rotherlithe,
then the center of iron industry in Britain England
(Ref 7, p 30) 1558–1603. During this period Elizabeth I
1525. Important improvement in BkPdr was (born in 1533) ruled in England. She succeeded
achieved in France by control of the grain size Mary I, during whose rule the Henry VIII Navy
(Ref 64, p 2-2) was neglected and many of the ships deteriorated.
1533. In order to create a big Navy, Henry VIII At that time Philip H of Spain (born in 1527
of England needed money which he got by con- and King 1556–1 598) was ‘planning to attack
fiscating the properties of Roman Catholic England by means of newly constructed ships
Churches and Monasteries. This money per- which formed the “Invincible Armada”. Eliza-
mitted him to create a Navy, which at the time beth then ordered John Hawkins to restore the
of Henry’s death (1547) amounted to 53 ships, Navy and Francis Drake to construct a large
all equipped with bronze cannons. With the Gunpowder Plant at Waltham Abbey (Ref 58,
 H 129

p 63). Several other milk were installed at that with incendiary mixts and provided with a
,period and the monopoly was conferred upon fuse which was supposed to ignite on firing of
Evelyn family (Ref 7, p 17). This took place, proplnts. These shells were dangerous to use
accdg to Marshall 1 (Ref 11, p 23), a few years because they often broke inside the bore. The
later than 1561 fust successful hollow shells and shrapnel are
1560. Compns of two Swedish Gunpowders briefly described in next item
as listed by Nambo (Ref 66, p 39) were: 1588. Accdg to Marshall 1 (Ref 11, p 31), the
a) saltpeter 50.0, sulfur 16.7 & charcoal 33.3% first really successful explosive shell was employed
b) saltpeter 66.7, sulfur 16.7 & charcoal 16.7% at the sieges of Wachtendonck and Bergen-op-
1560. Compn of English Gunpowder “Whitehorne” Zoom, Holland. This was due to the employ-
was, accdg to Marshall 1 (Ref 11, p 20): salt- ment of newly invented igniter (fuse) by an
peter 50.0, sulfur 16.6 & charcoal 33.3% Italian master gunner refugee from Parma. The
1569. Compns of two Japanese Gunpowders fuse apparently consisted of a tube (or pipe),
are given by Nambo (Ref 66, p 38): a) salt- filled with slowburning powder, which was driven
peter 77.6, sulfur 10.7 & charcoal 11 .7% into fuse-hole of the shell. This type of fuse was
b) saltpeter 76, sulfur 12 & charcoal 12% made to burn 14 to 20 seconds, corresponding to
1578. Accdg to Marshall 1 (Ref 11, p 27), ranges 1000 to 2000 yards in the mortars, which
the first instrument for testing Gunpowder was were always used instead of cannons for throwing
devised by Bourne. Up to that time, the only shells. Such shells were used for the destruction
test was to burn a small quantity to see how of stone fortifications and ships; against men
much residue would be left. The instrument of they were not very effective, as there was usually
Bourne consisted of a small metal cylinder with time to get away from them or to extinguish
a heavy metal lid on a hinge. The lid was pre- the flame of fuse by water or sand. Until after
vented from falling by a rat~het, and the angle the introduction of watches, which were in-
to which it rose when powder was fired inside vented in 1674 by Christian Huygens of Holland
the cylinder measured the strength. A much (1629–1695), no convenient means existed for
better instrument was invented in 1627 (qv) testing the time of burning of a fuse. In the
1587. English Navy, under Admiral Drake, at- middle of the 18th century fuses were made of
tacked and destroyed the Spanish galleons as- beechwood with a hole down the middle fdled
sembled in Cadiz in preparation for the attack with fuse powder. They were of different
against England (Ref 58, pp 66–7) lengths. Great accuracy “was not required of
1588. After repairing ships damaged at Cadiz them until Capt Mercier, during the siege of
and rounding up more of them, Philip II sent, Gibraltar in 1779, proposed to fire shells from
early in 1588, 132 ships forming the “Invincible cannons instead of mortars or howitzers. Ac-
Armada” against English 40 warships and 150 curate fuses were also required for the Shrap-
merchant ships equipped with guns, under Lord nel, invented by Lt Strapnel ca 1784 and of-
High Admiral Lord Howard of Effingham. The ficially adopted by British Govt in 1803. These
Armada came late in July to Plymouth, where fuses were replaced after 1831 by Bickford fuse,
it was attacked by the English, who destroyed described in Vol 2 of Encycl, p B1 12-L (Ref 11,
many ships by burning them. The remaining pp 32 & 38)
ships escaped across the channel to Calais, but 1595. Accdg to Marshall 1 (Ref 11, p 31) and
they were pursued and attacked again. Finally, Nambo (Ref 66, p 39), compn of German Gun-
the Spanish Admiral decided to escape to Spain powder was: saltpeter 52.2, sulfur 21.7 & char-
thru North Sea. This happened to be very rough coal 26.1%
and it contributed to destruction of many 1597. Chinese Gunpowder of Ming Dynasty
ships. By the time Armada arrived at Spain, contd: saltpeter 80.66, sulfur 5.64 & charcoal
there were less than 50% of ships, while English 13.70% (Ref 66, p 38)
lost no ships (Ref 58, pp 67–8) 16th Century, End. Accdg to Chalon (Ref 8,
1588. Accdg to Colver (Ref 12, p 497), early p 228), quoted by Marshall 1 (Ref 11, p 27),
hollow shells were used by Chinese. They the French compn of “Poudre noire” of pro-
were made of earthenware. They were filled portion 6:1:1 (meaning saltpeter 75.0, sulfur
 H 130

12.5 & charcoal 12.5%) has been adhered to 1621. Accdg to Nambo (Ref 66, p 38), the
there more or less ever since. It is also listed Chinese Gunpowder for propulsion described by
by Nambo (Ref 66, p 39) as of year 1598 Wu Pei Chih of Ming Dynasty, contained:
Note: It is mentioned by Marshall 1 (Ref 11, saltpeter 77.0, sulfur 9.5 & charcoal 13.5%
p 27), that German powder contg saltpeter 1627. According to Marshall 1 (Ref 11, p 27),
66.6, sulfur 16.6 & charcoal 16.6% was more a much better instrument for testing BkPdr
satisfactory than French powder and that the. than that of 1578 (qv) was devised by Curten-
German Cocoa Powder was ballistically the best bath. This consisted of a heavy conical shot
BkPdr ever made which rested on the mouth of small mortar and
1606. Accdg to Nambo (Ref 66, p 28), the could travel vertically upwards along a stretched
Chinese Gunpowder for general purpose, de- wire provided with series of catches to stop
scribed by Wu Pei Chih of Ming Dynasty contd: the shot from falling down
saltpeter 75.0, sulfur 12.5 & charcoal 12.5% 1627 and Later. Black Powder in Mining. “Accdg
1608. Accdg to Marshall 1 (Ref 11, p 27), to Dutton (Ref 58, p 90), a Hungarian engineer,
Danish BkPdr “contd: saltpeter 68.3, sulfur Kaspar Weindl, experimented in blasting ore near
23.2 & charcoal 8.5% the town of Selmeczbanya by means of BkPdr.
1611–1632. During the rule of Swedish King From that time, use of BkPdr for breaking ores
Gustavus Adolphus (born in 1594) many im- spread to Germany, Sweden and other countries.
provements in military weaponry were intro- Accdg to Marshall 1 (Ref 11, p 33), blasting was
duced. He is considered by Dupuy & Dupuy probably introduced to England in 1670, and
(Ref 69, pp 522–24) as the father of modern in 1689 Th. Epsly Sr started to use BkPdr in ~
field artillery and of the concept of massed, Cornish mines
mobile artillery fire. His 3-pounder regimental Accdg to O. Guttmann, as quoted from
cannon, illustrated on p 524, looks like a Marshall 1 (Ref 11, pp 33–4): .“When bore-
modern weapon. He was also the inventor of holes first came into use they were made with
an improved paper cartridge which is illustrated iron-mouthed borers, fairly large – nearly 3
in Vol 4 of Encycl, p D755. This invention inches in diameter, and then closed with a
permitted an increase. in the rate of fire. For wooden plug termed the shooting plug.
further development of cartridges, see year 1826 Henning Hutmann in 1683 employed a kind of
Gustavus Adolphus was the initiator and drilling-machine. In 1685 clay tamping and in
successful participant of “The Thirty Years’ 1686 firingtubes began to be used. In 1689
War” (1618–1648), which started as a religious paper cartridge cases were used to replace the
war between Protestants and Catholics. The older form of leather, and in 1717 bore-holes
War, which involved several nations, is de- of smaller diameter came into vogue. The use
scribed in Ref 69; pp 533–46. The King per- of the chiselborer dates from 1740, blasting
sonally was engaged in many battles and was the untouched breast from 1767 (first at
killed in 1632 at the battle of Lutzen. Then Zinnwald)”
Bernard took command and the war continued 1635. Accdg to Marshall 1 (Ref 11, p 26)
until 1648. As result of peace treaty of and Nambo (Ref 66, p 39), English Gunpowder
Osnabriick, Sweden received an indemnity, of Government Contract contd: saltpeter 75.0,
and substantial Baltic coastal territories belong- sulfur 12.5 & charcoal 12.5%
ing to Russia, and to Catholic part of Germa,ny 1637. Accdg to Nambo (Ref 66, p 38), the
1615. Accdg to Dupuy & Dupuy (Ref 69, p Chinese BkPdr for bursting charges, described
523), the true fusil or jlintlock musket was in- by Tien Hung of Ming Dynasty contd: saltpeter
vented by French gunsmith LeBourgeos. It 82, sulfur 9 & charcoal 9%
was perfected as a sporting weapon about 1630, 1643-1715. During the rule of Louis XIV,
but was not adopted for military purposes until the Great of France, an Army of nearly 400
1670 in France and then later in other European thousand men, serving as volunteers, was or-
Armies. By ca 1680, someone – possibly S. ganized and its frontiers were fortified by
Vauban (1 633–1 707) – invented the ring bayo- famous military engineer Vauban (1 633–1 707):
net, which left the bore clear for firing Louis XIV equipped his infantry with f7int
 H 131

muskets, which replaced arquebus and matchlock. Reise & Millon reported that a mixt of powdered
His muskets were equipped with bayonets and AN and charcoal exploded on being heated to
paper cartridges, which by 1700 allowed the 170°. In 1867 Ohlsson & Norrbin patented
firing of two rounds per minute instead of pre- its use in mining expls, and in 1870 A. Nobel
viously one round. Some infantrymen were purchased their patent (Vol 1 of Encycl, p
put on horses and the resulting cavalry became A342-L). Nobel then introduced a series of
known as dragoons. At Essonne, near Paris, a AN expls, called Extra Dynamites and Am-
Gunpowder plant was constructed which manufd monium Nitrate Gelatins. During WWI, AN
an improved product in seven sizes from finely found extensive application in its mixt with
ground grains for handguns to walnut size pel- TNT (such as Amatol and Ammonal) or with
lets for the large cannons. The use of large- other HE’s such as Di- and Tri-nitronaphtha-
grain pdr increased the range 1 or 2 miles. To- lene (Vol 1 of Encycl, p A341 and Tables on
wards the end of his rule, corruption, abuse & pp A355 & A356 (See also Vol 5, under DY-
inaccurate payment developed and the number NAMITE, p D1 583 and as “Do-It-Yourself”
of available volunteers stopped. These corrup- Ammonium Nitrate-Fuel Oil Explosives in Vol
tions and huge debts were passed in 1715 to 5;pp Di528&D1529
Louis XV (17 10– 1774) and finally to Louis The latest development in AN-contg expls
XVI (born 1754, deposed in 1792 due’ to re- is its mixtures with fuel oils. Such expls are
volution and guillotined in 1793). The first known as AN-FO and their brief description
universal conscription was introduced in August is given in Vol 6 of Encycl, pp F21 1-R to F213,
1793 (Ref 58, pp 72–88) under Fuel Oils
1646. Bofors Industries (Aktiebolaget Bofors) 1666. Chain Shot was invented by DeWitt of
of Sweden was established to become one of Holland, for use against the rigging. of ships. It
the world’s largest companies manufg expls, consisted of two balls or half balls united by a
proplnts, ammo and weapons. A brief de- chain (Ref 11, p 31) (See under Grape Shot in
scription of its activities is given in VoI 2 of Vol 6 of Encycl, p G126-L & R
Encycl, pp B218 to B220 1669. Accdg to Dutton (Ref 58, p 114),
1647. Accdg toNambo (Ref 66, p 39), the phosphorus was discovered by a German chem-
compn of Swedish Gunpowder of Nye was: ist named Brand, who prepd it from urine
saltpeter 66.6, sulfur 16.7 & charcoal 16.770 1689. Accdg to Feldhaus, SS 2, 218 .(1908),
1647. Master-Gunner Nye, in his “Art of as quoted in Marshall 1 (Ref 11, p 22),
Gunnery”, described the instrument of 1627 Thomas Epsly Sr started the use of Gunpowder
(qv), and also proposed that the strength of in Cornish mines, England
powder be measured by firing bullets from a 1689-1725. Accdg to Dupuy & Dupuy (Ref
pistol into clay, or by firing a ball from a 69, p 645), the Czar Peter I (The Great, born
mortar and finding out how far it travelled. in 1672) completely reorganized Russian Army
This mortar test was adopted by French as and Navy, equipping them with latest arms. This
“mortier ~prouvette” and was rdso used by permitted him to win the “Great Northern War”
other countries (Ref 11, p 28). Further im- (1 700–1721) against Sweden, lead by the great-
provement in testing was done in 1742 (qv) est warrior of that time, King Charles XII, born
17th Century, Middle. Accdg to Marshall 1 in 1682, ruling during 1697–1718 (Ref 69, pp
(Ref 11, p 34), it seems that K chlorate was 614–617). By the treaty of Nystadt (1721),
known to Glauber (1603-1668), but it was Russia recaptured the Baltic provinces ceded to
not investigated until about 1786 (qv), when Sweden during “The Thirty Years’ War” (1618–
Count C.L. Berthollet lived (See Vol 2 of 1648), lead until his death in 1632 by the
Encycl, p BI06-R) great Swedish King Gustavus Adolphus (born
1654. Ammonium Nitrate (AN) was first prepd 1594, ruling 161 1–1632) (Ref 69, pp 533–46)
by J.R. Glauber (1 603– 1668) who also prepd 1696. The Swiss used drills of tempered iron
Na sulfate. It was not until begiming of the for drilling boreholes in rocks during blasting
19th century that it started to be used as a with BkPdr thru Alps in constructing the
replacement for K nitrate in BkPdr. In 1840 Albula Road, the main thoroughfare for wagon
travel (Ref 58, p 93)
 H 132

18th Century, Beginning. Accdg to Marshall 1 1742. Accdg to Marshall 1 (Ref 11, p 28),
(Ref 11, p 36), flintlock was invented, but Robins placed the mortar described ‘by Nye in
accdg to other sources it was in the middle of 1647 (qv) on a more scientific basis by the
17th century. Its other name was firelock and invention of the ballistic pendulum by means
it replaced the wheel-lock. A brief description of which the actual velocity of a projectile
is given in Vol 4 of Encycl, pp D754–55). could be measured
The improved types of flintlocks were used by 1745. Electric cap was invented by Dr Watson
the British as late as 1850 and by the Ameri- of England and improved in 1749 by B. Frank-
cans as late as the end of Civil War (1865) lin of US, but the device was forgotten until
18th Century. Cannons, which since the 16th 1830 when Moses Shaw was granted a patent
century were cast in bronze, started to be cast for a similar device. It was a “high tension”
in iron. Until the 2nd half of the 19th century, cap. The first “low tension” cap was developed
a cannon consisted simply of a block of cast by M. Shaw with the assistance of Dr R. Hare
metal with a smooth-bore machined out and a (Vol 1 of Encycl, p B186-R)
vent drilled near the breech. It is true that The biggest contribution to the construction
the breech-loading guns were made at a much of modern cap was done by L.A. Burrows of
earlier date (See illustrations on pp 21, 22 & dupont Co begiming about 1937 (Vol 1 of
37 of Greener’s book of 1910), but they were Encycl, p B187 & p B363-L, giving a list of
not adopted because the breech leaked (Ref his inventions)
11, p29) 1765. Accdg to Dupuy & Dupuy (Ref 69, p
1707. Chronographs. The earliest device was 665), J.B. deGribeatival (17 15–1 789) began to
conceived by Cassini, but the first practical revolutionize French Artillery, and his 4-, 8- &
instrument based on his idea was constructed 12-pound guns and 6-inch howitzers were later
in England in 1740 by Robins. This instrument used by Napoleon
underwent in later years many improvements, such 1766. Henry Cavendish (1731–1810), the Bri-
as by Hutton (1775), Didion-Morin-Piomb ert. tish physicist and chemist, was the first to
(1836), Piombert (1860) and Minarelli-Fitz- identify hydrogen (Ref 58, p 113)
gerald (1 900–01). Other older devices are 1771. Picric Acid (PA) was first .prepd by
listed in Vol 3 of Encycl, p C305, while more Woulfe on treating silk with nitric acid. It
recent devices, such as of LeBoulang6, Aber- was used as a yellow dye, and its expl props
deen, Mettegang, Pin Chronograph, etc are de- were not discovered until 1871 (See also 1843)
scribed on pp C306 to C318 (Ref 11, p49&Ref 12, p6)
1738. Closed Bomb or Vessel. The first re- 1772. Daniel Rutherford (1749–1 819), Scotch
corded attempt to measure the pressure generated botanist, first identified nitrogen (Ref 58, p 113).
when Gunpowder was fired in a closed space Do not confuse with Lord Ernest Rutherford
(such as bomb or a gun barrel) was made in (1871–1 937), Brit physicist noted for his
1738 by d’Antony in Italy. This was followed research on radioactive transformation and dis-
in 1742 by Robins in England, d’Arty in France integration of nitrogen
(1760) and by Count Rumford in Germany 1774. Swedish alchemist K.W. Scheele ( 1742–
(1792). More accurate measurements could be 1786) separated from saltpeter its ““fire-air”,
obtd in the 19th century, such as using in- now known as oxygen. He also obtd glycerin
struments invented ca 1860 independently by and identified chlorine and fluorine (Ref 58,
Maj T,J. Rodmarr in US and by Gen N. Mayev- p 112)
skii in Russia. Other devices were of Sir A. 1780. Potassium Chlorate was discovered by
Noble & Sir F. Abel of England and of M. C.L. Bertollet, and he prepd some expl mixts
Deprez, E. Sarrau & P. Vieille of France. Bichel contg it (See Vol 2 of Encycl, p B107-L). Two
Bomb was invented in 1898 in Germany. In disastrous explns in 1788 & 1792 during pul-
Russia the Dolgov Bomb has been used. It verizing and mixing the expls contg it stopped
consists of a vertical cylinder. All of these its use for a while (See Vol 2 of Encycl, pp
bombs are described in Vol 3 of Encycl, pp C190 to C197 & C202, and also under 1850.
C330 to C345 Chlorate Explosives
 H 133

1782. Ballons & Airships and Their Applica- town in 1799, explosive rockets were u;ed
tion in War. Under this title there is described with some success
in Vol 2 of Encycl, pp B 10–B 11 their historical 18th Century, End. Accdg to Marshall 1 (Ref
development. The first successful balloon was 11, p 28), practically every country had come
invented in 1782 by brothers Mongolfier of to use Gunpowder of compn: saltpeter 75.0,
France, and ever since then attempts have been sulfur 10.0 & charcoal 1570
made to use them for military purposes, such 19th Century, Beginning. Accdg to Colver
as for observation and later for dropping bombs (Ref 12, p 498), considerable use was made of
(See under year 1849, Bombs, Aerial) red-hot iron shot particularly in combat with
The most ingenious application of balloons wooden ships
guided only by prevailing winds was made by 19th Century, Beginning. Ammines or Ammo-
the Japanese against US territory in 1944. It niateswere invented, but they were not sys-
is briefly described in Vol 2, p B 11-L and more temized and explained until 1893 when Alfred
fully by R.W. McKay in Engineering Journal Werner introduced his theory of coordinated
28, 263–67 (1945), under the title “Japanese compounds. Many of them are explosive, as
Paper Balloons” can be seen from Tables in Vol 1 of Encycl,
1784. Accdg to Guttmann, as quoted from pp A277 to A282
Marshall 1 (Ref 11, p 26), presseswere intro- 1800. Accdg to Marshall 1 (Ref 11, p37),
duced to compress the mill-cake BkPdr before Mercury Fulminate was invented by Edward
coming. It was in order to obtain really com- Howard, who ‘described it in a paper before the
pact grains of BkPdr Royal Society
1784–1785. Shrapnel shell was invented by 1802. Eleuth&e Ir(h~e du Pent de Nemours,
Brit Lt Shrapnel to use against troops in the French immigrant, began the manuf of BkPdr
open (Ref 11, p 31). It partly replaced case- at a mill situated on the banks of Brandywine
shot, described in Vol 2 of Encycl, pp C24-R Creek, near Wilmington, Delaware. The compn
& C25-L. A brief description of Shrapnel was approx: saltpeter 75, sulfur 10 & charcoal
shell is given in Colver (Ref 12, p 497). It 15%. The manuf was continued until 1921
was adopted in 1803 by British Govt for (Ref 52, p 3)
military purposes 1805. Accdg to Marshall 1 (Ref 11, pp 36–37),
1786. Potassium Chlorate, supposed to be the Rev A.J. Forsyth, a Scotch clergyman, made
discovered by Glauber in the 17th century a sporting gun with detonator lock. He patented
(middle) was prepd by C.L. Bertollet in pure the device (which is described in Vol 4 of Encycl,
state and its props detd. He proposed using p D75 5). As the device was initiated by the
it in lieu of K nitrate in BkPdr, but abandoned blow of a hammer, it was the original percussion
the idea after disastrous expln during its manuf lock. The device was not adopted by the
in 1788, which killed several persons. The British ‘Ordnance because it was not considered
first successful mixts using K chlorate were suitable for military purposes. Before many
Cheddites (See Vol 2 of Encycl, p C 155ff and years elapsed, Forsyth’s device was displaced
Marshall 1 (Ref 11, pp 35–36) by a copper tube or cap contg Mercuric Fuhni-
1789. Accdg to Marshall 1 (Ref 11, p 26), at ‘ nat e. It is not certain who invented the MF cap.
Faversham, England the powder was compressed Accdg to H. Wilkinson, J. Shaw of Philadelphia
by means of a screw-press, while the hydraulic invented a steel cap in 1814, a pewter (alloy of
presseswere introduced in the 19th century tin with some lead) cap in 1815, and copper
1789. Uranium was obtd by German chemist cap in 1816. J. Egg of London seems to have
M.H. Klaproth (1 743–18 17), who also obtd adopted the idea from Shaw. Pr6at and De-
titanium and zirconium. Uranium was obtd boubert of Paris patented in 1820 caps filled
by roasting radioactive pitchblend (Ref 58, p 114) with MF and AgF, respectively. E.G. Wright
1792. Accdg to Marshall 1 (Ref 11, p 33), the of Hereford published in 1823 a paper on the
Indians fired rockets in the defense of Seringa- MF cap, contg much information. Frederick
patom, but they did not appear to have done Joyce was the first to make a real success of
much damage, while at the siege of the same percussion cap ca 1824
 H 134

The next important step was to combine were produced, such as mauve and alizarin.
shot, powder and cap in one cartridge, which Aniline was also prepd and this gave on nitra-
could be inserted in the breech of the arm. In tion the very powerful Tetranitroaniline which
1836 Lefaucheux introduced his pin-fire breech- is described in Vol 1 of Encycl, pp A425ff.
loading shotgun, the barrels of which were Other important expls obtd on nitration of
made to drop as in the modern weapon to allow products of distillation of coal tar were Di- and
the cartridges to be introduced. About 1853 Trinitrobenzene (VOl 2 of Encycl, pp B46ff
the English and French gun-makers introduced and Nitronaphthalenesr which will be described
the center-fire hammer gun, which fired car- under Naphthalene and Derivatives
tridges having a cap in the middle of the base Dr vonHofmann moved back to Germany in
of the cartridges, but the first really successful 1874 where he established a large scale coal tar
center-fire gun was that made by Daw in 1861 industry
(Ref 11, p 37) 1826. Cartridges for Ammunition. It was
More detailed description of capped cartridges mentioned under 1350. Bullets and. under 1611 –
is given in Vol 4 of Encycl, p D756-L 1632 that the first successful paper cartridge was
1807 to 1815. Accdg to Marshall 1 (Ref 11, p invented during the rule of King Gustavus Adol-
33), CO] Congreve of the Hanoverian Army phus of Sweden (161 1–1632). This type of
(later Sir W. Congreve), independently from cartridge was not, however, self-sustained be-
Indians (See 1792AD) developed, sometime be- cause it was not provided with a primer which
fore 1807, a rocket, the most powerful device was not known at that time. The first self-
of its kind that had been used in warfare. It contained paper cartridge was invented in 1826
proved very effective at Copenhagen and and improved on in 1831. The first metallic
“Walcheren in 1807 and at the passageof the cartridge was invented in 1846 by Houiller of
Adour in 1813, but it was at the battle of Leipzig Paris. It is known now as “pin-fire cartridge”.
in 1813 that it achieved its greatest renown. It He also invented the “rim-fire cartridge”. The
also rendered good service at Waterloo in 1815 first successful “center-fire cartridge” was in-
and during the War of 1812 between the US and vented in 1858 by Morse and improved by Col
Gt Britain Berdan. It was adopted in 1865 by the US
Since the Napoleonic Wars, the improvements Army. Previously to this (1854) Smith &
in ordnance have been so great that the rocket Wesson developed a successful metallic cartridge
ceased to be used as a weapon. However, it for revolvers. Further development of cartridges
continued to be used for signaling and illumi- and their construction are described in Vol 2 of
nating purposes, until it was displaced to Encycl, pp C73 to C76
a great extent by star shell 1826. Aniline was first prepd by Unverdorben
1819. Accdg to Marshall l“(Ref 11, p 26), (Vol 1 of Encycl, p A406-L)
Col Congreve introduced his granulating ma- 1831. Safety Fuse invented by W. Bickford
chine for BkPdr which is described on p 82. (See Vol 2 of Encycl, p B 112-L) and in 1840
It has been used in England for many years the Bickford fuse was adopted by the English
1823. Accdg to Colver (Ref 12, p 4), MF military authorities. In 1836 a factory was
(Mercuric Fulminate) was proposed by Wright started in US, in 1839 in France, and in 1844
as an igniter of Gunpowder in Germany. Before 1840 guttapercha-covered
1825. Accdg to Dutton ,(Ref 58, pp 156–57), fuse had been adopted for blasting under water.
the Rev Dr Clayton began in England investi- Various modifications have since been invented,
gation of products on distillation-of coal tar, including fuse cased in metal “Colliery Fuse”
which was obtd from bituminous coal. He (patented in 1886 by Sir G. Smith), which
isolated benzene, creosote, naphthalene and emits no sparks; and various sorts of “instantaneous
other chemicrds. Most of his products were fuses”, which burn very rapidly and enable many
later nitrated, giving expls. The investigation shots to be fired simultaneously (Ref 11, p 38)
was continued by A.W. vonHofmann (1818– 1832. Ammonium Perchlorate was first prepd
1892), who came to England from Germany by Mitscherlich (Ref 70, pp 26 to 28)
and by W.H. Perkin (1838–1907). Many dyes 1832–1833. French chemist H. Braconnot of
 H 135

Nancy found that on treating starch (in cold) In this ignition was effected by a needle being
or wood (in hot) with coned nitric acid there’ driven right thru the base of the cartridge into
was obtd a viscous liquid, which on addn of a disk of fulminating material. In spite of some
water deposited a white powder which, on drying, defects, such as escape of gas and rusting of
dissolved in ether-alcohol mixture and easily needle, the gain in rapidity of fire caused it to
burned when ignited. It was named xyloidine be maintained in general use during the wars” of
but is actually Nitrostarch (Ref 44, p 240 & 1848, 1866 and 1870. The French adopted
Vol 2 of Encycl, p C 101-L) (See also Ref 31a, Chassepi3t in 1866, which was a considerable
p 245) improvement upon the Prussian rifle. At
1833. Nitrostarch (NS) was first prepd by about the same time, the English rifle of Mr
Braconnot, who called it xyloidine. Pelouze J. Snider, an American, was invented. This
prepd it, in 1838, in purer condition and rifle was considerably improved by Col Boxer
studied its props. It was used in the US during by adopting a brass case instead of paper as
WWI and WWH as demolition expl and for burst- in previous rifles (Ref 11, p 38)
ing charges (Ref 70, pp 246 to 248) 1841. Ammonium Picrate was first prepd by
1834. The earliest attempt to nitrate aromatic Marchand and used in 1869 by Brug&e as proplnt
nitrocompounds was by E. Mitscherlich ( 1794– (Ref 70, p 138) (See also 1909)
1863), in Germany, who nitrated benzene to 1843. Picric Acid (PA), discovered in 1771 by
m-DNBz and toluene to MNT’s (Ref 12, p 18) Peter Woulfe (inventor of 2- or 3-necked bottle)
1837. Accdg to Dutton (Ref 58, p 125), but not identified, was rediscovered by A. Lau-
Emanuel Nobel, father of Alfred Nobel, invented, rent (1 807– 1853). He prepd it by nitrating
at 35 years of age, a torpedo. It exploded and phenol or Dinitrophenol with nitric acid and
wrecked his home. He was ordered to leave identifying it as Trinitrophenol. He did not
Stockholm. So he went to Russia to operate a recognize it as an expl, but found that some of
torpedo factory near St Petersburg. He settled its ‘salts are expl. When the price of phenol
in Russia and his sons, including Alfred, were became reasonable, PA started to be used as
educated there. When Crimean War broke (1853) a fuel in expl mixts, while its salts were used
his torpedoes (or rather mines) loaded with NG-NC as expl additives (See also under 1871 and 1885)
prevented the British fleet from approaching (Ref 11, p 49)
Cronstadt, which was the fortress guarding St 1844. Prof C.F. Sch6nbein of Urdv of Basel
Petersburg. After the war, Emanuel, with (1799-1866), discovered ozone (Ref 11, p 39)
Alfred and Oscar, returned to Sweden, while 1845. Scho,nbein on treating cotton with
Robert & Ludwig remained in Russia to work mixed nitric-sulfuric acid during a short
in Baku oil fields. They became millionaires time (in order not to destroy fibrous structure)
1837-1838. Prof T.J. Pelouze of Paris (1807– obtd, after washing with large amt of w and
1867) nitrated (other than starch) cellulosic drying, a very combustible product which was
substances, such as paper, and called the resulting named “coton-poudre”. The product was tried
product xylokiine, which was sol in eth-alc. in mining (Ref 31a, pp 241–48; Ref 44, p 240
He rdso treated cotton fibers with coned nitric and Vol 2 of Encycl, p C 101-L, under CELLU-
acid, without allowing them to be destroyed. LOSE NITRATE)
He plunged the nitrated fibers in large amt of fvote 1: Dutton (Ref 58, pp 119–20) said that
cold water, followed by several washings and Schonbein discovered NC by accident. He wiped
then drying. The product was highly combustible nitric-sulfuric acid spilled in the kitchen with his
but insol in eth-alc. This was not xyloidine wife’s cotton apron. Then he rinsed the apron
but a higher nitrated product as was proved by with water, hung it to dry over a hot stove and
Pelouze in 1646. He named it pyroxyline or then he heard a loud expln. He repeated the
pyroxyle (Ref 3 la, pp 245–46; Ref 44, p 240 nitration using another apron, which he rinsed
& Vol 2 of Encycl, p C101) and dried more carefully than the first one.
1840. Accdg to Marshall 1 (Ref 11, pp 37–38), Then he cut from the apron a strip and lighted
the Prussians adopted a breech-loading rifle, the it with a match. The strip rapidly burned with-
Zundnagelgewehr, invented in 1838 by Dreyse. out leaving any ash
 H 136

IVote 2: Accdg to Davis (Ref31 a, p 247), Sch6n- cussion cap, a time-fuse (or rather time-fuze)
bein’ also described the nitration of cane sugar, which was initiated by the shock of discharge
which was performed in December 1845, but of the projectile from the gun. On the latter
he deliberately refrained from telling how he date Moorsom introduced the first shell fitted
prepd NC. His Nitrosugar, prepd as described with a fuze actuated by the shock of impact
by Davis (Ref 31a, pp 247-48), was dried at of the shell
low temp. At 100° it was semi-liquid and at 1847. Mannitol Hexanitrate or Hexanitromannitol
higher temps gave off red fumes. When heated was first prepd in Italy by A. Sobrero. N. Soko-
more strongly, it deflagrated suddenly and with loff of Russia examined in 1878 its expl props.
violence Used as secondary chge in detonators and blast-
1846. Otto of Brunswick described in Allgemeine ing caps (Ref 70, pp 197 to 200)
Zeitung of Ott 5, 1846 procedure for making 1847. A big expln killing 21 men took place
NC very similar to coton-poudre of Sch6nbein at Faversham (England) factory manufg Gun-
(Ref 44,. p 240) cotton by the Schtkbein method. After this
1846. W. Knopp of Leipzig, Heerben, & Kar- Hall & Sons, who were the contractors, refused
marsch of Hanover and J. Taylor of England to proceed with the manuf. About the same
described prepn of coton-poudre by nitrating time there were disastrous Guncotton explns at
cellulose with mixed nitric-sulfuric acids (Ref Vincennes and Bouchet, and these produced
31a, p 250 & Ref 44, p 240) such an effect that no more Guncotton was
1846. Italian chemist, A. Sobrero, obtd on manufd in England & France for the next 16
treating glycerin with mixed nitric-sulfuric a years (Ref 11, p 39)
very expl liquid which he called glyci%ine ful- 1847. In France, the “Commission du Pyroxyle”
minate or pyroglyc~n”ne (Ref 44, p 241) was formed, charged with investigating the pos-
1846. Sauerbrey of Switzerland started to sibility of replacing BkPdr with NC (plus some
manuf rifles using fulmicoton and exported dextrin) as rifle proplnt, but the idea was aban-
them to various countries, chiefly to Austria, doned after violent explns at Vincennes and
but this stopped in 1848–1850 (Ref 44, p 241) Bouchet (Ref 44, p 241)
1846. Schi5nbein proposed using coton-poudre 1847. Gladstone of England, by exercising
as more powerful replacement of poudre-noire special precautions, was able to determine nitro-
(BkPdr) (Ref 44, p 241) gen content of pyroxyline as 12.75 %,’ which
1846. Dr Bley of Bernberg prepn NC by ni- corresponds to pentanitrate, while the xyloidine
trating sawdust and suggested its use in lieu of corresponded more nearly to trinitrate (Ref 44,
BkPdr (Ref 31a, p 251) p 252)
1846. John Hall & Sons of Faversharn, England 1847. Crum of England nitrated cotton (pre-
started to manuf coton-poudre by the method viously bleached by special process) until he
of Schonbein, but this was abandoned after a could introduce no further nitrogen into the
terrible expln on July 14, 1847 which de- molecule. After washing and drying the product
stroyed the plant (Ref 44, p 241) it was anrdyzed by nitrometer method which
1846–1847. R. B6ttger of Frankfurt on Main gave 13.69% N. Nitration was done by mixed
(1806–1887) prepd “coton-poudre” independently nitric- sulfuric acid as described in Davis (Ref
of Schonbein. They joined in obtaining a patent, 31a, p 252)
including one for US, under the title: “Improve- 1847. Cyan uric Triazide, first prepd by Cahors,
ment in Preparation of Cottonwool and Other and in 1887 the process was improved by James.
Substances as Substitutes for Gunpowder” (Ref Taylor & Rinkenbach prepd it in 1923 & 1927
31a, p 249; Ref 44, p 240 & Vol ~ p CIO1-L) in pure state and detd its expl props (Ref 70,
1846-1850. Accdg to Colver (Ref 12, p 498), pp 66–68). See also Vol 3 of Encycl, pp C590-R
the first real advances in fusing of shells were & C591-L
made at that time. Early shell fuses have been 1849. Bomb, Aerial. After the invention of
made with the intention of their being _ignited balloon (aerospace) by Brothers Mongolfier in
by the flame of the proplnt chge. Then Free- 1782, several attempts were made to use balloons
born designed, by an adaptation of the per- for throwing bombs from the air. One of the
 H 137

first such attempts was made during the siege of nique was applied in 1884–85 by E. Mach &
Venice by Austrians in 1849. A brief descrip- P. Salcher to ballistic studies. In 1909 C. Cranz
tion of this operation is given in Vol 1 of Encycl, designed an apparatus called “Ballistische
p B225-R. Not much was done after this in Kinematograph” capable of taking 50000 frames
the 19th century because in 1899 aerial bombing per second and an improved app capable of
was forbidden by the Hague Convention. In taking 100000 fps was designed in 1912 by
1903, the Wright Brothers constructed a success- C. Cranz & B. Glarzel. A description of Cameras
ful aeroplane, and in 1907 the restriction on is given in Vol 2 of Encycl, pp C 13 to C 19 and
aerial bombardment was lifted. By 1910 nearly in this Vol under High Speed Photography, pp
all nations started experimenting with planes H104ff
dropping such bombs. The earliest recorded use 1850. Electric Friction Machine suitable for
of bombs dropped from a plane was by the field use was invented by Baron von Ebner of
Italians ca 1911 during the war in Tripoli. More Austria. After being improved in 1869, it was
successful was the use of improved bombs by used in the blasting of Hoosac tunnel (Vol 2
the Spanish during the war in Morocco. During of EncyclY pp B 187-L & B2 12-L)
the first 3 months of WWI no bombs were 1852. The Committee appointed by Conf6d6ra-
dropped because the planes and dirigibles were tion Germanique, to which Schonbein & B6ttger
not equipped for this purpose, but on Aug 30, proposed in 1846 the cessation of their method,
1914 a single German plane dropped bombs on refused the proposition (Ref 44, p 241)
Paris and one of the bombs penetrated into a 1853. Baron von Lenk, representing Austria,
crowded subway station, killing and mortally was happy that Prussia did not obtain the pa-
wounding 1000 persons. Then Germans also tent of Schi5nbein & Bottger dealt directly with
used Zeppelins in night raids on London. Con- them to obtn the method. He started to work
siderable aerial bombing was done during the on improvement of stability and possibility of
Spanish Civil War (1 936– 1939), but the great- adopting the improved powder as cannon pro-
est use was during WWII. For further develop- pellant (Ref 44, p 242)
ment of aerial bombing, see Vol 2 of Encycl, 1853. Emmanuel Nobel (1801 – 1872), father
pp B226–B232, German bombs of WWII are of Alfred Nobel, installed sea mines of his in-
described and illustrated in PATR 2510 (1958), vention in Baltic Sea to protect Russian fortress
pp Ger 14 to Cer 20 (See also under the year Cronstadt and City of StPetersbourg against
1782) British Fleet during the expected Crimean War
1850. Chlorate Explosives. After disastrous (See Vol 5 of Encycl, p D1585-L)
explns of 1783 & 1792 with mixts using K 1853–1856. During Crimean War, K.I. Kon-
chlorate (discovered in 1780 by C.L. Berthollet), stantinov constructed in Russia several pyro-
there were no applications of chlorate until about technic rockets (Ref 71, p 16)
1850. One of the earliest chlorate expls was 1853–1865. Beginning with one artillery
Augendre Powder listed in Vol 1 of Encycl, p battery using NC as proplnt, the number in-
A507-L. The mixt was, however, too sensitive creased to thirty, although the powder caused
for use. The problem of desensitization was erosion of the bore and occasional cracks in
solved in 1871 by H. Sprengel. Still better the walls of projectiles. While these problems
expls were developed in 1881 & 1888 by E. preoccupied the artillerists, a terrible expln
Turpin and in 1897 by Street. A fairly complete took place in 1863 at Simmering, near Hiten-
list of chlorate explosives is given in Vol 2 of berg (of the Gunpowder factory erected in
Encycl, pp C202 to C209 1853). A 2nd expln took place in 1865 at
1850. Accdg to Nambo (Ref 66, p 39), the Simmering near Vienna, and this provoked the
French Gunpowder of the Napoleon 111Army Imperial Edict of 11 Ott, 1865 prohibiting
contd: saltpeter 75.6, sulfur 10.8 & charcoal manuf of NC in Austria. This expln broke the
13.6% negotiations with France and US, to whom
1850. Cameras, High-Speed-Photographic. The von Lenk proposed his method (Ref 31a, p
fiist attempt to photograph a rapid event was Z53 & Ref 44, pp 241–42) -
made by H.F. Talbot of. England, and his tech- 1854. Introduction of the earliest Dynamite
 H 138

called Magnesial’nyi by Russian officer V.F. descriptions under the year 1865). Some success
Petrushevskii.. It consisted of NC absorbed by was achieved ca 1882 by using Brown-, Chocolate-,
powdered magnesit or magnesia. It was used or Cocoa Powder in larger caliber cannons. Their
“in Siberia for blasting in gold mines (Ref 71, use was discontinued ca 1900, when fully col-
p 10 and Vol 5 of Encycl, p D1 586-L) loided NC smokeless proplnts replaced them (Vol
1854. Epichlorohydrin was prepd by M. 2 of Encycl, pp C29–C30) (See also year 1888)
Berthelot (Ref 49, p 74) 1861. Guanidine (Gu) was first prepd by
1854. F. Pisani prepd 2,4,6,Trinitroaniline, Strecker (Ref 3 la, p 374)
also known as Picramide (Vol 1 of Encycl, pp 1861-1865. Period of American Civil War.
A409-R & A41 O-L) Sometime prior to this, Gen Rodman invented
1857. Lammot du Pent introduced a new caselesspropellant, called “Mamoth”, for use
formula, less expensive BkPdr by replacing the in cannons. It is briefly described in Vol 4
Indian saltpeter (K nitrate) with the much of Encycl, pp D754-R & D755-L
cheaper Chile saltpeter (Na nitrate) (Vol 5 1862. John Tonkin of England proposed to
of Encycl, p D1587-L) pulp Guncotton using a beater similar to
1858. Peter Griess discovered Diazocompounds “hollander” of paper industry. This produced,
(Ref 12, p 5) and in 1860 he prepd Diazodi- after thorough washing with water, more stable
nitrophenol, also known as Dinol (Vol 2 of NC than the unpulped material (Ref 3 la, p
Encycl, p B59; Vol 5, p D1 160-R and Ref 70, 253 & Ref 44, p 242)
pp 99 to 102) 1862. Tonkin proposed using pulped NC as an
1858. Accdg, to Marshall 1 (Ref 11, p 29), a ingredient of the following compm Na nitrate
Committee recommended the introduction of 65, charcoal 16, sulfur 16 & NC 3% (Ref 31a,
rifled ordnance into the British Navy, and from p 254)
that time there has been rapid and continuous 1862 & 1863. Baron von Lenk took out patents
improvements in all sorts of @rns. The intro- in Engiand in the name of R&ry to protect his
duction of the buffer has made the guns much method of purification of Guncotton. A factory
steadier. Breech-loading guns were reintro- was erected in 1863 at Stowmarket to make CC
duced, and the mechanism of breech greatly by his method, but it soon exploded (Ref 11,
improved. To meet the requirements of the p 40)
longer and more accurate camons, the grains of 1863. Frederick Abel, the chemist of English
Gunpowder were gradually increased in size so War Dept, started experiments and manuf on a
as to make them burn more slowly small scale of GC in the Royal Gunpowder
1859. Ethyleneglycol, Ethylene Oxide and Factory at Waltham Abbey and succeeded in
Ethyleneglycol Ether were prepd by Ch.A. obtaining by 1865 more stable product than
Wurtz (Ref 49, pp 7, 74 & 114) that of von Lenk (Ref 11, p 40) (See also below
1859. Diethyleneglycol prepd simultaneously under 1865)
by A.V. Laurenco & Ch.A. Wurtz (Ref 49, p 158) 1863, Accdg to Colver (Ref 12, p 18), Wilbrand
1859. Polyethyleneglycol was prepd by A.V. was the first to prepare TNT, but it was not as
Laurenco (Ref 49, p 177) pure as that of Hepp, prepd later (1880)
1860. Baron von Lenk introduced bronze 1863. Dioxane was prepd by A.V. Laurenco
guns in Austria (Ref 11, p 40) (Ref49, p 119)
1860. Accdg to, Gorst (Ref 71, p 7), rifled 1863. Triethyleneglycol prepd by A.V. Laurenco
weapons started to be used in Russia & Ch.A. Wurtz (Ref 49, p 170)
Note: British and French troops had such 1863. The 1st Nitroglycerin Plant was built by
weapons already during Crimean War A. Nobel at Helenborg, Sweden. It blew up in
1860 and After. Cannon Propellants. Up to 1864, killing the youngest Nobel and a chemist
about 1860’s Black Powder was used exclusively (Ref 58, p 126 & Vol 5 of Encycl~ p D1586-R)
as cannon and rifle propellant. Then attempts 1864. After expln at Helenborg, Nobel was
were made to replace it with smokeless proplnts forbidden by Swedish Govt to build another
made from incompletely colloided Nitrocellu- plant near any habitation. So he constructed
lose. These proplnts were too, fast burning (See a small plant, on a barge moored in the center
 H 139

of Mallarsee (Ref 58, p 126 & Vol 5, p DI 586-R) ration with Dewar) a smokeless proplnt described
1864. Baron von Lenk took out a US patent in Vol 1 of Encycl, p Al-R. Another Abel’s
for manuf of his NC (Ref 11, p 40) smokeless proplnt is listed on p A2-L
1865. Nobel obtd permission~of Ger Govt to 1866–1867. A. Nobel invented Guhrdynamit
construct a plant at Krummel, near Hamburg (Vol 5 ofEncycl,pD1586)
(Ref 58, p 126 & Vol 5, p D1586-R) 1866–1867. Abel’s “Researches on Guncotton”
1865. After obtg permission from Swed Govt, demonstrated that the material after proper
Nobel constructed a new plant at Vintervicken purification is far more stable than thought to
and another plant in Norway, which at that be. Moisture or exposure to sunlight did not
time was united with Sweden and Denmark harm it, and only exposure to elevated temp
(Ref 58, p 126 & Vol 5, p D1586-R) slowly decompd it. Abel found that in NC
1865. Jaworsky nitrated toluene with better produced at Waltham Abbey by nitration with
results than did Mitscherlich in 1834 (Ref 12, 18 parts of mixed acid, there was ca 1.62%
p 18) soluble in eth-alc. He detd its N content as
1865. Sir Frederick Abel of England proved 11.87%, while insol NC contd N=13.83%. He
that pulping followed by thorough washing calcd that the highest nitrated substance must
(such as done by Tonkin) improved the stability contain 14.1470 N, as was previously suggested
of NC because it helped to remove traces of by Crum (Ref 31a, pp 255–56)
acids (and of other impurities) found inside the Note: Abel’s researches were described more
fibers. He also showed that pressing of pulped fully in JChemSoc 20, 3 10–57 & 505–76 (1867)
material into sheets, discs, cylinders and other 1867. Borlinetto proposed a mixt of PA (Picric
forms would cause NC to burn less violently Acid) 10 parts, Na Nitrate 10 & K Chlorate 8.5
in the gun; The compressed blocks of Guncotton parts as substitute for Gunpowder (Ref 12, p 7)
prepd by him were an improvement over the 1867. Swed inventors J.H. Norrbin & C.J.
yarn of von Lenk, but they still were too fast, Ohlsson proposed mixtures of pulverized AN
not ballistically uniform and damaged the guns. with sawdust or charcoal as absorbent for NG
The compressed blocks were, however, very (Vol 5 of Encycl, p D1587-R) (Also Ref 11, p 42)
suitable for blasting purposes (Ref 3 la, p 254 1867. Swed inventor Bj6rkmann patented the
& Ref 44, p 242) mixture called Seranin (Vol 5 of Encycl, p
1865. Prussian Officer Schultze invented a D1587-R) ,.
sporting proplnt consisting of small pieces of 1867. Abel’s Stability Test using KI-starch
nitrated wood previously treated by special paper is described in Vol 1 of Encycl, p A2-L.
process. The nitrated wood was washed with It was modified in 1907 by Dupr6, becoming
water contg small amt of Na carbonate, followed known in England as “Heat Test” (Ref 44, p
by coned soln of K & Ba carbonates and drying 250)
(Ref 31a, p 287 & Ref 44, p 242) 1867. Abel of England and Trauzl of Austria
iVote 1: Accdg to MarshaIl (Ref 11, p 47), the, proposed to replace kieselguhr with Guncotton
Schultze powder was the first successful smoke- as absorbent for NG. The resulting expl was
less powder exudable because GC was not gelatinized (Vol
Note 2.’ A detailed description of “Sporting 5 of Encycl, p D1 587-R)
Smokeless Propellants” is given in Vol 2 of 1867. Nobel obtd BritP 1345 covering the de-
Encycl under “Bulk and Condensed Powders”, vice called fulminate blasting cap, which contd
pp B322 & B323-L MF (Mercuric Fulminate). This cap was crimped
1865. Sir F. Abel patented a process for manuf to one end of safety fuse and then inserted in
of Guncotton, granulated by means of an aq Dynamite cartridge (Vol 5 of Encycl, p
soln of gum arabic. He also proposed to granu- D1588-R) (See also Ref 12, p 4)
late mixts of Guncotton and Collodion Cotton 1868. A company was formed in England to
using a small amt of methanol or eth-alc to manuf Schultze’s sporting smokeless powder,
gelatinize CC in the mixture (Ref 31a, p 254 invented in 1865, and a factory was constructed
& Ref 44, p 242) in 1869 at Eyeworth in the New Forest. The
Note: Sir Abel also later patented (in collabo- greatest success was achieved after the method
 H 140

of prepn was modified by Griffiths. The This made it possible to use large blocks of wet
powder was very popular with sportsmen on Guncotton in Naval mines with comparative
account of the light recoil and absence of smoke safety (Ref 31a, p 256; Ref 44, p 242 & Ref
as compared with BkPdr (Ref 11, p 48) 12, p 5)
1868. Schultze of Prussia patented the expl Note: The compressed Guncotton contg about
Duanin, consisting of NG and partly nitrated 18% moisture proved to be so successful that
wood (Nitrolignin), but this mixt was exudable it was adopted by several countries (especially
(Vol 5 of hcyCl, p D1 587-R) by Russia) for loading not only of sea mines
1868. Accdg to Dutton (Ref 58, pp 135–37), but also of Whitehead torpedoes and cannon
the first Amer Dynamite plant was constructed shells. Russian Artillery used it during the
in California at a spot called Rock House Russo-JapaneseWar (1 904– 1905), but it proved
Canyon near San Francisco. It was manned to be inferior to Japanese shells loaded with
by Chinese, but supervisors were American. The Shimose (cast Picric Acid). Senior author of
plant, consisting only of Shacksj was called this Encycl, who served in 1917 in the Russian
“Giant Powder Co”. Great opposition to Dy- Navy, remembers that torpedoes on his destroyer
namite was encountered from a plant constructed of 1905 vintage were loaded with compressed,
at Santa Cruz, “The California Powder Works”, moist Guncotton
manufacturers of BkPdr. When, however, the. 1869. Nobel was granted Engl patent for use
Great Comstock Lode was discovered BkPdr as absorbent for NC mixts of combustibles
was found to be too weak to blow the hard (woodmeal, charcoal, rosin, starch) with oxi-
rock of Mount Davidson and only Dynamite dizers (K or Na nitrates) (Vol 5 of Encycl, p
could do it. The increased demand made the D1 588-L). The resulting expls are now known
management of Giant Powder Co push their as Dynamites With Active Base
Chinese workers harder and harder to meet 1869. Di%ignolle, Brug?re and Abel recommended
the demand, and as a result of this hurry the using salts of PA, especially K, Amm or Na
plant blew up in Nov 1869, killing two Ameri- Picrates in mixts with K nitrate and charcoal
cans and all Chinese. This accident did not as proplnts and fillers for projectiles (Ref 12, p 6)
discourage the Nobel Co, and another larger 1869. Fontaine proposed a mixt of K Picrate
and safer plant was constructed on the sand and K Chlorate for loading torpedoes (Ref 12, p 6)
dunes south of what is now known as Golden 1869. Brug>re proposed a mixt of Amm Picrate
Gate Plant. A large Chinese crew was assembled 54 & K Nitrate 46% for loading shells, while
and a German chemist was sent from Euro’pe as Abel recommended Amm Pier 40 & K Nitrate
Superintendent. The first 23 years of Giant 60% (Ref 12, p 6)
Company exemplify in dramatic terms the intro- 1869. Beilstein & Kuhlberg investigated ni-
duction of Dynamite in the US. During that tration of toluene with mixed nitric-sulfuric
periodY five successive plants, each larger than acid of various concns and isolated for the
the previous ones, were wrecked by explns first time several isomers of mono- and dinitro-
and in all 83, mostly Chinese men died. This toluene. They also prepd in 1870 TNT, but did
did not matter because the Giant Co’s capital not prepare Trinitrobenzene. At about the same
amounted to 2 million dollars time, mono-, di-, tri- and tetra-nitronaphthalenes
A detailed history of development and use were prepd (Ref 12, p 18). Trinitrobenzenes
of explosives in the US is given in the book of were prepd in 1882 by P. Hepp
Van Gelder & Schlatter (Ref 14) 1870. J. Howden of San Francisco, Calif
1868. E.A. Brown discovered that dry compressed proposed replacing Guhrdynamite by a Dyna-
Guncotton could be made to detonate very vio- mite consisting of NG 75 absorbed by 25 parts
lently by initiation with a fulminate detonator of a mixt consisting of pulverized sugar, K ni-
such as Nobel already used for exploding NG. trate and Mg carbomte. This was known as
Shortly afterwards he made the further im- Howden’s Dynamite (Vol 5 of Encycl, p D1 588-L).
portant discovery that wet Guncotton could be 1870. Nobel bought the patent of Norrbin &
exploded by the initiation of a small quantity Ohlsson which covered the use of AN as an
of dry Guncotton (the principle of the booster). “active base”. The patent also included the
 H 141

expl contg AN 80, NG 10–14 & charcoal 1873. Nobel obtd BritP 1570 for AN Dyna-
6– 10%. These expls became known as “Awrj mite, in which particles of AN were waterproofed
monium Nitrate Dynamites” (Vol 5, p D 1588-L) by stearine, ozocerite, etc (Vol 5 of Encycl, p
1870. Ethyleneglycol Dinitrate or Glycol Di- D 1588-L)
nitrate, in pure state, was prepd by L. Henry 1873. Sprengel reported that PA in conjunc-
(Ref 49, pp 130& 148; Ref 70, pp 143–45; tion with suitable oxidizer forms a powerful
and Vol 6 of Encycl, pp E259-R–E266–L) expl (Ref 31a, p 166). However, he did not
1870. 2,4,6-Trinitrobenzoic Acid and Its Salts apply his discovery to practice as did Turpin in
were prepd by F. Tiemann & W.E. Judson (Vol 1885, who invented modern High Explosive
2 of Encycl, pp B73 & B74) Shell (Ref 12, p 1886)
1870. Adoption by the Russian Armed Forces 1874. Accdg to info given in Encycl, Voi 2,
of the single-shot rifle invented by American p B46-R, Dinitrobenzenes became known
General Berdan but not accepted by the US 1875. After disastrous expln at the explosives
Govt. In its modified and simplified form it plant of Messrs Ludlow at Birmingham, killing
was used, under the name of Berdanka, for 53 persons, the Brit Govt, on recommendation
many years. It was partly replaced in 1891 of Col Sir V.D. Majendie, passed the “Explo-
(qv) by 5-cartridge rifle. (See Vol 2 of Encycl, sives Act”, which established the Inspectors of
p B101-R and Vol 4, p D756-L) Explosives who were given power to inspect
1870–1871. F. Volkmann obtd two Austrian all magazines and factories in order to see that
patents for prepn of proplnt named Collodine. operations are carried out in a reasonably safe
Its detailed description is given in Vol 3 of reamer. As a result, the number of deaths in
Encycl, p C394-L (Ref 44, pp 242–43) expls factories was very greatly reduced. The
Note: The patents on Collodine were classified provisions of the English Explosives Act of 1875
by Austrian Govt, and its manuf by private have been largely adopted by foreign countries,
plants forbidden. It was not until 1909 that British Colonies and India (Ref 11, pp 46–47)
its compn was published by O. Guttmann 1875. Nobel obtd BritP 4179 which covered
(1855–1910) (Ref 44, p 243 & Ref 11, p 48) Gelatins and Blasting Gelatin (Vol 5, p D1 588-L)
1871. Accdg to Marshall 1 (Ref 11, p 29), 1876. Nobel proposed using as antifreezes in
P (pebble) BkPdr was made by cutting large Dynamites: methyl-, ethyl-, amyl-, or isoamyl-
cubes from pressed BkPdr slabs nitrates, but these substances were too volatile
1871. Dr H. Sprengel, the inventor of vacuum (Vol 5, p D1589-L)
pump, took out patents for a whole series of 1876. Accdg to Gorst (Ref 71, p 10), it was
mining expls made by mixing together on the decided in Russia to load artillery projectiles
spot, just before the expl was required, an oxi- with compressed Pyroxylin contg 18–20%
dizing substance with a combustible one. They water. As the original method of loading proved
were exploded by a fulminate detonator. As to be unsatisfactory, it was necessary to develop
oxidizers he mentioned nitric acid and K chlorate a new method which was not completed until
and as combustibles carbon bisulfide, petroleum, the beginning of 1890
Nitrobenzene, Nitronaphthalene and many other 1877. Nitroguanidine (NGu) was first prepd by
compds (Ref 11, p 43 & Ref 12, p 7) Jousselin, but only beginning in 1900 did it
1871. Sprengel reported that Picric Acid (PA) start to be used in proplnts. During WWI NGu
by itself could be detonated by means of fulmi- was used by the Germans as an ingredient of
nate. but this led to no practical results until bursting charges (Ref 70, p 241 and Vol 6 of
E. Turpin started to use it beginning 1885 as Encycl, p G158). It was used during WWII
filler for HE Shell invented by him (See under and later in triple-base proplnt Gudol (Vol 5,
1885 & 1843) (Ref 11, p 49) pp D1537 & D1538)
1872. Accdg to Blasters’ Hdb (Ref 62, p 4), 1877. A Commission was appointed in France
Howden’s Dynamite (See under 1870), which to investigate the problem of ignition of jire-
was stronger than Guhr Dynamite, was used in damp. In the report made in 1880, it ad-
construciton of Musconetcong Railroad tunnel, mitted that there was then no explosive known
1 mile long, near Easton, Penna that would not ignite fire-damp (called “coal-
 H 142

damp” by Marshall (Ref 11, p 45) by C. Graebe, and they were studied at Pica-
1877. Wohlenberg & Sandstrom proposed tinny Arsenal in 1951 by S. Livingston and in
o-MNT as an antifreeze, which proved to be 1952 by D.B. Murphy et al. The results of their
better than those proposed by Nobel in 1876 studies were confidential at that time (Vol 2
(VO15, p D1 589-L) of Encycl, pp C48–C50)
1877–1878. Accdg to Dutton (Ref 58, p 153), 1880. Coal Mining Explosives, Testing for Per-
the Turks used, during Russo-Turkish War, the missibility. It seems that the earliest tests were
propellant prepd by treating NC with volatile conducted in France, judging by the paper of
solvent E. Audibert, AnnMines 12, 278–98 (1937), but
1878. In order to deal adequately with the many there seems to be no testing gallery until one
new inventions ,relating to, expls, the French was erected in 1907 at Li6vin which was de-
Govt created the “Commission des Substances stroyed during WTW. The earliest gallery seems
Explosives” and Prof M. Berthelot (1827–1 907) to have been erected in 1890 in England at
was appointed as its President (Ref 11, p 45 Hebburn-upon-Tyne. This was followed by
and Vol 2 of Encycl, p B104-R) the gallery erected in 1891 in Austria at
1879. Tetryl or 2,4,8-Trinitropheny lmethyl- Mrihrisch-Ostrau. A brief description of gal-
nitramine was first prepd by Michler & Meyer leries known to about 1965 is given in Vol
and studied in 1883 by van Romburgh, in 1886 3 of Encycl, pp C370–C378
by Mertens. It was not used as an expl until 1881. Prismatic Gunpowder was manufd by
WWI (Ref 31a, p 175 & Ref 70, p 339) molding hexagonal prisms of pdr and pressing
1879. Hellhoff took out several Brit patents them in. a special press (Ref 11, p 29)
for Sprengel expls contg nitric acid either 1881. Schultze’s Smokeless Powder became
enclosed in glass tubes or absorbed in fossil very popular with sportsmen (See 1868), and
flour or similar material (Ref 11, p 43) it was decided to construct another factory. This
1879. Compression (or Crusher) Test of Hess factory ,at Hetzbach in Hesse-Darmstadt was com-
is described in Vol 3 of Encycl, p C492 pleted in 1883 (Ref 11, p 48)
1879. Nobel obtd patent covering Ammonium 1882. The next successful smokeless proplnt
Nitrate Gelatins, known as Ammongelatins: was developed at @e Explosives Co, England
This was the last patent granted to Nobel (Vol and became known as “EC Powder” (Ref 11,
5, p D1588-L) p 48). Its compn and props are described in
1880. TNT (Trinitrotoluene), also called Trot yl, Vol 5, pp E6-R to E8-R .,
was made in very pure state by P. Hepp (Ref 11, 1882. Brown or Cocoa prismatic powder was
p 265) (See also under the years 1891 & 1902 made by, the Germans, and in spite of attempts
and Ref 12, p 18) to keep the method of rnanuf secret, it was
1880. The first du Pent NG & Dynamite being made in England at Waltham Abbey two
plant, known as Repauno Works, was constructed years later (kef 11, pp 29–30) (See also Vol
at Gibbstown, New Jersey (Vol 5 of Encycl, p 2 of Encycl, p B173-L)
D1587-L) 1882. The size of cannons greatly increased
Note.’ Accdg to Dutton (Ref 58, pp 141–43), and at the bombardment of Alexandria, the
the RepaunoPlant manufd Dynamite until 1954, British had 16-inch cannons weighing 80 tons
when it was converted to chemicals. There were each. Such weapons required very dense and
in 1960 other du Pent Dynamite plants, the very large grain powder (Ref 11, p 30)
largest located on the Potomac River near Mar- 1882. W.F. Read & D. Johnson patented iri
tinsburg, W. Virginia. It was operated by remote Germany a sporting proplnt prepd by. agglomerat-
control robots ing and hardening the NC grains by moistening
1880. S.R. Divine took out patents for Sprengel their surface with eth-alc. This proplnt was
expls consisting of K chlorate & liquid combustibles. adopted in England by the Explosives Company
One of such expl, Rackarock, was used in 1885 at Stowmarket, England and manufd under the
for blasting of Hell Gate in New York Harbor name of “EC Powder’;. It proved to be Suc-
(Ref 11, p 43) cessful and was used for many years not only
1880. Tetranitrocarbazoles were first reported in shotguns but also as EC Blank Fire Powder
 H 143

(Ref 31a, p 289; Ref 44, p 243 and Vol 5 1884–1896. Nearly simultaneously and inde-
of Encycl, pp E6-R–E8-R) pendently of Max von Duttenhofer, Paul Vleille
Note 1: Accdg to Marshall (Ref 11, p 48), the of France (1854–1934) invented in 1884 a
pdr was very successful and a separate company “ completely colloided single-base NC proplnt.
was formed which constructed a factory at Originally called “poudre V“ (V stands for
Green, near Dartford in Kent Vieille). It was renamed “poudre B“ in honor
Note 2: Powders of von Lenk, Schultze and of General Boulanger, then Minister of War. It
EC were “too quick for, use in rifled firearms. was adopted in 1886 for military rifles as BF
For this purpose it has been found neces~ry (poudre B 5 fusil), in 1888 for field camons as
to destroy entirely the structure of the original as BC (poudre B ?i canon de campagne) and in
cellulose by thoroughly gelatinizing it 1896 for marine camon as BM (poudre B de
1882. P. Hepp prepd 1,2,4-Trinitrobenzene and marine). These propellants and their modifica-
1,3,5-Trinitrobenzene, while 1,2,3-Trinitroben- tions were used as late as WWII (See also ,Vol 2
zene was prepd in 1914 by G. Korner & A. of Encycl, pp B 1 & B2 and C32-L) (See also
Contardi (See Vol 2 of Encycl, pp B48 & B49) Ref 31a, pp 292–94; Ref 44, p 244 & Ref 11,
1882. After introduction of rifled cannons by p 49)
French and British during Crimean War (1 853– 1884. 1,3-Diamino-1,3-trinitrobenzene first
1856), it was found by the Germans that ordi- prepd by Noelting & Collin, was also prepd in
nary BkPdr is too quick for larger caliber wea- 1888 by Barr and in 1902 by Blanksma (Ref
pons. After prolonged research, the prismatic 70, pp 95–98 and Vol 5 of Encycl, p D1 130-R)
brown powder, C/82, made from partly carbo- 1885. Prussian Govt established at Neunkirchen
nized’ charcoal, was introduced (See also Vol the first testing station for investigating mining
5 of Encycl, p D1 580-R, under Duttenhofer). explosives, which included a testing gallery.
Then the Russians introduced in 1886 a brown The method was soon adopted by other countries
pdr contg 19.6% of partly carbonized rye straw, (Ref 11, p 45)
78.4% K nitrate and 2% sulfur (Vol 2 of Encycl, Note: Such grdleries and method of testing are
p B173.L) described in Vol 3 of Encycl, pp C368-R to
Note: The above description was only partly C378-L. See also Nao6m (Ref 16, p 396)
reported by P. Tavernier in Ref 44, pp 243–44 1885. Accdg to Colver (Ref 12, pp 5, 7, 11
1883. Prepn of Tetryl (or Tetralite) was first
& 12), the discovery by French scientist E.
described by van Romburgh in RecTravChim
Turpin (1 848– 1927) of detonating properties
2, p 108. Quoted from Marshall 1 (Ref 11, p
274) of PA (Picric Acid), was followed by its adoption
1883-1884. M. von DuttenhofeI (1 843–1 903) for filling HE shell of his design (See next item)
nitrated brown charcoal (used for prepn of C/82) Note: Accdg to Marshall (Ref 11, p 44), H.
by Schultze’s method to obtain colloided rifle Sprengel was the first to draw attention to the
powder RCP (Rottweiler Cellulose Pulver) which fact that PA by itself could be initiated by a
was adopted by the German Army in 1884, but powerful detonator and was a very powerful
its compn was kept secret until 1887 (See also expl, but no practical use was made of his
Vol 5 of Encycl, p D1581, under “Duttenhofer’s discovery (See year 1873)
Smokeless Propellant”) (Ref 44, p 244) 1885. In this year, the French Govt adopted
1884. Ammonites are expk consisting of AN the HE Shell designed by E. Turpin, using as
and nitrated derivatives of naphthrdene. The a filler Picric Acid, designated as Me%nite. Its
original expl was known in England as “Miner’s
construction was essentially the same as modern
Safety Explosive”. Some Ammonites contd TNT
Hi~ Explosive Shell. It is described on p 11
and were used for military purposes. A detailed
description is given in Vol 1 of Encycl, pp of Ref 12 and illustrated there, but not repro-
A307-R to A31O-L. Some Ammonites used by duced here
Germans during WWII as Substitute (Ersatz) Following is a historical development of
Explosives contd RDX. They are listed in PATR projectiles given by Marshall 1 (Ref 11, pp
2510 (1958), p Ger 44 and on p E122 of Vol 30–1):
5 of Encycl
 H 144

The fust projectiles used were made more or 1885–1886. Accdg to Colver (Ref 12, p 14),
less like arrows with metal “feathers” and metal three varieties of PA expls, invented by E.
arrow-head’s. They were soon found unsuitable Turpin, were introduced in France. The first
and replaced by round shot made of stone, lead, variety known as Explosif de Turpin consisted
iron or bronze. All these materials remained in of powdered PA either pressed alone, pressed
use for several centuries, but stone was mostly with the addn of soln of a binder (such as gum
used for large cannons. This was because it is arabic or collodion), or by pouring the molten
less expensive than metal and also because the mat erial into cent ainers of suitable form. Al-
barrels of early camons would not stand the most a; soon as PA was introduced for military
strain of discharging heavy materirds. Lead and purposes, a mixt of 70 parts PA & 30 of Gun-
iron bullets were usually employed in small arms. cotton dissolved in 45 parts of acetone (or
Attempts were made very early to throw from ether-alcohol) was used under the name of
cannons incendiary missiles such as had been Melinite This was 2nd variety. Then later
previously discharged from catapults, etc. In Guncotton was discarded and straight PA was
order to prevent the extinguishing of flame during heated at 130–1 35° and poured directly into
flight, the projectiles (mostly stones), smaller shells. This was the 3rd variety, and the name
than the bore of the canno~ were smeared over was M61inite (called Lyddite in England). The
with incendiary matter and wrapped in cloth tests conducted in 1892 at LeBouchet showed
soaked in the same material. This method was that shells loaded with cast PA were safe and
used in 1469 at the siege of Weissenburg. Ano- very powerful
ther incendiary, the “red hot shot”, was dangerous M61inite (PA) was used in France for more
to use because it could ignite prematurely the than 25 years, and only during WWI was it re-
powder charge in the gun, This difficulty was placed by TNT (Trotyl, in Fr)
overcome in 1579 when Stephen Batory, King Note 1: Since the mp of PA is relatively high
of Poland, placed a thick wet pad on top of (122.50), the pouring process required to melt
powder charge prior to introducing the hot-shot. PA to that high temp was rather dangerous.
Hot-shots were used with great effect by the Various additives have been suggested to lower
English in the defense of Gibraltar in 1782 the mp. Several low mp mixts were suggested
Hollow projectiles (shells) filled with BkPdr by Girard, and four of them are listed in Colver
could not be made until casting of metal was on p 15. Most interesting of them is: PA/TN-
developed. But a sort of weak shell was made Cresol in molecular proportion 1:1. Its mp
of earthenware, or by joining two metrd hemi- is 78°
spheres. These were filled with a slow-burning Note 2: PA is very poisonous and it dyes skin
powder well rammed, and provided with an yellow, and this is hard to wash out. These
igniter, which was lighted by the flame of pro- were probably the reasons why PA was eventu-
pelling charge, and burned for a few minutes ally replaced by other HE’s, such as TNT, PETN,
before reaching the charge in the shell. Better RDX, etc
results were obtd with an igniter, invented in 1886. Brown or Cocoa Powder was manufd at
1588 (qv), or with fuse invented by Bickford Okhta Plant, near StPetersburgh, Russia (Vol
in 1831 (See Vol 2 of Encycl, p Cl 12-L). The 2 of Encycl, p Bl 73-R)
shells for early muzzle-loading rifled cannons 1886. Accdg to Gorst (Ref 71, p 14), I.M.
were provided with studs to fit into rifling and Chel’tsov proposed to load shells and mines
with copper plates (gas-checks) over the base to with a mixt of AN 72.5 & AmmPicrate 27.5%,
prevent the escape of gasespast the shell. For named by him Gromoboy
some of the early rifled breech-loading guns, the 1886. The British had 16.25-inch cannons
shells were coated with lead, but now they are weighing 110 tons which required very dense,
provided with copper bands near the base to very large grain BkPdr, but it was soon replaced
take the rifling and prevent escape of gases. by smokeless powder (called now smokeless pro-
Originally shells were filled with BkPdr, but now pellant). With this proplnt it was possible to
they are filled with HE’s, such as TNT, Comp B, propulse a s&ell weighing a ton a distance of
etc 20 miles (Ref 11, p 30)
 H 145

1887. P. Vieilfe devised in France the stability 1888. Munroe-Neumann Effect or Shaped Charge
test known as “l%preuve ~ 11O°C de Vieille” Effect was accidentally discovered by C.E. Munroe
(l%preuve au premi?re rouge), but it proved to of the US, but was not put to practical applica-
be of no practical value until it was modified by tion until 1910 when C.E. Neumann of Germany
Commandant Lepidi and became known as proposed using the effect in the manuf of ex-
“l%preuve 5 la resistance totalis~e” (Test for plosive ammunition (Vol 4 of Encycl, pp D442
Total Resistance). Both of these tests, of which to D454)
the 2nd test became French official, are de- 1888. PA (Picric Acid) was adopted by the
scribed in Vol 1 of Encycl, p XXI, under “Re- German Govt, under the name Granatfullung 88
sistance to Heat Test” (Gfg 88). It consisted of PA pressed in card-
1887. Another Commission was appointed in board or metal containers. It was used for
France to inquire into coal-mine explosions. ffling shells, land mines, depth- and demolition
Influenced by Berthelot’s work and theories, charges. It was used as late as WWII, under the
its attention was directed to the question of name Fi,illpulver 88, listed in PATR 2510, p Ger
the heat evolved by an explosive and the resuh- 46-R (1958), as Filler No 2
ing temperature of the products (Ref 11, p 45) 1888. Triaminotrinitrobenzene was first prepd
Note I: As a result of the work of the Com- by Jackson & Wing. More recently (1928), it
mission, a max temp of 1500°C for expls used was prepd by Fliirscheim & Holmes (Ref 70,
in coal layers (explosifs grisou-couche) was pp 364 to 366). Its uses are not indicated in
established; and 1900°C for expls used for Ref 70
blasting rock in gaseous coal mines (explosifs 1888. PA was adopted in England under the
grisou-roche) (Vol 3 of Encycl, p C369-L) name of Lyddite (Ref 11, p 50); then later in
Note 2: Methods of calculating heat and temp Italy as Pertite and in Japan as Shimose (Ref
of expln are described in Vol 3, pp C447-C449) 21, p 386)
1888. In Germany and in England it was re- 1888. Alfred P. Nobel (1833–1 896), famous
cognized that the temp of expln is only one of scientist (born in Sweden, raised and educated
the factors in making an expl safe or dangerous in Russia, and worked in Sweden, Germany &
to use in fiery mines. Consequently, reliance USA), prepd a double-base smokeless proplnt
has been placed more upon testing in galleries, by replacing camphor of Celluloid (Vol 2 of
which are intended to imitate as nearly as pos- Encycl, p C95-L) with NG. He called the
sible conditions in the mines. The Committee proplnt Ballistite. In 1889 he prepd Ballistite
was appointed in England in 1888 and a trial directly from Collodion Cotton (Vol 2 of Encycl,
gallery at Hebburn CollieW completed in 1892 p C 103) and NG using the “solventless” method
(1890?). After experimenting with various expls of Lundholm & Sayers. More detailed de-
until 1895, the use of several expls, mostly scription is given in VO12 of Encycl under
based on AN (Ammonium Nitrate) was re. Ballistite on pp B8–B9 (See also VOI 3, p C400
commended. Based upon the results obtd by and Ref 31a, pp 293–95).
this Committee, the Coal Mines Regulation 1888. .Dr W. Kellner prepd in the laboratory of
Act of 1906 was founded. Following this Act, F. Abel the double-base proplnt Cordite (See
a gallery was constructed at Woolwich Arsenal Vol 3 of Encycl, p C532-L)
and another more lately at Rotherham (Ref 11, 1889. Cordite, the 2nd successful double-base
p 46) propellant, was patented for the British Govern-
Note: More detailed description of this subject ment by F. Abel & J. Dewar and adopted as a
is given in Vol 3 of Encycl, pp’ C372 & C373) military proplnt. It was Cordite Mark 1 or CSPI
1888. Cyclotrimethylene Trinitrosamine was (Cordite Smokeless Powder ) (See Vol 3 of
discovered simultaneously by Griess & Harrow Encycl, p C532-L; also Ref 31a, p 295 & Ref
and by Mayer. It was studied in 1895 by Duden 44, p 246)
& Scharff and in 1896 by De16pine (Ref 70, pp 1889. A. Nobel proposed using DPhA (Di-
86-90). It was used during WWII in Germany phenylamine) as stabilizer for his Dynamite
under the name R-Salz (PATR 2510, p Ger 170-L) (Ref 44, p 250)
See also Vol 3 of Encycl, p C633 1890. Accdg to Dutton (Ref 58, pp 144-46),
 H 146

attempts to use Dynamite as bursting chge in Curtius, (Vol 1 of Encycl, p A536)

artillery shells were unsuccessful, because it 1891. Lead Azide was first prepd by T.
blew up inside the barrels, thus destroying Curtius (Vol 1 of Encycl, p A545)
them and wounding or killing persomel. In 1891. Ch.E. Munroe of the US prepd a double-
order to reduce the muzzle velocity, pneumatic base proplnt, Indurite, by gelatinizing Gun-
camons operated by compressed air were invented. cotton with about an equal amt of Nitrobenzene.
Here the Dynamite shell was propelled with lower Indurite was not found ,suitable for use in
velocity than possible in using a proplnt. At cannons (See Vol 2 of Encycl, p C32-L and
that time Americans were still using a brown Ref 31a, p 296 & Ref 44, p 246)
variety of BkPdr, while all European countries 1891. C. I-Russermann with the Griesheim
switched to smokeless propellants. In 1890, Chemical Plant began the manuf of TNT, for-
the US Navy built the ship USS Vesuvius which merly (in 1880) prepd by Hepp in the labora-
had mounted on her bow three monster air tory. In 1901 the manuf was begun by the
cannons which hurled shells weighing a thousand Carbonite Co and some expl firms soon fol-
lbs each and contg 600 lbs of Dynamite with lowed. The first country to adopt it for mili-
some NC. An electric storage battery inside tary purposes was Germany (1902), as Spreng-
each shell ignited, on impact, NC which de- munitwn 02. Other countries soon followed,
tonated the Dynamite. Great things were ex- such as Italy (1907), under the name Tritolo
pected of Vesuvius when in 1898 it attacked and Russia (1909), under the name of Trotil.
Santiago, Cuba, but they were not fulfilled be-, In the English Service it was formerly known as
cause the range of air-cannons, 1 mile, was T. N.T., but later as Trotyl. In the US it is
shorter than the range of battery at the fort called TNT and was adopted for military pur-
of Santiago. After this the US Congress de- poses in 1912 (Ref 11, p 265; Ref 18, p 20;
cided to remove the air-cannons Ref 64, p 2-4 (L) and Ref 71, p 12). It
1890. Hydrogen Azide and Hydrazoic Acid started to replace M;linite in France as a
were first prepd by T. Curtius and then investi- bursting charge just before, WWI
gated by D. Mendel~eff (Vol 1 of Encycl, pp 1891. D.I. Mende16eff (Mendeleev) of Russia
A537-R “to A542-R) (1 834–1907) invented, quite. independently of
1890. Tetranitrocarbazole, first prepd by C. Vieille (who kept secret his poudre B), a com-
Graebe. A better method was developed in plet ely colloided smokeless proplnt prepd by
1912 by Casella Co, and this method is still gelatinizing with eth-alc the NC of N 12.44%,
used. TeNCbz is suitable as component of which contained sufficient oxygen for complete
igniter and pyrotechnic compns (Ref 70, pp combustion to CO & water. He called the
328–30) proplnt Pirokolodion (Pyrocollodion). It was
1890. Cuprous Azide was first mentioned by adopted as “service” proplnt in newly de-
T, Curtius in Ber 23, 3023, but was not pro- veloped, by Mossin and Nagan, cal .30 (7.62mm),
perly investigated. History of later work is 5-cartridge rifle called “TrekMineynaya Vintovka”
given in Vol 1 of Encycl, p A534 (Three-Line Rifle) (See Ref 51, pp Rus 22-R&
1890. A. Wohl proposed polymerized glycerin Rus 23-L and Vol 2 of Encycl, .p C32-L where
as a gelatinize for Dynamites, but it was not the N content of Pyrocollodion is erroneously
very satisfactory because it diminished strength given as 13.44 instead of 12:44%)
& brisance of Dynamite, made it too difficult Note: P. Taverriier did not say in his descrip-
to detonate and affected adversely its oxygen tion in Ref 44, p 246, that Mende16eff prepd,
balance (Vol 5 of Encycl, p D1 589-L) independently from Vieille, a NC contg 12.447.
1890–1891. Mercurous Azide was prepd by N and named it Pirokolodion (Pyrocollodion),
T. Curtius (Vol 1 of Encycl, p A591) but said further that Lt Bernadou patented a
1890–1891. Silver Azide was prepd by T. single-base proplnt contg at first CP2 with
Curtius (Vol 1 of Encycl, p A598) 12:45% N and later pyrocollodion with N=
1890–1891. Sodium Azide was prepd by T. 12.60%. All this is wrong. Lt Bernadou did
Curtius (Vol 1 of Encycl, pp A601 & A608) not know the compn of French CP2, but he
1891 .Hydrazine Azide was prepd by T. knew the compn of Mende16eff’s Pyrocollodion,
 H 147

which was only similar to CP2 Austro-Hungarian Army and this lasted until
Accdg to the books of: Lt John B. Bernadou, 1918, when its entire supply was blown up in
US Navy (1858–1908) (Ref 2a) and of Van I@v, Russia. Its compn was never officially
Gelder & Schlatter (Ref 14, p 812–21), also revealed, but it was suggested that it was either
listed in Vol 2 of Encycl, p B 104 and described straight Ammonium Trinitro-m-cresylate /Ckesy-
on p C32-L, Lt Bernadou, while serving as lite) or its mixt with PA. More information
US Naval Attach6 in StPetersbourg, learned in on this subject is given in Ref 11, p 17 and in
1895 the method of prepn of Mendel$e~s proplnt Vol 5 of Encycl, pp E8-R to E9-L
(He did not know the secret of Vieille’s “poudre 1892. 5-Amino-1H-tetrazole was first prepd
B“) and decided to introduce it in Amer Navy by J. Thiele and examined in 1954 by L.F.
in preference to Indurite. After investigating Audrieth & J.F. Currier at Univ of Illinois
ballistic properties of Pyrocollodion, Bernadou and by D.B. Murphy, J.P. Picard, P. Rochlin
found that better ballistic props as a cannon & S. Helf at Picatinny Arsenal. Was recom-
proplnt could be obtd if N content of NC were mended as cooling agent in proplnts. Its salts
raised from 12.44% to about 12.6’ZO.He gela- and nitrated derivatives are explosive (Vol 1
tinized NC with eth-alc and called the resulting of Encycl, pp A258-L to A260.R) [See also
proplnt “Pyrocellulose Powder” or simply 5-Nitroaminotetrazole of Lieber, p A260-L]
“Pyre”. It was adopted in 1897 by the US 1894. Styphnic Acid(2,4,6-Trinitroresorcinol)
Navy and used in 1898 during Spanish American was first prepd by Hauff (Ref 11, p 281)
War. US Army adopted “Pyre” in 1899. Large 1894. Tetryl (or Trinitrophenylmethylaniline),
scale manuf began in 1900 at a newly built first described in 1883 by van Romburgh was
“US Naval Powder Plant”, Indian Head, Md commercially manufd in Germany and tested
(now known as US Naval Ordnance Station). as to its usefulness by military authorities
Picatinny Arsenal, Dover, NJ, started its manuf (Ref 12,, p 27)
in 1907 (Ref 31a, p 297) 1894. Hydrazine, Anhydrous was prepd in
Note: Dutton (Ref 58, p 154) stated that Russia 1894 by Lobry de Bruyn, but its salts were
rearmed its Army in 1896 with Mende16efrs pro- prepd in 1875 by Emil Fischer, who coined
pellant and that this proplnt modified by Lt the name “hydrazin”. Its derivs were investi-
Bernadou was adopted in 1901 by the US Govt gated during WWII by Col L.F. Audrieth. More
1891. It is the year of introduction by the information is given in this Volume under
Russian Armed Froces of 5-cartridge, cal 7.62mm Hydrazine and Derivatives
rifle invented by Mossin and Nagan. It is known 1894. Mercuric Azide was prepd by M. Berthe-
as trWdineytraya vintovlca (three-line rifle). It lot &P. Vieille (Vol 1 of Encycl, p A590)
is briefly described in ArmyOrdn 30, 83–85 (1946) 1894. Accdg to Gorst (Ref 71, p 11), attempts
and in PATR 2145 (1955), pp Rus 22-R & Rus to use Melenit (Russ name for PA) in shells of
23-L cannon type 1877 were unsuccessful and the
1892. Tetranitrooxanilide was prepd by A.G. idea was abandoned
Perkin and used as a component of BkPdr 1894. Butanetriol Trinitrate was first prepd by
type expls and of pyrotechnic compns (Ref 70, Wagner & Ginsberg. A new method of prepn
pp 331 –34) (See also Hexanitrooxanilide) was devised in 1948 by the US Rubber Co, and
1892. Hexanitrooxanilide was first prepd in its props were evaluated in 1948 by the US
England by A.G. Perkin. Used in pyrotechnic Naval Powder Factory. Used as expl plastici-
compns (Ref 70, pp 170–72) zer for NC (Ref 70, pp 40–42)
1892. Aminoguanidine and Derivatives were 1895. The Ammonium salt of Hexanitrodi-
first prepd by J. Thiele (Vol 1. of Encycl, p phenylamine, known as yellow dye “Aurantia”,
A2 10) (See year 1928 for Nitraminoguanidine manufd by the Chemische Fabrik Griesheim,
and Its Salts) proved to be a valuable explosive (Ref 12, p 25)
1892. Zinc Diazide was prepd by W. Wislicenus 1895. Adoption by the Russian Govt of modi-
and in 1898 by T. Curtius & J. Rissom (Vol 1 fied revolver Nagan, invented in 1880’s by
of Encycl, p A624) Nagan. It is a 7.5mm (0.295-inch) weapon
1892. Ecrasite (Ekrasit) started to be used by using 5 cartridges with bullets hidden in them.
 H 148

It is described, with illustration of its cartridge, Curtius & A. Darapsky prepd Mn(N3)2 (Vol 1
in PATR 2145 (1955), p Rus 11-R of Encycl, p A590)
1896. The AB Bofors, Nobelkrut of Sweden 1898. Nickel Diazide, Basic was prepd by T.
patented a smokeless proplnt which was prepd Curtius & J. Rissom, and then in 1900 T.
by glueing and compressing together several Curtius & A. Darapsky prepd Ni(N3)2 (Vol 1
layers of different components. The outer of Encycl, p A593)
layers were slow burning, while the speed in- 1898. Potassium Azide was claimed to be prepd
creased progressively towards the inner layers by L.M. Dennis & C.H.” Benedict, and in the
(Ref 44, p 246) same year by T. Curtius & J. Rissom (Vol 1
1896. Introduction by P. Vieille of 2% amyl of Encycl, p A595)
alcohol as stabilizer for smokeless propellant 1898. Rubidium Azide was first prepd by
did not produce satisfactory results, especially L.M. Dennis & C.H. Benedict and also by T.
in cannons of large caliber, and the amount Curtius & J. Rissom (Vol 1 of Encycl, p A596)
was increased in 1906 to 8%. Nevertheless, 1898. Strontium Diazide was prepd by the
two disastrous explns took place on battleships same persons as above (Vol 1 of Encycl, p
16na in 1907 and Libert 6 in 1911. Both explns A620)
were ascribed to spontaneous ignition of poudre 1898. Thalium Azide was prepd by the same
BAm stored in their powder magazines (Ref 44, persons as above (Vol 1 of Encycl, p A622)
p 248 & Ref 31a, p 308) 1898. Azotetrazole was prepd by J. Thiele,
1897–1898. It is presumed that Research and its expl salts were recommended by E. von
Establishment at Spandau, Germany, proposed Herz and by H. Rathsburg for use in detonators.
to treat grains of small arms’ proplnts on the Its derivatives were described by L.F. Alllieth
outside with slow-burning substances like cam- & J.F. Currier in Univ of Illinois Rept, “De-
phor. Such proplnts were progressive to a rivatives of 5-Aminotet razole”, pp 22—23 (1954)
certain extent. The GerP 120201 of 1898 (See Vol 1 of Encycl, pp A659 & A660)
proposed treating grains of NC with aromatic 1898. Simon Thomas developed stability test,
nitrocompds, such as DNT (Ref 44, p 246) which is described in Ref 28a, p 80). It was
1897-1898. Cheddites were invented in 1897 modified in 1920 and became the “Dutch Test”
by E. Street of England, and several varieties or “Loss of Weight Test”, described in Vol 5
of original compn were patented in 1898. A of Encycl, p D1580-R
detailed description with several tables is given 1899. Potassium Dinitrobenzfuroxan, first
in Vol 2 of Encycl, p C155 to C164 prepd by P. von Drost, was examined at PicArsn
1898. Cadmium Diazide was prepd by T. Cur- in 1954 and 1955. It is used in priming compns
tius & J. Rissom (Vol 1 of Encycl, p A526) (Ref 70, pp 302 to 305)
1898. Calcium Diazide was prepd by T. Cur- 1899. Cyclotrimethylenetrinitramine called RDX
tius & J. Rissom (Vol 1 of Encycl, p A527) or Cyclonite, was first prepd by Henning of
1898. Chromium Triazide was prepd by T. Germany and he named it Hexogen. He used it
Curtius & J. Rissom (Vol 1 of Encycl, p A530) for medical purposes. Then Brunswig prepd it
1898. Cobalt Triazide was prepd by T. Cur- in 1916, but it was E. von Herz who recognized
tius & J. Rissom (Vol 1 of Encycl, p A531 ) in 1920 its value as an expl. The first one who
1898. Cupric Azide was prepd by T. Curtius prepd it in fairly good yield was G.C. Hale of
&J. Rissom (Vol 1 of Encycl, p A532) Picatinny Arsenal (in 1925). Then nothing
1898. Iron Azide or Ferric Triazide was prepd was done until 1940 when J. Meissner of
in soln by T. Curtius & J. Rissom, but it was Germany developed a continuous method of
not until 1917 when L. Wohler & F. Martin manuf. In 1940, Drs Ross & Schiessler of
prepd it again and isolated it (Vol 1 of Encycl, Canada developed a process which did not re-
pp A543-L to A544-L) quire the use of hexamine as a starting material,
1898. Lithium Azide was prepd by T. Curtius but the most important work on nmnuf and in-
& J. Rissom (Vol 1 of Encycl, p A588) vestigation of RDX was done by W.E. Bach-
1898. Manganese Diazide, Basic was prepd by mann. Four methods of manuf of RDX were
T. Curtius & J. Rissom, and then in 1900 T. developed in Germany (Vol 3 of Encycl, pp
 H 149

C611 to C626). Expl mixtures based on RDX and Trinitrotoluene could be in”expensively
are described on pp C626 to C630. See also manufd (Ref 12, p 17)
Ref 70, pp 69–75 1900. Germans started to use in their NC rifle
1899. Oxyliquit, invented by Linde, consisted proplnts either 0.5 or 1.0% DP~ as a sta-
of liquid air (or oxygen) absorbed in wadding, bilizer (Ref 44, p 250)
charcoal or other org material. As these mixts 1900. Barium Diazide was prepd by T. Curtius
were hard to detonate, kieselguhr was sub- (Vol 1 of Encycl, p A523-L)
stituted as absorbent with an addn of petroleum. 1900. Konovalov of Russia prepd some expls
It was inconvenient to use, as the cartridge had by laboratory nitration of aliphatic derivs of
to be fired within 5 to 1$ reins of its prepn. It petroleum, using weak nitric acid under pres-
was tried in Austria and used in construction of sure, but the yields were poor (Ref 12, p 29)
the Simplon tunnel (Rcf 11, p 44) 1900. Accdg to Gorst (Ref 71, p 15) it was
1899. Aluminized Explosives. The addn of proposed in Russia to replace MF (Mercuric
Al to increase the performance of expls was Fulminate) detonators with those in which 3/4
first proposed by R. Escales of Germany and of MF was replaced by Tetryl or Trotil (TNT)
patented in 1900 by G. Roth. For more details 1900. Chromatography, a physical method of
see Vol 1 of Encycl, pp A146 to Al 51 separation in which the components are parti-
1899. Ammonal, originally contg AN, charcoal tioned between two phases, was invented simul-
& Al was proposed by R. Escales and patented taneously and independently by American geolo-
in 1900 by G. Roth (Vol 1 of Encycl, p A287) gist D.T. Day and Russian botanist MS. Tsvet
(See also year 1917 for Austrian Ammonal T) (Tswett). Their methods and later modifica-
1899. Tritonal 80/20 (TNT 80 & Al 20%) was tions are described in Vol 3 of Encycl, pp C289
developed in the US as filler for bombs. The to C298. Qualitative method of separation of
addn of Al to expls was proposed in 1899 by ingredients by adsorption was known for cen-
Escales and patented in 1900 by Roth, but it turies. This is described on p C289-R
was not properly’ investigated until 1943 and 1901. Hexanitrobiphenyl was first prepd by
1944 at PicArsn by W.R. Tomlinson Jr and F. Ullmann & J. Bielecki (Vol 1 of Encycl, p
proposed as filler for bombs of high blast ef- B1 24)
fect (Ref 64, pp 7-68 & 7-69 and Ref 70, pp 1901. Accdg to Colver (Ref 12, p 21), manuf
386–90) of TNT by the method of P. Hepp, as improved
1900. It was proven during South African War by C. Hdussermann, was conducted in 3 stages:
(1899–1902) that Brit proplnt Cordite Mk 1, 1) Nitration of toluene to MNT, using relatively
which contd 58’?Lo NC, caused very excessive weak spent mixed acid; 2) Nitration of MNT to
erosion in gun barrels. As a result of this, DNT using stronger acid and 3) Nitration of
the amt of NC was reduced to 30%, NC was DNT to TNT using strong acid with oleum.
increased to 65, and mineral jelly was 5!Z0 This method, which proved to be more econo-
(Ref 44, p 247& Vol 3 of Encycl, p C532-L) mical than direct nitration of Toluene to TNT,
1900. It was also shown during South African was used in the US until WWII, when Dr I.A.
War that shells loaded with Lyddite (Engl Grageroff introduced the so-called “reverse
name for PA) were less satisfactory than those process”. This method was twice as rapid.
loaded with Black Powder. This was caused Many plants switched to Continuous Methods
by incomplete deton of PA, which was attri- (See Vol 3 of Encycl, p C505)
buted to the faulty construction of detonators 1901. Accdg to Colver (Ref 12, pp 20 & 24),
(Ref71, p 11) German expls industry unreservedly adopted the
1900 is the year of discovery by the Badische manuf of TNT, mostly by the method of Hepp
Anilin- und Sodafabrik of “contact process” as improved by I-Gussermarm (See above). Some
for manuf of strong sulfuric acid and oleum, factories used their own modifications and used
which was less expensive than the chamber names, such as Trotyl, T.rynol, Trolit, etc. The
method. As such acid was required for mixed names Triphstit and Plastrotyl were used for
nitric-sulfuric acid to nitrate aromatic hydro- TNT worked-up with DNT, MNT and a small
compds to tri- or higher states, Trinitrobenzene amt of NC
I

H 150

1902. Accdg to Colver (Ref 12, p 23), Germany produced very noxious fumes contg chlorine
was the first country to adopt TNT for mili-
1904. 2,3,5,6-Tetranitroanisole was prepd by
tary purposes, mostly as filler of HE shells. Its
J. Blanksma (Vol 1 of Encycl, p A454-R)
official name was Fullpulver 02 (Fp 02). It is
1904. Introduction of Obermuller Stability
listed in PATR 2510 (1958), p Ger 46-R as
Test “which consists of heating 1 to 2g NC in
Filler No 1
a small tube under vacuum at 135–1 40° and
1902. Dr Edeleanu & G. Filiti of Rumania
measuring the pressure of evolved gas by va-
took out a patent for manuf of nitrocompounds
cuum manometer (Ref 38a, pp 87–88)
from petroleum, but they found no practical ap-
1904-1905. 2,4,6-Trinitroanisole or Methyl
application (Ref 12, p 27)
Picrate was patented for use in smokeless proplnts
1902. Germans proposed using cyanamide, di-
in mixt with an equal amt of Pyrocelhrlose (Vol
cyandiamine or tricyandiamine as auxiliary
1 of Encycl, p A452-R)
stabilizers in their proplnts (Ref 44, p 251)
1905. The problem of producing quite satis-
1902. Introduction of Bergmann-Junk Stability
factory antifreeze remained unsolved until S.
Test. It is described in Vol 2 of Encycl, pp
B102-R to B103-L (See also Ref 44, p 251) Nauckhoff ‘of Sweden published his work in
1902. Accdg to Colver (Ref 12, p 23), Germans ZAngewChemie 18, pp 11 & 55 (1905), in
also used TNT for demolition purposes, under which he formulated the requirements for a
the name Sprengmunition 02. It replaced satisfactory antifreeze and gave a list of compds
Sprengmunition 88, which was PA (Picric Acid) which might prove to be suitable
1902. Cordeau d6tonant, developed in France, 1906. Centralizes were first investigated in
was improved in 1907 by L. Lheure. This type’ Germany at the Zentralstelle ftir wissenschaft-
of cordeau was introduced in 1913 in the US lich-technische Untersuchungen zu Neubabels-
by the Ensign-Bickford Co (Vol 3 of Encycl, bert (Central Laboratory for Scientific & Tech-
pp C530 & C531). Addnl info is given on pp nical Research at Neubabelsberg) as possible
D103 to D 106, under Detonating Cords or De- stabilizers for smokeless proplnts. Several for-
tonating Fuses mulations were developed which proved to be
1903. Accdg to Tavernier (Ref 44, p 252), very successful. A detaiIed description is given
Rottweil Fabrik of Germany proposed vaseline in Vol 2 of Encycl, pp Cl 26 to C140
with 1–2% Na bicarbonate as muzzle-flash 1906. Accdg to Gorst (Ref 71, pp 15–16, it
suppressor. This was replaced in 1907 by soap was proposed in Russia to use LA (Lead Azide)
or rosin in lieu of MF (Mercuric Fulminate) in com-
1903. Until this year no satisfactory antifreeze pound detonators with Tetryl and later with
for NG was found, and many industrialists pre- Ten (PETN). Much work on improvement of
ferred not to use any of those previously pro- LA detonators was done by Col A.A. Solonina.
posed, but let ordimry Dynamite be defrosted He also worked on detonators contg Lead
in winter. The disastrous expln of 1902 in Trinitroresorcinate, called in the US Lead
Greisenau Mine, Germany, took place during Styphnate (LSt)
defrosting of Dynamite and encouraged the 1906. After publication of Nauc~offs paper
renewal of research on antifreezes. In 1903 (See under 1905), W. Will proposed TeNDG
the SA de Poudres et Dynamites of France (Tetranitrodiglycerin) as an antifreeze, but it
introduced DNT and TNT as antifreezes. They never was used in Germany. It was used in
did not lower the fr p of NG sufficiently. The the US since 1912 (Vol 5, p D1 589-R)
Glycerin Dinitrate (GDN) proposed in 1903 by 1906. Accdg to Tavernier (Ref 44, p 252),
A. Mikolajczak in Gelatin Dynamite was not WASAG patented as muzzle flash suppressors,
very satisfactory because it lowered the strength organic salts (such as tartrate, oxalate or citrate
of Dynamites too much (Vol 5 of Encycl, p of sodium)
D1 589-L) 1906. Dr C. Claessen patented in Germany the
1904. The Dynamit AG of Germany proposed use of totally substituted ureas as stabilizers
DNCH (Dinitrochlorohy drin) as an antifreeze. in smokeless proplnts. These substances can
This compd was satisfactory, except that it be subdivided into derivs of sym-N,N’-diphenyl-
 /

H151

ureas and asym-N,N-diphenylureas. Some of 1909. Accdg to Colver (Ref 12, p 18), low-
them served as gelatinizes nitrated aromatic hydrocarbons, such as MN-
sym-N ,N’-Diphenylureas were investigated Naphthalene, MNBz & MNT started to be used
beginning in 1906 at the Central Laboratory in coal mining expls based on AN. This was
for Scientific and Technical Research at Neu- because of their stability and insensitivity to
babelsberg, near Berlin and named Centralizes. shock & to ignition
There were developed Nos 1, 2, 3, 4 and Butyl 1909. Accdg to Gorst (Ref 71, p 12), Russia
Centralizes, all good stabilizers for NC’s, es- started to use Trotil (TNT) for loading shells
pecially No 1. More detailed description is 1909. Silvered Vessel Test, devised by Sir
given in Vol 2 of Encycl, pp C 126-R to C 140-R Robertson for detn of stability of Cordite, was
asym-N,N-Diphenylureas, known now as d~scribed by F.L. Nathan in JSocChemInd
Acardites were described before WWI by J.P. ““:’ 28, 443 (1909), and briefly described by Reilly
Reudler in Rec 33, 49–55 (1914). We were (Ref 28a, p 81) and in Vol 1 of Encycl, p
able to describe them in detail because Dr Hans XXIV. It is also known as “Waltham Abbey
Walter, who worked with them during WWII Test”
in Germany, gave us some info which is not in 1909. Accdg to P. Tavernier (Ref 44, p 252),
the literature (See Vol 1 of Encycl, pp A7-R one of the greatest German discoveries was
to A9-L). Especially useful was Drs H & B Pulver ohne L6sung (POL), called in Fr Poudre
Walter’s help in description of Analytical Pro- saris dissolvent (psd) and in Engl Solventless
cedures (See Vol 1, pp A9-L to Al O-R). P. Powder (or Propellant). Its discovery was at-
Tavernier described Acardites in MP 38, pp tributed to Brunswig & Thieme, although many
307–08 & 329,(1956) other scientists contributed to development of
1906. Hexanitroazobenzene prepd by E. such proplnts
Grandmougin & H. Lehmann and recommended 1910. B. Flurscheim patented the prepn of
by T.L. Davis for use in boosters (Vol 1 of 2,3,4,6 -Tetranitroaniline, one of the most
Encycl, pp A649–A650) powerful expls. It was used during WWl by
1906. Adoption by French Navy for large ca- the Germans and Japanese (Vol 1 of Encycl,
liber cannons of poudre B Marine with 8% pp”A411 to A413)
amyl alcohol as stabilizer (poudre BAms) in 1910. Beginning in Ott, DPhA became the .
lieu of previously used BAm2. (Ref 44, p 249) only stabilizer used in French proplnts, but
1907. Adoption in 1906 by the French Navy there were supplies contg amyl alcohol and
of proplnt with 8% amyl alcohol stabilizer did one of the battleships, Libert6, had in 1911
not prevent the disastrous expln in 1907 of a fire resuhing in eXphI of poudre B(Am8) of
battleship 16na. As a result of this, previously 1906 vintage. The ship was partially destroyed
tested DPhA (diphenylamine) was approved as (Ref 44, p 249 & Ref 31a, p 308)
stabilizer of Naval cation proplnt, which be- 1910. Tetracene, described in Vol 6, p G169
came known as “poudre B(Bo)” (Ref 44, p 249) as Guanylnitrosaminoguanyl Tetrazene was
(See also Vol 1 of Encycl, p A395-L) first prepd by K.A. Hofmann et al. The most
1907. Vezio Vender of Italy patented as an extensive studies were done in 1931 by Rinken-
antifreeze for Dynamites, mixed glycerol esters, bach & Burton
such as Dinitroacetin with Dinitroformin [Ref: 1910–1911 & 1913. Dr C. Claessen developed
Ss 2, 21 & 195 (1907)] a procedure for prepn of solventless proplnts
1909. Ammonium Picrate (AmmPicr), Dunnite contg about 30% NC. In his process the
or Explosive D, was standardized in the US as slightly wetted blend of NC–NC, known as
a bursting charge for AP (Armor-Piercing) galette (cake), with some additives was fed
shells (Ref 64, p 2-3). Its prepn and properties between two rolls (heated to 85–95° by hot
are described in Ref 70, pp 136–39, where it water circulated in them) in order to obtain
is stated that AmmPicr was first prepd in 1841 the mass in the form of a sheet. This is
by Marchand and in 1869 used by Brugkre in called “lamination”. Then the sheet passed
admixture with K nitrate as a proplnt. Used thru a press to be drawn in the desired form.
as an HE after 1900 (See also 1841) In order to facilitate the prepn of such proplnts,
 H152

some low N content NC was included in the 17, 175 (1914)] . It proved to be the best
cake or about 570 of NM –Na oxalate was in- antifreeze for Dynamites and was found to
corporated. Aromatic nitrocompds with rep’s be suitable as a substitute for NG. Large
below 100°, such as DNT or TNT were also quantities of NGc were used in Germany
recommended. The 1st Ger solventless proplnt, during WWI. As an antifreeze it was used in
RPC/12, contd 70% of blend of NC’s, resulting mixts of 20/80 –NGc/NG (Vol 5 of Encycl,
in a N content of 11 .7%, NC 25 and 5% of p D 1590-L & R). Prepn and properties of
Centrality. It was made in large grains and, EGcDN are described in Vol 6, pp E259-R
since it was solventless, the time consuming to E278-L, under ETHYLENEGLYCOL DI-
operation of- solvent proplnts was not required. NITRATE
The proplnt was used in large caliber cannons 1912–1914. ‘Russian proplnts were based on
(Ref 44, pp 252-53) Pyrocollodion of Mendeleeff. They contd 1% of
After 1911. As a result of disastrous explosions DPhA stabilizer and were in the form of tubes
of battleships 16na (1907) and Libert6 (191 1), US proplnts were based on @roceUdose
it was decided to investigate various stabilizers introduced by Lt Bernadou. They contd 1%
besides DPhA, such as naphthalene, MNNaph- of DPhA and were usually multitubular in
thalene, carbazole and DPhNitrosamine. None form
of them proved to be better than DPhA (Ref Italian proplnt, manufd from 1896 at the
31a, p 309 & Ref 44, p 250) Royal Powder Factory at Liri was Solenite,
1912. Carbonit AC patented the following which was similar to Brit Cordite contg about
expls: Hexanitrodipheny lamine, Hexanitrodi- 35% of NG. It consisted of 1/3 Guncotton,
phenylsulfide, Hexanitrosulfobenzide, Hexa- 1/3 Collodion Cotton and 1/3 NG with added
nitrodiphenyloxide and Hexanitrodiphenyl vaseline (replaced later by Centrality), Be-
(Ref 12, pp 25 & 26) ginning in 1910, the Soci6t6 Nobel of Avig-
1912. Accdg to E.M. Symmes (translator of liona manufd C2, which was a variety of
Naofim’s book), DGTeN (Diglycerin Tetra- Brit Cordites but in the form of tubes. Italians /
nit rate) introduced in 1906 by W. Will as an manufd also Ballistite of high NG content
antifreeze was not used in Germany, but it which contd 0.5% of aniline as stabilizer (Ref
was used in the USA to a very large extent 44, p 253)
until about 1926 (See footnote 5 on p 202 1913. Compression (or Crusher) Test of Kast
of Ref 16 and in Vol 5 of Encycl, under is described in Vol 3 of Encycl, p C493
Diglycerol, p D 1261-L) 1913. A.S. Flexer of Vienna patented a pro-
1912. Modified British Cordite MD used in cess for manuf of nitrocompds from petroleum
rifles, changed its form from cords to small and tar but they found no practical application
tubes (Ref 44, p 253) at that time (Ref 12, pp 27–28)
1912. TNT, first prepd in 1891 (qv) by G. 1913. WestfNisch-Anhaltische Sprengstoff AG
Hdussermann and adopted in 1902 by the (WASAG) devised solventless proplnts with
Germans, in 1907 by the Italians and in 1909 low NG content in which stabilizers-plasticizers
by the Russians. It began in 1902 in the US were anilides of org acids in which hydrogen
to replace PA, and then in 1912 became the of imide group was replaced by a radical:
standard bursting charge for HE shell for the ethyl or methyl acetanilide. The same Society
mobile artillery of the US Army (Ref 64, p proposed using esters of carbonic acid in which
2-4 and Ref 70, pp 350–58) two hydrogens were replaced by radicals, such
1912. Nitroisobutylglycerol Trinitrate or as diphenylurethane or methylphenylurethane.
Trimethylolnitromethane Trinitrate was first This permitted reducing the temp of lamination
prepd by Hofwimmer. Used as expl gelatinize to 82° (Ref 44, pp 25 1–52)
for NC (Ref 70, pp 244 & 245) 1914. Lead Styphnate (LSt) or Trinitroresor-
1912 & 1914. Although Nitroglycol (NGc) or cinol was first prepd by E. von Herz (Ref 70,
Ethyleneglycol Dinitrate (EGcDN) was known pp 193–96)
since 1904, it was not properly described 1914. G. Spica of Italy proposed using phen-
until before WWI [See MP 16, 73 (1912) and anthrene as stabilizer in solventless proplnts
 H153

with low NC content (Ref 44, p 254) this section under the years 431–404BC
1914. Cordite SC, Solventless was developed 1915. Dr C. Claessen patented in Germany a
at Waltham Abbey, England (Vol 3 of Encycl, smokeless proplnt with volatile solvent, stabi-
p C532-R) lized by introducing a large quantity of eutectic
1914. Trotyl (TNT) started to replace in mixt DNT–TNT (Ref 44, p 251)
France MfJinite (PA) as bursting charge 1915. Amatols (TNT+AN) were developed by
1914–1918. World War 1. Prior and during the British in order to extend the available
the War many explosives, serving as substitutes supply of TNT which was scarce (Vol 1 of
or supplements of TNT, were developed in Encycl, p Al 58)
Germany, Austria, Russia, Italy and Great 1916. Dr C. Claessen patented solventless
Britain. The most important were mixtures NC–NC proplnt contg alcylaryl- or diary l-
of HE’S (such as TNT, TNX, TNN and others) cyanarnides as stabilizers (Ref 44, p 251)
with AN and Al were: Amatols (British) (TNT 1916. Ballistite 50/50, invented by Nobel,
with AN in various propns) (Vol 1 of Encycl, was manufd as proplnt for mortars. It was
pp Al 58 to A164); Ammonals (Austrian & US) partially replaced by Attenuated Ballistite,
(TNT or other HE with AN& Al) (Vol 1 of which contd 25% NC and 15% DNT. The
Encycl, pp A287 to A292) and Alumatol German name, Wurfelpulver (W), was assigned
(British) consisting of AN 77, TNT 20 & Al to Ballistite 50/50 used in mortars (Ref 44,
3%, used for filliig bombs and trench mortar p 252)
shells (Vol 1, pp A141-R & A142-L). In Russia 1916-1917. Single base NC proplnts were used in
Col A.A. Solonina proposed using mixt of rifles and in the shape of tubes in some cannons.
Trinitro-m-xylene (Ksilil, in Rus) with AN & As gelatinize for such proplnt an ether-ale mix-
Al for loading hand grenades (Ref71, p 14) ture ‘was often used, and as stabilizer diphenyl-
WWI. Incendiary bombs developed at that amine (DPhA). Some NC–NG proplnts, gela-
period were not very effective and compara- tinized by acetone, contd small amts of organic
tively easy to extinguish (Vol 2, p B243-R) nitrates. As stabilizer they used DPhA and
1915, April 22. Modern Chemical Warfare later Centrality or Acardite. They were surface-
began with the German attack at Ypres, France, treated by Centrality or by aromatic nitrocompds.
when 5700 barrels of chlorine gas were released Such NC-NG proplnts were used in large cali-
against French and Canadian trenches. The ber cannons (Ref 44, p 252)
attack was most effective because it was unex- 1917. Austrian Ammonal T was developed by
pected and many casualties resulted. This R. Fbrg to be used in underwater expls, such
“gas-cloud method” was soon replaced by as torpedoes and depth charges. It consisted
“&emical shells” which were widely used of AN, Al & TNT (Vol 1 of Encycl, p A291 -L
during WWI. Although “chemical warfare” & table on p A290)
was outlawed after WWI by the Hague Con- 1917. Accdg to Tavernier (Ref 44, p 252),
vention, all great nations continued develop- WASAG patented as muzzle flash suppressor
ment of new agents. The most efficient was K chloride (0.5 to 5g)
Germany who developed before WWII several 1917. Ardeer Cordite was introduced (Vol 3
“nerve gases”, such as Trilons described in of Encycl, p C532-R)
PATR 2510 (1 958), p Ger 204-L and in Vol After WWI. Metriol Trinitrate or Trimethylol-
2 of Encycl as GA & GB on p C167-R. They methane Trinitrate was prepd in Italy and in
are also described in Vol 5, pp D 1308-R to 1927 in Germany. Used as an ingredient of
D1 309-L, under Dimethylaminocyanophos- rocket proplnts (Ref 70, pp 206–08). Its
phoric Acid, Monomethyl Ether. A compre- prepn and uses in Germany during WWII are
hensive list of chemical warfare agents de- described in PATR 2510 (1958), p Ger 113
veloped during WWI & WWI1 by various countrie s 1920. Accdg to Davis (Ref 31a, pp 31 1–13),
is given in Vol 2 of Encycl, pp C166 to Cl 73, transformation of DPhA during aging was con-
under “Chemical Warfare Agents” ducted beginning in 1920 by Desmaroux,
A brief description of the use of poisonous Marqueyrol & Muraour and Marqueyrol &
and smoke gasesin ancient times is given in Loriette; also by Davis & Ashdown (See also
 H 154

Vol 5 of Encycl, pp D1417-R to D1418-L) (1965) and a briefer description in Vol 5 of

1920. ,Cardox is a device for breaking coal in Encycl, pp D1 232 & D1 233-L (See also Ref
gaseous mines by the pressure,produced on 49, p 168)
heating liquefied carbon dioxide. It is briefly 1927. Trimethyleneglycol was first described
described in Vol 2 of Encycl, p C67-R. Simil- by A. Rayner, but it was mentioned in 1895 “
ar devices, Airdox and Armstrong Air Breaker, by Noyes & Watkins as occurring in some
were developed in, 1930 in the US. More glycerols (Ref 49, pp 206& 209) ‘
successful were Hydrox developed in 1955 1928. B. Fliirscheim & E. Holrns prepd
and Chemecol developed by du Pent Co be- 2,3,4,5 ,6-Pentanitroaniline in the pure state
fore 1958. They are also Hydraulic Coal and found it to be a most powerful expl,
Bursters (See Vol 3 of Encycl, p C434) comparable to RDX & PETN. It was stable
1921. It was known that some stabilizers while the same‘expl prepd in 1910 in impure
act also as gebtinizers or colliding agents state was unstable (Vol 1 of Encycl, p A414)
Davis (Ref 31a, pp 320–22), under the title 1928. Nitraminoguanidine and Its Salts were
“Gelatinizing Agents”, describes results of in- prepd by R. Phillips & J.W. Williams (Vol 1
vestigation in France beginning in 1921 by of Encycl, pp A21O-R to A21 2-L and A213-R
Marqueyrol & Florentin of a number of esters, 1929. PVN (polyvinyl Nitrate) was first prepd
amides, urea derivatives, halogen compds, ke- in Germany and patented in 1938 in the US.
tones and alcohols as possible gelatinizes of Its uses are not indicated (Ref 70, pp 3 15–17)
soluble and insoluble NC. In 1922, Davis in- 1929. Accdg to Dutton (Ref 58, p 174),
vestigated many compds and gave in his book the first cyclotron was built in the USA
on p 322, a Table listing parts by wt required 1929. Copper Chlorotetrazole first prepd by
for complete gelatinization of Pyrocellulose
(See also Vol 3 of Encycl, p C398-L, under
R. Stol16 et al. More recently (1955), it was
prepd and investigated at PicArsn as possible
J
the title “Colliding Agents”) ~ng~edient of pr~ary compns (Ref 70, pp 63
1923. 0. Turek prepd 1,3,5-Triazido-2,4,6- to 65)
trinitrobenzene and described its prepn and 1930. Dipentaerythritol Hexanitrate (DPEHN),
properties in Chim&Ind(Paris) 26, 781 (1931) obtd as impurity in PETN by W. Friederich &
(See Vol 2 of Encycl, pp B43 & B44) W. Brun was also prepd in 1945 at PicArsn by
1923. W. Borsche, Ber 56B, 1942, described S. Livingston and at Hercules Powder Co Lab
1,3,4,5- & 1,2,4,5-Tetranitrobenzenes, both of at Radford, Va (Ref 70, pp 119–21 and Vol 5
them very expl (See also Vol 2 of Encycl, p of Encycl, p D1413)
B50 and Ref 70, pp 378–80) 1930-1931. Lead Azide, Dextrinated started
1925. R.C. Moran prepd 2-(2’,4’,6’-Trinitro- to be used in the US, replacing gradually M,F
N-nitranilino)-Ethanol Nitrate, also known as (Mercuric Fulminate) in priming compns (Vol
Pentryl. Not to be confused with Pentryl of 1 of Encycl, pp A545-R and A552-L). Plain,
A. Stettbacher, which designates mixts of PETN impure LA was first prepd in 1891 by T. Cur-
& TNT known in the US as Pentolites (See Vol tius, but it was not until 1907 when T. Hero-
1 of Encycl, pp A425–29 and Ref 31a, p 229) nius of France succeeded in using it in explo-
1927. Continuous Methods of Manufacture of sives industry. It started to be used in 1920
Explosives. The first successful method was in Europe, but in the US only dextrinated LA
invented by Schmid of Austria, but some at- was allowed beginning 1930–3 1 (Ref 70, p 185)
tempts were made as early as 1864. De- 1931. Propyleneglycol, although first prepd in
scription, with flow sheets is given in Vol 3 1859 by Ch.A. Wurtz, it was not used until..
of Encycl, pp C501 to C510 for the methods 1931 when it was produced on commercial
of Schmid, Biazzi, German and Bofors scale by Carbide & Carbon Co (Ref 49, p 203)
1927. Diethyleneglycol Din,itrate was thorough- 1931. Glycerol Monolactate Trinitrate, patented
ly examined by W.H. Rinkenbach and its cur- in the US by Ch. Stine & Ch. Burke, was in-
rent method of prepn was patented in 1928 by vestigated in 1946 at PicArsn as possible expl
A. Hough. A detailed description is given in plasticizer for NC (Ref 70, pp 140–42)
the book of T. Urbaiiski, Vol 2, pp 149–54 1931. 2,4-Dinitrotoluene (2,4-DNT) obtd
 H 155

earlier as an impurity in crude TNT, was used for use in JATOS were developed beginning 1940
in some expl mixtures (Ref 70, pp 116–18) (Vol 3 of Encycl, pp C464-C474)
1933. Anilinotetrazole and Its Derivatives 1941. R.C. Elderfield prepd N-(2,4,6-Trinitro-
were first prepd by R. Stoll~ et al (Vol 1 of N-nitranilino)-Trimethylolmethane Trinitrate, de-
Encycl, p A437-R) signated as Heptryl, and called by G.B. Kistia-
1933. Pentrinit is a mixture of 20–50% of kowsky N-Nitro-N-picryl-trimethylobnethyl-
PETN with 80–50% NC. It was developed by amine Trinitrate. It proved to “be HE compar-
A. Stettbacher (Ref 41, pp 83–4) able in power and sensitivity to PETN (Vol 1
1933. Hexonit is a mixt of 20–50% RDX of Encycl, pp A441 -R & A442-L)
with 80–20% NC. It was developed by A. 1941. Lead Nitraminoguanidine was prepd and
Stettbacher (Ref 46, p 111) examined at Picatinny Arsenal by A.J. Phillips.
1934. Lead-2,4dinitroresorcinate was prepd It was later recommended by L.R.V. Clark for
and exarqined at PicArsn by J.D. Hopper and use in primers and detonators (Vol 1 of Encycl,
later (1944) by K.S. Warren (Ref 70, pp 187-89) pp A212-R & A213)
1934–1935. “G” Pulver. This proplnt was de- Prior to WWII Cartridge-Actuated Devices
veloped in Germany under the direction of (CAD’s) or Propellant Actuated Devices. The
Gen Uto Gallwitz. It was a “cool” double- first successful devices for pilot’s quick escape
base proplnt in which NC was replaced by from a plane were developed by the Germans.
DEGcDN or TEGcDN (Vol 3 of Encycl, p They called them “Schleudersitzpatronen” and
C400-R and pp C511 & C512) equipped them in many of their fighter planes.
1935. Ball Powder was developed by Fred The British equipped their planes having speeds
Olsen of Olin Mathieson Chemical Corp (Vol greater than 400mph with such devices begin-
2 of Encyclj pp B11–B16) ning in 1945. The Americans started the study
1935. Accdg to Dutton (Ref 58, p 143), the of emergency escape as early as 1940, but it
World’s largest Dynamite Plant was const rutted was not until 1947 that the first device was
near Modderfontein, South Africa. It was standardized. It was named “MI Personnel
operated by the African Explosive and Chemi- Catapult” (Vol 2 of Encycl, pp C70 to C72)
cal Industries Prior to WWlI. Composition B or Cyclotol,
1936. Pentaerythritol Trinitrate or PETRIN. developed by the British, consisted of a mixture
Nitration products of PETN contg not more of RDX with TNT in various proportions. Some
than 3-N02 groups were patented in Germany mixts contd wax. Its modifications as standard-
in 1936, but pure PETRIN was not prepd until ized during WWII in the US were: Compositions
1954 (Ref 70, pp 265–68) B–2; B–3; B4 and B. Desensitized (Vol 3 of
Encycl, pp C477-R to C484-L) (Ref 70, pp 46–50)
1937. Baratol, which is the mixture of Ba
nitrate and TNT (Tel), was developed by the Prior to WWII. Under Dimethylarninocyano-
British and used during WWH (Vol 2 of Encycl, phosphoric Acid, Monomethyl Ester are described
ppB18&B19) in Vol 5 of Encycl, pp D 1308-R to D1 309-R
1937. Gudolpulver was a “cool” proplnt de- German Nerve Gases, such as Sarin, Tabun, Triion
veloped in Germany by Dynamit AC Plant. It and Soman. They are also described in PATR
consisted of NC, DEGcDN & NGu (Nitro- 2510 (1958), p Ger 204-L, under Trilons
guanidine) (Vol 3 of Encycl, p C401 -L) Prior to WWlI. Cyclotols, which are mixtures of
1939. This year may be considered as the be- Cyclonite (RDX) with TNT in various propor-
ginning of work on development in the US of tions were developed by the British and standard-
atomic (or nuclear) energy. This work is ized in the US (Ref 70, pp 76–85) and Vol 3
briefly described by C.G. Dunkle in Vol 1 of of Encycl, pp C477-R to C484-L under Compo-
Encycl, pp A500ff sition B Type Explosives and Cyclotols)
1940. Composite Propellants, consist of finely Prior to WWII I were developed in Switzerland
ground oxidizer (such as inorg perchlorate or and Germany extremely toxic nerve gases, de-
nitrate) in a matrix of a resinous or elastome- scribed under Trilons in Ref 56, p Ger 204-L
t ric material which serves as a fuel. The proplnts WWll. Items Developed or Standardized During
 H 156

WWll. Ethylenedinitramine, EDNA or Haleite, Amer expl developed to replace the Brit more
first prepd in 1887 by Franchimont & Kiobbie sensitive Torpex (Vol 3 of Encycl, p D19-L
and developed in 1935 as a military explosive and Ref 70, pp 91 to 94)
by G.C. Hale,. was sta!ldardized during WWII WWII. Lead-4,6-dinitroresorcinol, Basic was
as a component of EDNATOL (EDNA+TNT) prepd by the British for use in electric detona-
serving as bursting charge for bombs and shells tors (Ref 70, pp 190 to 192)
(Ref 70, pp 131-R and 154). See also Vol 6 WWII. Nipolits are types of NC–DEGDN–
of Encycl, pp E238ff PETN propellants or expls patented by Dr
WWII. EDNATOL (EDNA 55 & TNT 45%). E. von Holt, the inventor of Holtex (See
See previous item and Ref 64, pp 7-74 & 7-75 under year 1958). Compns and some props
and Ref 70, pp 130–32) of Nipoiits are listed in PATR 2510 (1958),
WWII 1. Cyclotetramethy lene Tetranitramine or p Ger 117
Homocyclonite (Code named HMX, which WWII. Bombs, Incendiary were very efficient
means “High Melting Explosive), was prepd and hard to extinguish. They did more damage
in 1943 by W.E. Bachmann (OSRD Rept 1981) to. the buildings than did, other bombs. A brief
and investigated at PicArsn by S. Livingston and description of such bombs and the damage in-
O.E. Sheffield, et al (Ref 64, pp 7-64 to 7-66 flicted by them during WWIi is given in Vol 2
and Ref 70, pp 173–77) of Encycl, pp B235 to B237
V–1 (Buzz Bomb) is described in Ref 56, p WWII. Composition A, developed by the Bri-
Ger 213-L tish, consisted of RDX 9 ~ & beeswax 9%. When
V-2 (Rocket) is described in Ref 56, p Ger standardized in US, beeswax was replaced by
213-R synthetic wax and the expl became Composi-
WWII. Pentolites, of which 50/50–PETN/TNT tion A-2. Other modifications were Compo-
mixture is the most important, was standardized sitions A-3; A-4 and A-5 (Vol 3 of Encycl, pp
for use in shaped charges, bursting charges and C474 to C477)
demolition blocks (Ref 64, pp 7-69 to 7-71 WWlI. Composition C, developed by the British,
and Ref 70, pp 272–75) was a plastic RDX demolition expl. As stan-
WWII. Tetrytols, of which 70/30–Tetryl/TNT, dardked in the US, it consisted of RDX 88.3
castable mixture is the most important in mili- & a nonexplosive plasticizer 11.7%. Its other
tary applications. It was standardized for use modifications were Comp C-2; C-3 and C-4.
in burster type of chemical sheik and in de- The C-4, known as Harrisite, was developed be-
molition blocks (Ref 64, p 7-72 and Ref 70, fore 1950 by K.G. Ottoson at Picatinny Arsenal.
.pp 341–49) Their compns are given in Vol 3 of Encycl, pp
WWII. Picratol (PA 52 & TNT 48%) was de- C484 to C488
veloped as insensitive, castable filler for AP WWII. Azon Guided Missile, developed during
bombs and shells (Ref 64, pp 7-72 to 7-74 the War, is briefly described in Vol 1 of Encycl,
and Ref 70, pp 285 to 287) p A662-R
WWII. Torpex (RDX 42, TNT 40 & Al 18%) WWII. Bangalore Torpedoes were developed
developed by the British for use as a filler of and are described in Vol 2 of Encycl,’ pp B16–
warheads, mines and torpedoes (Ref 64, pp 7-77 B18
& 7-78 and Ref 70, pp 259 to 263) WWII. Baronal, consisting of Ba nitrate, TNT
WWII. HBX–I (High Blast Explosive–l) is a & Al, was described in 1942 in OSRD Rept
modification of Torpex. its compn & props 1035 (Vol 2 of Encycl, pp B21 & B22)
are given on p 7-79 of Ref 64 and in this Vol WWII. Cast Double-Base Propellants for Rockets,
of Encycl (See also Ref 70, pp 156 to 158) developed at the beginning of 1944 are described
WWII. Demolition Explosives and Cratering in Vol 2 of Encycl, pp C84 to C86
Charge are described in Vol 3 of Encycl, pp WWII. Flashless Cordite contg NGu (Nitro-
D54 to D61. Se also Ref 64, pp 7-84 & 7-85 guanidine) was adopted as the best, after in-
WWII. Military Dynamites are described in vestigation beginning in 1921, of various addi-
Ref 64 p 7-84 tives to Cordites (Vol 3 of Encycl, p C533
WWII. DBX (Depth Bomb Explosive) is an and Ref 30, p C536-L)
 H 157

WWII. Cyclotetramethylenetetranitramine, WWlI. PTX–1 (Picatinny Ternary Explosive)

called HMX by the British and also known as is a eutectic mixt of RDX 30, Tetryl 50 &
Octogen was described in OSRD Rept 652 TNT 20%. It was developed in 1943 at PicArsn
(1942) and in Vol 3 of Encycl, pp C605-R and used in land mines and demolition charges
to C61O (Ref 70, pp 306 to 308)
WWIl. RDX or Cyclonite. See 1899. C yclo- WWII. PTX-2 consisted of RDX 44–41,
trimethylenetrinitramine PETN 28–26 & TNT 28–33%, developed in
WWII. Demolition Explosives. Wide use was 1943 at PicArsn and used in shaped charges (Ref
made in demolition practice of shaped charges, 70, pp 309to 311)
which utilize the Munroe-Neumann Effect, de- WWII PVA-4 (Polyvinyl Acetate–4) is a semi-
scribed in Vol 4 of Encycl, pp D442 to D443. plastic expl contg RDX 90, polyvinyl acetate 8
US demolition shaped charges are described in & DBuPh 2%. It was developed inCanada and
Vol 3 of Encycl, p D58, while US plain de- used in demolition charges. (Ref 70, pp 312 to
molition charges are on p D57. British, French, 315)
German, Japanese and Russian charges are on WWII. RIPE. Mixture of RDX 85 & Gulf Crown
pp D58 to D60 E Oil 15%; developed in the US as a plastic de-
WWII. Depth Charges are described in Vol 3, molition expl (Ref 70, pp 3 18– 19)
pp D86 & D87 WWII. Hybrid Rocket ‘Propellants are described
WWII. Destructors are described in Vol 3, pp in this Vol
D92 to D96 WWII. PH–Salz (Ethylenediamine Dinitrate)
WWII. Detonating Cords or Detonating Fuses was used by the GErmans in mixts with AN
are briefly described in Vol 3, pp D103 to and other ingredients for filling some shells
D106 (See also 1902. Cordeau d6tonant) (Ref 56, p Ger 131)
WWII. Shaped Charge Effect, discovered in 1888 1945. This year there were completed the first
by C.E. Munro and applied in 1910 to manuf of three atomic (or nuclear) bombs. The first bomb
expl items by E. Neumann, was “extensively was successfully exploded in the New Mexico
utilized during the war. The effect is described desert on July 16, 1945, and a second over Hiro-
under Detonation, Munroe-Neumann Effect in shima, Japan on Aug 6, 1945, and the third over
Vol 4 of Encycl, pp D442 to D454 Nagasaki on Aug 9, 1945. The bombs were of
WWII. Triethyleneglyml Dinitrate was .prepd Fission Type and of tens of kilotons (thousands
in Italy and then in Germany for use in “cool” of tons of TNT equivalent) (Vol 1 of Encycl, p
double-base proplnts, “G” Pulvern, of Gen. U. A499-L)
Gallwitz intended for hot climates like N. Africa. 1945. PLX (Picatinny Liquid Explosive) con-
It was also used as proplnt in the “Nebelwerfer” sisting of Nitromethane 95 & Ethylenedinitramine
(Ref 49, p 176 & Ref 70, pp 368-69) 5% was developed at PicArsn by L.H. Eriksen &
WWII. H-6 is a HE consisting of RDX 45, J.W. Rowen for use in mipefield clearing (Ref
TNT 30, Al 20 & D2 Wax 5% with 0.5% Ca 70, pp 298 to 301)
chloride added (Ref 70, pp 146 to 148) (See Note: Germans used during WWII similar liquid
also in this Vol of Encycl, p HI-L) expls under the name of Myrol, which are de-
WWlI. HMX (High Melting Explosive) is listed scribed in PATR 2510 (1958), pp Ger 115 &
as Cyclotrimethylene Tetranitramine Ger 116
WWII. Minol-2, Brit expl contg TNT 40, AN 1945. Tripentaerythritol Octanitrate was pa-
40 & Al 20% developed for use in depth bombs tented by J.A. Wyler of Trojan Powder Co,
(Ref 70, pp 209 to 212) Allentown, Penna. It was used as an HE and
WWlI. Trimonite. A castable mixt of PA 88– as possible gelatinize for NC (Ref 70, pp 382
90 & MNNaphthalene 12– 10% developed by the to 384)
British as an improvement over Tridite (PA 80 After WWlI. Composition D–2 which is not an
& DNPhenol 20%0). Used as TNT substitute in expl, but serves as an emulsifier and desensitizer
bombs and shells (Ref 70, pp 370 to 372) of expls like HBX–1, consists of wax 84, leci-
WWIl. PIPE is a mixture of PETN 81 and Gulf thin 2 & NC 14% (Vol 3 of Encycl, p C488-R) 4
Crown E Oil (Ref 70, pp 294 to 295) Compositions EL-387A and E L-367B, de-
 H158

veloped by the dupont Co, were slurry expls of 1957. Veltex is the name given to a series of
compns given in Vol 3 of Encycl, pp C488-R closely related NC compns prepd in 1957 at
& C489-L PicArsn by the solventless provess. They all
1848. The first Fusion Type Atomic Bomb contain a high percentage of solid HE. Hispano-
(also known as Hydrogen Bomb, H–Bomb or Suiza Co investigated them to determine their
Thermonuclear Bomb) was tested at Eniwetock suitability as Holtex type expls (See year 1958).
and proved to be successful. The bomb was of Veltex expls are proposed for use as high mechani-
several megatons (millions of tons of TNT cal strength machinable expls. Compn of Veltex
equivalent) (Vol 1 of Encycl, p A499-L & R) No 448 is: NC (13.15% N) 15.0, HMX 70.0,
1950. MOX (Metal Oxidizer Explosives) were de- NC 10.7, 2-NitroDPhA 1.3 & Triacetin 3.0%
veloped by National Northern, technical division (Ref 70, pp 391 to 394)
of the National Fireworks Ordnance Corp, West 1958. MASER and LASER. Accdg to “Time”
Hanover, Massachusetts, for use mostly in small magazine of July 12, 1968, pp 42—9, physicists
caliber antiaircraft shells. Their compns and props A. Schawlon & C. Townes described in 1958 a
are described in Ref 70, pp 213 to 225 device which was a variation of Townes earlier
1950. Trinitroethyl Trinitrobutyrate seems to Nobel prizewinning invention named MASER.
have been first prepd at NavOrdLab and then at The first working model of this device was built
Hercules and US Rubber Labs. It is a high in 1960 by physicist Maiman, who named it
oxygen content expl (Ref 70, pp 375 to 377) RUBY LASER. A brief description of these
1951. Ethylenegiycol Di(trinitrobutyrate) was and later developed devices is given in Vol 4
prepd at the US Rubber Co Lab, Passaic, New of Encycl, pp D436 to D440, compiled by C.G.
Jersey (Ref 70, pp 133 to 135) Dunkle, formerly of Picatinny Arsenal
1952, Dynamite, Medium Velocity, Military 1958. HTA–3 (High Temperature Explosive),
was developed by W.R. Baldwin, Jr at Hercules consting of RDX 49, TNT 29 & Al 2270, was
Powder Co Lab (Ref 70, pp 125 to 127) prepd at PicArsn by R. Brown & R. Velicky
1952. 2,2-Dinitropropy l-4,4,4-trinitrobuty rate (Ref 70, pp 178 to 181). See also in this Vol
was prepd by M.E. Hill at NavOrdLab (Ref 70, 1958. Octols 70/30 and 75/25 are mixts of HMX
pp 113 to 115) and TNT developed at Northern Corp as fillers
1952. Bis-(2,2-Dinitropropyl)-fumarate was for bombs and shells (Ref 70, pp 249 to 258)
prepd by M.E. Hill at NavOrdLab and in 1954 1958. Holtex was patented by Dr E. von Holt
by D.L. Kouba & H.D. McNeil of Hercules . of Hispano-Suiza Co, who died in 1962 in an
Powder Co (Ref 70, pp 107 to 109) automobile accident. Holt ex has several formu-
1952. PB–RDX (Plastic-Bonded RDX) was de- lations which are listed in Vol 3 of Encycl, pp
veloped by Los Alamos Scientific Laboratory of C396-L to C397-L
the University of California for use as a mechanical Ref Dr H. Freiwald of Saint Louis Laboratory,
strength expl. It consisted of RDX 90, poly- Germany; private communication, 12 Sept 1962
styrene 8.5 & dioctylphthalate 1.5% (Ref 70, Able.’ See,also in Vol 3 of Encycl, pp C396-L ff
pp 259 to 264) 1960. Detaclad Process or Explosive Cladding,
1953. Bis-(2,2-Dinitropropyl)-succinate was prepd also called Explosive Bonding was developed by
by M.E. Hill of NavOrdLab (Ref 70, pp 110 to the duPont Co (See Vol 3 of Encycl, pp D96 &
112) D97)
1953. HEX (High Energy Explosives) developed 1960. Detacord, Detaflex Flexible Cord Explo-
at PicArsn are described in Ref 70, pp 164 to sive and Detasheet Flexible Cord Explosives were
169 and in this Vol, p H73-L developed by the duPont Co (See Vol 3 of Encycl,
1956. Pentaerythritol Tetranitroacrylate or pp D97 to DIO1)
PETRIN Acrylate) was developed by Rohm and 1967. Accdg to Nambo (Ref 66, p 39), the
Haas Co, Redstone Arsenal Division (Ref 70, mining BkPdr of Nippon Kayaku Co, Ltd contd:
pp 269 ?0 271) saltpeter 64, sulfur 18 & charcoal 1870, while its
1957. Dynamite, Low Velocity, Military was sporting BkPdr contd: saltpeter 75.0, sulfur
developed at PicArsn by H.W. Voigt (Ref 70, 12.5 & charcoal 12.5%
pp 122 to 124) 1972. Accdg to Gorst (Ref 71, p 173), the
 H 159

average.compn of Russian Black Powder (called Army Ordnance Pamphlet (1920) (Available at ‘
[ “Dymny Porokh”, which means Smoke Powder) PicArsn Museum)
is saltpeter (mostly of K) 75, sulfur 10 & char- 14) A.P. Van Gelder & H. Schlatter, “History of
coal 1570 the Explosives Industry in America”, Columbia
Univ Press, NY (1927), pp 3ff (History of BkPdr
Refs for History of Explosives arrd Related Items: in the USA)
1) M. .Mhns, “Handbuch einer Geschichte des 15) P. Charbonnier, M6mArtilFran 7, 1227
Kriegswesen von der Urzeit bis zur Renaissance”, (1927 )!(Artillery)
Leipzig (1880) 16) Ph. Naotim, “Nitroglycerine and Nitrogly-
2) W.W. Greener, “The Gun and Its Development”, cerine Explosives” (Translated from Ger by E.M.
Cassell, Petter& Co, 1st Edn, London (1881); Symmes), The Williams & Wilkins Co, Baltimore
9th edn (1910) (See Ref 7) (1928), pp 1 to 22 (Discovery and Historical
2a) S.G. Romocki, “Geschichte der Explosivstoffe”, Review)
Berlin & Hanover, Vol 1 (1895) & Vol 2 (1 896) 16a) H. Desvergnes, ArmyOrdn 10, 191–94
2b) Lt J.B. Bernadou, “Smokeless Powder, Nitro- (1929) (History of development of military
cellulose and Theory of Cellulose Molecules”, powders)
J. Wiley, NY (1901) and 2nd Edn (1917) 17) L. Vermin, E. Burlot & H. Lecorch6, “Les
3) J. Daniel, “Dictionnaire des Mati&es Explo- Poudres et Explosifs”, Ch. B6ranger, Paris (1932)
sives”, Dunod, Paris (1902) (A brief history of (No history is described)
explosives is given by M. Berthelot in “Pr6face”, 18) P. Charbonnier, M6mArtilFran 11, ler, 2~me,
pp I to x, incl) 3sme & 4~me Fascicules (1932) (Artillery)
4) Col H.W.L. Hime, “Gunpowder and Ammuni- 19) E. McFarland, “Textbook of Ordnance and
tion”, Longmans, Green & Co, London (1904) Gunnery”, J. Wiley, NY (1932)
5) Sir Andrew Noble, “Artillery and Explosives”, 20) Marshall 3 (1932), 1–2 (Early History);
Dutton Co, NY (1906) 3–5 (Development of Gunpowder); 6–8 (Pro-
6) R. Escales, “Schwarzpulver und Sprengsal- gress of Explosives in the Eighteenth and Nine-
peter”, Veil & Co, Leipzig (1910) teenth Centuries)
7) W.W. Greener, “The Gun and Its Develop- 21) A. Stettbacher, “Schiess- und Sprengstoffe”,
ment”, Bonanza Books, M, 9th Edn (1910), J.A. Barth, Leipzig (1933), pp 3–18 (Geschicht-
Chap I, “Early Arms”; Chap II, “The Invention licher ~erblick)
of Gunpowder”; Chap 111,“Early Artillery”; 22) T. Urbaiiski, M;mArtilFran 13, 825–42
Chap .IV, “Early Hand Fire-Arms”; and Chap V, (1934) (Le centenaire de la nitrocellulose)
“The Percussion System” (The book is available 23) G.C. Stone, “A glossary of Construction,
from Publishers Central Bureau, 33-20 Hunters Decoration and Use. of Arms and Armor in All
Point Ave, Long Island City, NY 11 101) Countries and in All Times, Together With Some
8) P.F. Chalon, “Explosifs Modernes”, Ch. Closely Related Subjects”, J. Brussel, NY (1934)
B6ranger, Paris (191 1), 228 (Over 3000 illustrations from the Stone Age to
9) G.W. MacDonald, “Historical Papers on Mo- WWH – an exhaustive alphabetical listing and
dern Explosives”, Whittaker, London (1912) description of 10000 kinds of arms and armor
10) Col H.W.L. Hime, “The Origin of Artillery”, thruout recorded history, in a 700pp.volume)
Longmans, Green & Co, London & NY (191 5), (Available from Publishers Central Bureau, Dept
pp 120, 127 & 231 353, 33-20 Hunters Point Ave, Long Island City,
11) Marshall 1 (1917), 11–22 (Early History), NY 11101)
12–34 (Development of Gunpowder); 35–50 24) A. Basset, M6mArtilFran 13, 529–78 (1934)
(Progress of Explosives in the Eighteenth and (Bibliography on Artillery; more than 1000 refs
Nineteenth Centuries) are listed)
12) Capt E. de W.S. Colver, “High Explosives”, 25) A. Basset, M6mArtilFran 14, 881–1280(1935)
Van Nostrand Co, NY (19 18), pp 1–29 (History (Essais sur l’histoirique,des fabrications d’arme-
of High Explosives); 496–501 (History of HE ment en France)
Projectiles); 501–05 (History of Shell Fuzes); 26) J. Pepin Lehalleur, “Trait6 des Poudres,
563–64 (History of Fuses) Explosifs et Artifices”, Bailli&e, Paris (1935),
13) Anon, “History of Trench Warfare Materiel”, 15–1 9 (Historique du di%eloppment de la pyro-
technic)
 H 160

27) C. Beyling &K. Drekopf, “Sprengstoffe und Rascher, Zurich (1948), 1–5 (Geschichtlicher
Zundmittel”, J. Springer, Berlin (1936), 1–5 ~erblick)
(Geschichtliches) 42) A.D, Blinov, “Kurs Artillerii’ (Artillery
28) T.J. Hayes, “Elements of Ordnance”, J. Course), Voyenizdat, Moscow, Vols 1 to 12
Wiley, NY (1938) (No specific pages for history) (1948–1952) (Available in the Library of
28a) J. Reilly, “Explosives, Matches and Fire- Congress)
works”, VanNostrand, NY (1938) (Describes 43) Albert Manucy, “Artillery Through the
various physical & expl tests) Ages”, US Govt Printing Oft, Washington, DC
29) V. Muthesius, “Zur Geschichte des Spreng- (1949) (National Park Serv Series History No 3)
stoffe und des Pulvers”, Hoppenstedt, Berlin (A short illustrated history of cannon)
(1941) [Reviewed by Dr Hassenstein in SS 37, 44) Paul Tavernier, “Evolution Historique des ,
111–12 (1942)] Poudres Saris Fum6e”, MP 32, 239–53 (1950)
30) E.E. Sancho, “Quhica de 10SExplosivos”, & CA 47, 9014 (1953) (A Historic Development
A. Aguado, Madrid (1941), pp 263–61 (History of Smokeless Powders) (The various stages are
of Black Powder and Ammunition & weapons discussed that led to the discovery and formu-
using it) lation of smokeless powder. Accomplishments of
31) M.M. Johnson, Jr & C.T. Haven, “Ammunition, various countries are given, with the more im-
Its History, Development and Use”, W. Morrow, portant dates up to the first World War)
NY (1943) 45) LeRoux, RevIndustMin6rale 33, 276–84
31a) T.L. Davis, “The Chemistry of Powder and (1952) (History of development of expls in-
Explosives”, J. Wiley, NY (1943) dustry)
32) M. Meyer, “Explosives”, T.Y. Crowell Co, 46) A. Stettbacher, “P61voras y Explosivos”,
NY (1943), 1–4, 58, 118 & 155–56 (History) G. Gill SA, Buenos Aires (1952), pp 1–5 (Re-
33) J.R. Newman, “The Tools of War”, Double- sefia historica) ~
day, Doran, NY (1943), pp 3–31 (Modern War- 47) W. Gutmann, Sprengtechnik 3/4, p 39
fare); 33–46 (History of Small Arms); 69-108 (1952) (Chronological list of some expls, proplnts
(History of Field Artillery); 109–175 (History of and ammunition manufd in Germany betw 1858
Fortification and Siegecraft); 176–203 (History and 1937)
of Tanks); 204–67 (History of Tools of Sea War); 48) ‘C. Belgrano, “Gli Esplosivi”, Hoepli, Milano
268–363 (History of Tools of Air War) (1952) (History of explosives and related items
34) Gen U. GaHwitz, “Die GescKtitzladung” is not found) [See 2nd edition (1974)]
(Cannon Charge), Heereswaffenamt, Berlin (1944) 49) G.O. Curme Jr & F. Johnston, “GIYcoIs”,
(Engl transln available at PicArsn Library) Reinhold, NY (1952), pp 7, 74, 114, 119, 130,
35) W. Hassenstein, SS 39, 1“–9, 22–6 & 37–42 148, 158, 168, 170, 176, 177, 203, 206 & 209
(1944) (The Chinese and the Discovery of Powder) 49a) E. Tunis, “Weapons. A Pictorial History”,
36) M. Vivas, R. Feigenspan & F. Ladreda, WorldPubgCo, Cleveland, Ohio (1954)
“P61voras y Explosives Modernos”, J. Morata, 50) Gen J.F.C. Fuller, “A Military History of the
Madrid, Vol 1 (1945), pp 25–8 (Algo de historia) Western World”, Funk & Wagnalls Co, NY, Vol 1
37)A. P6rez Ara, “Tratado de Explosivos”, Edi- (1954), pp 464& 469-70 and Vol 2 (1955),
torial “Cultural SA”, LaHabana, Cuba (1945), p 12
133–48 (Bosquejo hist6rico acerca de la p61vora 51) B.T. Fedoroff et al, “Dictionary of Russian
ordinaria) Ammunition and Weapons”, PATR 2145 (1955);
38) Maj T.C. Ohart, “Elements of Ammunition”, PB 159927, Available from NTIS
J. Wiley, NY (1946) (No history of ammunition 52) W.Y. Carman, “A History of Firearms”,
I
is given) StMartin’sPress, NY (1955), 1–11 & 157–62
39) J. Weir, Nature 158, 83–85 (1946) Nitro- 53) B.E. Schaar, “History of Accidental Scien-
glycerine and Guncotton” (A Double Century) tific Discoveries”, Schaar & Co, Chicago 7, 111
(Historical Review) (1955) (Discoveries of Dynamite, acetylene, pe-
40) G.M. Barnes, “Weapons of World War II”, troleum jelly, etc are described)
VanNostrand, NY (1947) 54) Anon, “Principles of Artillery Weapons”,
41) A. Stettbacher, “Spreng- und Schiesstoffe”, TM 9–3305-1 US Dept of Army, Washington,
 H 161

DC (1956), 4–8 & 12–15 Tokyo International, Tokyo, Japan. The paper
55) J. Pawle, “The Secret War 1933–1945”, contains nearly 100 entries and 30 refs of which
W. Sloane, NY (1957) (Story of the develop- only 4 are Western. The entries are arranged in
ments by the British Navy of some special wea- chronological order. Mr Gunther Cohn of
pons and devices) Franklin Institute reviewed the paper in Expls &
56) B.T. Fedoroff et al, “Dictionary of Explo- Pyrots5(11), 1972
sives, Ammunition and Weapons” (German 67) H. Ellern, “Military and Civilian Pyrotechnics”,
Section), PATR 2510 (1958); ASTIA Document Chemical Publishing Co, NY (1968) (2nd Edn)
AD 160636, Available from NTIS (National (No specific pages for history)
Technical Information Service), US Dept of Com- 67a) M. Lindsay, “One Hundred Great Guns: An
$
merce, Springfield, Virginia 2215 1; pp Ger I & Illustrated History of Firearms”, Walker & Co, ~~ #’
Ger 11 (Historical uses of expls in Germany NY (1967); reviewed in Ordn 53,99 (1968). —> d,4’
durkg WWI and WWII) Gorrrres, the earliest firearms, are listed dn pp
57) M. Giua et al, “Trattato di Chimica Indus- 29–33. (See also “Gonne” in Vol 6 of Encycl,
trial”, UTET, Torino VI (l), 1959, 6–10 p G 120-R)
(Storia) 68) Coil, “Blasters’ Handbook”, Published by
58) W.S. Dutton, “One Thousand Years of Ex- E.I. duPont & Co, Wilminton, Del (1969), pp
plosives, from Wildfire to the H–Bomb”, Winston,, 1–6 (Early History of Explosives); pp 7–24
Philadelphia (1960), pp indicated under the years (DuPont’s Role Today) (See also Ref 62)
in text 69) R.E. Dupuy & T.N. Dupuy, “The Encyclo-
59) ‘R.E. Oakeshott, “The Archeology of Weapons, pedia of Military History from 3500BC to the
Arms and Armor from Prehistory to the Age of Pr@sent”, Harper & Row, NY & Evanston (1970),
Chivairy”, Illustrated by the Author, Prager, NY pp 1–4 (Warfare begins); 15 (Early Chinese mili-
(1960) tary organization) and other pp indicated in the
60) J.R. Partington, “A History of Greek Fire text of this compilation)
and Gunpowder”, Heffer, Cambridge, England 70) Anon, “Engineering Design Handbook, Pro-
(1960) perties of Explosives of Military Interest”, US
61) S. Fordham, “High Explosives and Propellants”, Army Materiel Command Pamphlet AMCP
Pergamon Press, London & NY (1966), 15–16 706–1 77, Jan 1971, pp indicated in the text
(Brief history of expls & proplnts) 71) A.G. Gorst, “Porokha i Vzryvchatyiye
62) Coil, “Blasters’ Handbook”, Published by Veshchestva” (Powders and Explosive Substances),
E.I. duPont de Nemours & Co (Inc), Wilmington, Izdat Mashinostroyeniye, Moscow (1972), pp 5–17
Del (1966), pp 1–6 (Early History of Explo- (A brief historical description)
sives); 7–20 (DuPont’s Role Today) (See also 72) “Blasters’ Handbook”, 1973, Explosives
Ref 68) Division, Canadian industries Ltd, 6320 Dor-
63) A.V.B. Norman & D. Pottinger, “A History chester Bklg, W. Montreal, Quebec [Reviewed
of War and Weapons, 449 to 1660”, Crowell Co, in Expls4kPyrots 7 (1 2), 1974]
NY (1966), pp 13–224 73) C. Belgrano, “GIi Esplosivi”, Arti Grafiche
64) Anon, “MiIitary Explosives”, Dept of the Friulane, Udine, 2nd Edn (1974), 9–15 (Brevi
Army TechnicaI Manual TM 9–1 300-214, Nov cenni storiei sugli esplosivi)
1967, pp 2-4 to 2-6 (Development of Military
Explosives and Propellants)
65) W. Buehr, “Firearms”, Crowell Co, NY (1967), “Hive of Bees”. A Japanese pyrotechnic device
pp 1–186 of. WWII, which consisted of a six by one inch
66) Dr Heizo Nambo of Nippon Kayaku Co, Lt& cardboard (called Hive), mounted on a wooden
“Who Invented the Explosives’” Journal of the block and provided with a fuse. The “Hive” was
Industrial Explosives Socie~ of Japan 28, 322– filled with miniature BkPdr. charges (called
329 & 403–423 (1967). Japanese Studies in “Bees”)
the History of Science No 9 (1970). English W@ ignited by a fuse the “Hive” injected .
translation obtainable for $15, surface mail, from a plume of smoke followed by some object
Japan Publishers Trading Co, Ltd, PO Box 5030, shot at high speed and buzzed furiously away.
 H 162

This display was followed by a machine-gun I targets does not depend upon the strength of
succession of “Bees”,. which may be called min- the case (shell) but on the amount of the ex-
iature unguided BkPdr rockets launched from a plosive charge. In order to achieve low pressure
Roman candle in a gun of conventional design, the barrel
Refs: 1) Barry Rothman, Colt Industries, Fire- should be made longer and the chamber and
arms Div, Pyrotechnics Operation 2) Explosives cartridge case larger. Such guns were built but
& Pyrotechnics Vol 2, No 4, p 3 (1969) were found to be unsuitable because the pro-
pellant wa~ difficult to {ignite and it burned ir-
HMSO–Abbreviation for Her Majesty’s Stationary regularly (due to the low pressure:in the
Office (in London), which is the British Institu- chamber). Also, the initial velocity of the .
tion which corresponds to the US Government projectile varied from round to round which
Printing Office (in Washington, DC) means that no precision firing could be
achieved
HMT-See Hexamethylenetetramine in this Vol Better results were obtained in 1943 when
Dr. Hermann and collaborators of the Rhein-
HMTD–See Hexamethylenetriperoxidediamke metall-Borsig AG constructed the 8cm PWK 43
in this Vol (80mm Antitank Gun). The description of this
gun, called in French “canon antichar mod?le ‘
HMX (High Melting Explosive ,or Her Majesty’s 1943,” ~was given by Travers and Touchard “
Explosive). See CYCLOTETRAMETHYLENE-’ (Ref 3). They claimed th~t the “turbocanon
TETRANIT~INE in Vol 3, pp C605-R to Delamare-Maze,“ invented in France about 20
C6 IO-R. It exists in four polymorphs of which years earlier, may be considered as the pre- .
beta-HMX is described” on pp C606-R to C609-R decessor,of both the H/L and recoilless guns
and in AMCP 706-177 (1967), pp 173-77 The German gun, 8cm PWK 43, had a corn- -
paratively thin barrel with an inside diameter of
HMX-Nylon Plastic Bonded Explosive. See 81 mm and was 34 calibers long; the chamber
Nylon-HMX Plastic Bonded Explosive had an enlarged diameter (105mm) and much “ -
thicker walls. The projectile (fintail type, 81 mm
HNM: Hexanitromannitol. See Mannitaol in diameter, contained a shaped charge and
Hexanitrate in Vol 8 weighed 3kg) was inserted first in the bore (as
in separate-loading ammunition). This was
HNO. Abbrn for 2,4,6,2’,4’,6’-Hexanitro- followed by the cartridge (120mm long and 105
oxanilide, described under Oxanilide and mm in diameter) which contained the pro-
Derivatives and in AMCP 706-177 (1967), pellant. The cartridge was closed by means of
pp 170-’72 a disc provided with eight perforations (each
13mm in diameter). When the propellant burned
HNS. Abbrn for Hexanitrostilbene, also called - the pressure of the gases developed inside the
Hexanitrodiphenylethy lene. See Diphenylethylene- cartridge was about 850 kg/cm2 but the pressure
hexanitro in Vol 5, p D1456-R acting on the projectile was only 550 kg/cm2
because the, gases lost part of t,heir velocity
Hoch- und Niederuckkanone (High and Low on passing through the holes in the disc
Pressure Gun, abbreviated to H/L Gun) (Canon I
The relation between the high pressure inside
~ tu?re, in French). It has been known for a the cartridge case and the low~r pressure in the
long time that the lower the peak pressure in bore could be varied by increasing or decreasing
a gun the thinner may be the walls of the the size or number of the openings in the sep-
projectile. This means that for a given total arating disc. In order to protect the propellant
weight the projectile, used. in a gun with lower in the container from spilling and from moisture,
peak pressure, can contain more explosive and the perforated metallic disc was covered with a
do more damage to a target solid disc of paraffined cardboard
This is of particular importance in the use The ballistics for the H/L gun were worked
of shaped charges because the penetration of out by Travers and Touchard ‘;n France and by
 H 163

Corner in England p 247 3) A. I. Sprinz & H. H. Bullock of

Note: Corner stated that towards the end of Picatinny Arsenal; private communication 4)
WWII the Germans started to manufacture two PATR 2510, p Ger 90-L & R
light antitank guns: the 8cm PAW 600 and the
10.5cm PAW 1000, but does not describe them.
He also mentioned the 8.8cm W71 gun, which
was built on the “three-pressure principle”
Refs: 1) J.Corner, JFrarddinInst 246, 233 (1948)
2) J.Corner, “Theory of the Internal Ballistics
of Guns,” J.Wiley, NY (1950),pp3 12-327 3)
S.Travers & L.Touchard, M/mArtilFr 26, 835-
58 (1952) 4) Ibid, 27, 219-36 & 245-78
(1953) 4) PATR 2510 (1958), pp Ger 90-R
& Cer 91-L

Hochdruckpumpe (HDP) oder V-3 (High Pressure

Pqmp, called also “Busy Lizzie” or “Mtiltipede”)
a German constant-pressure gun developed
during WW 11 by Conders, an engineer of the
firm R6chling, Saarbrticken, and intended to
fire the Arrow (Needle) Projectile (qv) across
the Channel to London. The barrel, caliber
150mm (5.9”), was of unalloyed crucible
cast steel made up of a great many Y-shaped
sections, each 12 to 16 ft long. With a gun
about 450 ft long containing about 28 pro-
pellant chambers (distributed along the bore),
a muzzle velocity of about 4500 ft/sec and
a range of about 130 km was expected to
be achieved (when using a projectile 8 ft long
and weighing 150 lb)
The gun could lie on the ground without
any carriage on wooden and concrete blocks HDP Supergun
sloped at a 45° angle. The fin-stabilized, arrow (Vergeltungswaffe 3)
projectile was inserted in the barrel and the (V-3).+
base propellant charge electrically ignited. ~As
the projectile passed the separate Y-pieces, Hochexplosivkorper. Ger for High Explosives
additional propellant charges in the side arms (HE’s)
were electrically ignited one after another (in
pairs) thus accelerating the velocity of the Hochstatter Powder–patented in 1869 in ‘
projectile as it progressed along the gun barrel England was prepd by blending in wet condition
For servicing (reloading the Y-sections with KC103 (or. Pb(C103 )Z ), KN03 (or NaNOs).
propellant charges between the rounds), the charcoal and sulfur (or metallic sulfide) and
gun required a great many soldiers. It was impregnating paper or dry vegetable materials
planned to fire one round per gun every 5 with this mixture
minutes but this rate could not always be Refs: 1) Cundill (1889) in MP 6, 14 (1893)
achieved because the sections often exploded 2) Daniel (1902) 376 3) Giua, Trattato 6,
and it was necessary to insert new Y-pieces (1959)> 392
Refs: 1) L.E. Simon, German Research in
World War II, J. Wiley, ‘NY (1947), pp 191-3 Hohlladung (Ger for Shaped or Hollow Charge).
2) W. Dornberger, “V-2,” Viking, NY (1954), Considerable work was done in Germany before
 H 164

and during WW 11 on the development of Refs: 1) A. Stettbacher, Nitrocellulose 8, 83-84

shaped charges. Among the most prominent con- (1937) 2) O. W. Strickland et al, PB Rept ‘
tributors in this field were the personnel of 925, Appendix 3, p 46 and Appendix 7 (1945)
Kfimmel Fabrik, DAG. Among the shaped charge 3) H. L. Porter et al, CIOS Report 33-27 (1945)
weapons developed at Kriimmel may be 4) L. E. Simon, German Research in WWII,
mentioned: Wiley, NY (1947), pp 118-120, 188 5) A.
a) Magnetic anti-tank shaped charge weighing Stettbacher, Spreng- und Schiesstoffe, Rascher,
3 kg; blast penetration of armor was up to Ziirich (1948), pp 133-34 6) PATR 2510
250mm (1958), p Ger 91-L&R
b) Shaped charges for Faustpatrone, Panzer- Note: Gen description of Shaped Charge phe-
faust, Panzerschreck, etc nomenon is given in Vol 4, pp D442-R to
fVote: At Kriimmel it was found that the best D454-L under DETONATION, MUNROE-
explosives for shaped charges were RDX-TNB and NEUMANN EFFECT AND LINED CAVITY
next, RDX-TNT mixtures. Substituting PETN for EFFECT IN
RDX led to a decreasg in efficiency. The addit-
ion of aluminum powder was desirable but not Hoitsema’s Stability Test: One of two inter-
in large quantity connected U-tubes contains 1-2g of explosive,
Kr~mmel was not the only place where work while the 2nd tube contains glass wool impreg-
on shaped charges was conducted. Elsewhere the nated with a solution of 0.1 g diphenylamine (DPhA)
Germans developed a shaped charge shell which in 50rnl of 50~ sulfuric acid and 50ml of CP glyc- ‘
was shot from an 80mm mortar called erin. The first tube is heated for 15 minutes at
“Panzerwurfkanone”, and the warheads for sev- 110° and while heating is continued a current of
eral guided missiles pure COZ is passed through the tubes. If the DPhA
Historical Discovery of the hollow (shaped) reagent turns blue, a new sample is taken and the
charge (HoC) effect is usually attributed to test repeated at 10° lower” and so on until a temp
C. E. Munroe (USA) who described the effect in is reached at which the DPhA reagent no longer
the AmerJSci 36, 1888. It was claimed by H. turns blue
Schardin that Max von Fbkster of Germany had This test differs from Abel’s test in using
in 1883 already shown that bare hollow charges temperature of decomposition rather than time at
gave an enhanced effect along the axis of the constant temperature
charge. The first practical application of the Ref Daniel (1902), 679
HoC effect for demolition charges, sea mines,
torpedoes, projectiles etc, was patented in 1910 Hoko. Ger abbrn for Hochkonzentriert (Highly
by E. Neumann & the, Westf;lisch-Anhaltische Concentrated) Z3-ocessfor the manufacture of
Sprengstoff AG(DRP Anm W36269). Neumann’s 98-99.5% nitric acid, developed during WW II,
work is described in SS 6, 356 (191 1) and SS 9, and used in several German plants. In this process,
183 (19 14). Important work on military ap- the concentration of the weak acid (50%) was
plications of the HoC effect was done, prior to effected by mixing it with liquid nitrogen
and during WW H, by H. Schardin et al in Ber- tetroxide (Nz Oq) and adding the necessary extra
lin. Some work was also carried out by A. oxygen under 50 atm pressure in an autoclave
Stettbacher of Switzerland during this period. Descriptiorr of this method as practiced by
Note: According to A. J. Dere, Ordnance the IG Farbenind A-G subsidiary, the Wirtschaft-
Sergeant, October 1945, pp 3-13, hollow(shaped) liche Forschungsgesellschaft mbH (WIFO), Emb- 1
charge ammunition was used by the Germans sen, Kr Lbheburg is given in the following BIOS
in many 75mm caliber weapons. There were at Final Reports: 1232 (1947), pp 15-16 and 1442
least four types of such projectiles: H1, Hi/A, (1947), “pp 84-98
H1 /B and HI/C. Most of these projectiles are
briefly described in TM 9-1985-3 (1953). Some Hollings patented, in 1898 in England, the
projectiles of calibers 88mm, 100mm, 105mm method of preparation of compressed charges
and 150mm also had shaped charges of wet nitrocellulose in two stages: first by .
The following drawings represent some typical using a worm screw in a cylinder, provided with
German hollow charges. (See next page) numerous small perforations, followed by hy-
draulic pressing. During the first operation air
GERMAN HOLLOW
(SHAPED)CHARGES H 165

LfYK
‘..

/CL5cm Gr39
Rotffze

!
/OScmGr 3944’
 H 166

and excess of water are driven off, while in the Refs: 1) W. Van Beckum & G. J. Ritter, Paper
hydraulic press the NC assumes the desired TradeJ, “104 (19), 49 (1937) & CA, 31, 6458
shape, such as discs, blocks, etc (1937); 105 (18), 127 (1938)’ & CA, 32, 765
Refi DanieI (1902), 376 (1938); 108 (7), 29 (1939) and CA. 33.4017
(1939) 2) Marsh &“ Wood, Cellulose (1945)
Hollow Charge. See Hohlladung (Shaped Charge) p 3 (see p XIII, vol 5 for this abbrn) 3) Dor6e,
(1947), p 336
Hollow Charge Nose Attachment for AP Bombs.
Holtex. See Ref 7 thru Ref 11, pp C396-L to
C397-L and Addnl Ref K, pp C402-R to
C403-L in Vol 3 of Encycl

Holzmine 42. German Landmine developed

during WW II
Refi TM 9-1985-2 (1953), p 263

Homing Guidance Systems. A homing guidance

system may be defined as a guidance system by
which a missile steers itself toward a target by
In order to permit greater penetrating power means of a self-contained mechanism which is
from low altitudes some German 250 kg AP activated by some distinguishing characteristic
bombs had a hollow charge (weighing about 4 of the target. The homing guidance systems fall
kg) attached to the nose. This charge was under one of the three general types: active
detonated by its own nose fuze as soon as it homing, semiactive homing, and passive homing.
hit the armor. The explosion, of the HoC pro- There are possible permutations and combinations
duced a hole in the armor (as deep as 7 cm) of the three basic types, depending upon intended
which permitted the AP bomb to enter inside application. The basic homing types also may
the target. The AP bomb being provided with be employed in conjunction with other guidance
a short delay fuze did not explode until it w,as techniques. For example, the control of a missile
inside the target. In order to protect the bomb may involve several guidance phases each using
from premature detonation the space between a different guidance technique
the HoC and the nose of the bomb was filled An active homing guidance system is one in
with sawdust and cement which both the source of energy to illuminate the
Refs: 1) TM9-1985-2(1953), p 5 2) PATR target and the receiver of the energy reflected
2510 (1958), pp Ger 91-R & 93-L from the target are carried in the missile
The active homing guidance system, in its
Holmgrens: An explosive used in Sweden between simplest form, consists of a transmitter and re-
1903 and 1906 for filling shells and claimed to ceiver of energy, which enable the missile to
be more suitable for that purpose than PA. No detect the presence of the target, a computer
composition is given which predicts from the received energy the
Refi D.H. Hone, SS 1, 109 (1906) future position of the target, and missile control
surfaces which respond to computed signals in
Holocellulose: Cellulosic material obtainable from such a) fashion as to direct the missile to im-
wood after removal of lignin. The term there- pact with the target. The energy used to illu-
fore means total carbohydrates (cellulose and minate the target may be in the form of radio,
hemicellulose) present in the wood (Refs 1 & 2) light, heat, or sound waves. A missile which uses
Ritter (Ref 3) succeded in isolating holo- active homing guidance is completely independent
cellulose from wood pulp by repeated chlori- once homing starts; the missile does not require
nation, followed by extraction with alcohol energy transmitted from an external ,source or
containing 3% of monoethanolamine. The re- externally derived guidance intelligence
sulting product was white but changed color A semiactive homing guidance system is one
on standing wherein the receiver in the missile receives
 H 167

energy reflected from the target, the energy Homocyclonite. One of the names for Cycle-
tetramethylene-tetranitramine (HMX) described /@w
having been transmitted from a point external 1//0 / 59
to the missile. The semiactive homing guidance under Cyclotetramethylene-tetramine and
system consists of a receiver in the missile Derivatives in Vol 3, p C605-R
& ~9/
which detects the presence of the target, a
\\- @\’
computer (also in the missile) which predicts Homogenization and Homogenizers (See also
from the received energy the future position Emulsification and Emulsifiers). The term “homo-
of the target, missile control surfaces which genization ,“ according to Sloan (Ref 1), de-
direct the missile along the correct flight path scribes the process of putting incompatible or
for impact with the t~rget, and an externally immiscible components into a stablized, nearly
located transmitter which illuminates the homogeneoussuspension in a liquid medium. For
target. This external transmitter may be located instance, preparation of various cosmetic creams
at the missile launching station, or at a point may be accomplished by homogenization of fats,
separated from the missile launching station. talc, essential oils, coloring materials etc in
The transmitter may be a surface installation water. Homogenization can produce particles of
or it may be airborne. As in the case of active the order of 1 micron diameter, which are
homing guidance, the transmitted energy may smaller than encountered in most natural emul-
be in the form of radio, heat, or sound waves. sions, such as milk. As the smaller particles
The principal difference in the basic operation remain in suspension for a longer time than
of an active and a semiactive guidance system the larger ones, milk passed through a “homo-
is that the semiactive system is not independent genizer” (an apparatus used for “homogenization”)
of external sources. Its guidance intelligence is will not separate into cream and skimmed milk,
derived from energy transmitted from a point particles of fat and casein are smaller than in
external to the missile ordinary milk, better digestibility is achieved
A modified version of this semiactive tech- Many types of homogenizers are on the
nique has the transmitter located in the missile market, but the most conventional types
and the receiver of the reflected energy at some function by forcing the ingredients (at pressures
remote point. Computation of the desired flight of 500 to 3000 psi) past. a spring-seated valve.
path takes place at a remote point and suitable Emulsification occurs not only while the com-
commands are sent to the missile. This system ponents pass under the valve seat, but also when
is known as a quasi-active homing guidance they impinge against the retaining wall that
system surrounds the valve. The high velocity combined
A passive homing guidance system is a gui- with hydraulic shear, pressure release and im-
dance system wherein the receiver in the missile pact, transforms the dispersed phase into a very
utilizes energy emanating from the target. The fine state of subdivision
basic difference between the passive homing Refs; 1) J. H. Perry, Chem Engineer’s Handbook,
technique and the two preceding techniques is McCraw-Hill, NY (1950), pp 1167-1 168; C. K.
that energy from which the guidance intelli- Sloan, “Homogenizers”; 4th edit (1963),
gence is derived in the passive homing system p 21-17 2) Kirk& Othmer 5 (1950), p
is generated in the target; thus no other t rans- 706 (under “Emulsions”); 8 (1965), p 141
mitter is required. In this system, the. receiver, (under “Emulsions”)
computer, and missile control surfaces serve
the same functions as described for the pre- Honest John. Popular name for the US Army
vious systems. The energy emanating from the 762mm rocket system, a surface-to-surface
target may be in the form of heat, light, sound, tactical missile, employing a solid proplnt. It
or radio waves is launched from a rail-type launcher at an
Ret A. S. Locke, et al, “Guidance,” Van NOS- elevation which can be varied to obtn the
trand, NY (1955), pp 541-562 desired point of impact. Honest John carries
Note: See also Guidance System of a Missile either a conventional HE warhead or a nuclear
inVol 6, pG175 to G178 warhead
Ref OrdTechTerm (1962), p 156-L
 H 168
/

Honey (Miel in French). A sweet, sticky Hornet Ball Cartridge. See under Cartridge,
substance made by the honey bee from the Ammunition in Vol 2, ‘p C74-L
juices it collected from flowers. It can be
nitrated to: Horns. Metallic projections (lead, steel or
Nitrohoney (Nitromiel). Nitration is best copper) on top and/or sides of underwater mines,
conducted in mixtures of honey and glycerin, serving as initiators. Horns are of several types
using the acids and procedure described under but the most common is the “chemical horn,”
Nitroglycerin. The explosive properties of which contains glass vials filled with acid.
this mixed explosive are similar to those of When the ship hits one of these horns, it breaks ~
Nitrohydrin (qv). “Nitrohoney” was patented the glass vial and the acid then flows between
for use in the so-called Thunder Powder (qv) electrodes of a battery causing a current to be
Refi Daniel (1902), p 564 under Nitromiel generated. The current fires an electric detona-
and p 767 under “Thunder Powder” tor, which causes detonation of the main
charge of the mine
Hop Record of a Gun Carriage or Mount. The Refi Glossary of Ordn (1959), p 15 l-L; Ord-
hop is defined as the motion of the carriage (or TechTerm (1962), p 156-L
mount) from the instant of firing until equi-
librium is attained. The “hop” record is a Horse Detonator. The name given to the Ameri-
measure of the carriage (or mount) stability. can “M46” fuze because it can initiate much
The equipment and methods of testing are more effectively than standard fuzes, such as the
given in Ordnance Proof Manual No 40-78 (1943) Mark III. The “M46 fuze” cm be ‘Seal ‘Ven ‘ith
the worst exuding shell, where the standard fuzes
Ho-pao. A kind of incendiary charge resembling nearly always fail. It compensates for both de-
Greek fire, employed by the Mongols in the sensitized boost ers and bursting charges. In al]
13th century cases, it gives high-order detonations
Refi Daniel (1902) 377 Ret War Dept Tech Manual, TM9–1901
(1944), p 135
Hope patented in 1884 in England–Black Powder
in which part of charcoal is replaced by starch, Horsedung Explosive. A blasting explosive
flour, sugar, or other organic substances. Some composed of K nitrate 12 parts, horsedung dust
bitumen, or other solid hydrocarbons was includ- 1, charcoal 1 & sulfur 3 parts
ed in order to obtain more complete combustion Refi Deutsche Praeposit-Werke Karlsruhe, GerP
Refi Daniel (1902) 377 231598 (1907); CA 5, 2725 (1911)

Hopkinson’s Pressure Bar Test. See under Physi- Horsley Dynamites authorized in 1872 in Eng-
cal Tests for Determining Explosive and other land were prepd by mixing at least 73 parts. of
Properties in Vol 1 of Encycl, p XVI NG with the following pre-pulverized mixtures:
a) KC103 75 & gallnut 25% (Ref 3) or b)
Horn-Seifert Stability Test. In the original test of KC103 75, gallnut 12.5 & charcoal 12.5% (Ref
Horn, 2g of smokeless proplnt was heated to 1)
120° in a long test tube until brown fumes of According to Daniel (Ref 2), a mixt of KC103
nitrogen dioxide evolved. The degree of decom- & NG, known as Serarrine (qv) was p!oposed by
position of the proplnt was judged approximately Horsley. Another mixture, also known as Sera-
by the intensity of brown coloration as observed nine was proposed by Bjorkmann (Ref 2)
by looking down the length of the tube Refs: 1) Cundill (1 899) in MP 6 14 (1892)
against a disc of white porcelain (Ref 2) 2) Daniel (1902) 713 3) Giua, Trattato 6
Seifert (Ref 1) modified the test by intro- (1959), 392
ducing a test paper (methyl violet or rosaniline)
and observing the successive changes of color Hot Bar Test of High and Low Explosives. It
Refs: l) Seifert, Voyenske-Technicke Zpravy is one of the tests used for the determination
(Prague), 4, 42 (1927) 2) Reilly (1938) p 79 of ignition (deflagration or explosion) temper-

.
 H 169

ature. The test originated in Spain and is de- mean of the thermometer readings, when ex-
scribed in Marshall (Ref 3) under the name plosion occured, was taken as the temperature
“Temperature of Ignition.” The apparatus of ignition. This method was used in Spain
shown in Fig 83, p 436 is reproduced here for testing NC propellants. If the ignition temp
(qv) was 180° the sample was considered good; if it
was between 178° & 180°, it was serviceable;
if between 176° & 178° it had to be used
immediately; and if below 176° the sample was
destroyed
Note 1: Instead of heating the bar by gas
burners, it can be heated electrically, such af
described by E. Berl & G. Rueff in Cellu-
losechemie 14, 43 (1933). The bar, known as
Bloc Maquerrne, generally used in France for
determining melting points, could be adopted
for use in determining the ignition. (or. explo-
sion) point
Note 2: Fisher Melting Point Apparatus, de-
scribed by Fisher Scientific Co, Pittsburgh, Pa
(1970), p 640, can also be used for deter-
mining ignition (or explosion) temperature
Note 3: Hot bar and other methods for de-
termining ignition (or explosion) temperature
are described in the following refs
Refs: 1) A.P. Sy, JFranklInst 155, 171 (1903)
(Early US Ordnance method, also described in
Refs 2 & 4) 2) Marshall 2 (1917), 434-35
(same method as in Ref 1) 3) Marshall 2
(1917), 435 (Hot bar method) 4) Reilly (1938)
83 (same method as in Ref 1 is listed as
Deflagration Test) 5) PATR 2700, Vol 1 (1960)
pp XVI & XVII (description of two tests and
list of 11 refs) 6) AMCP 706-177 (1971), p 3
(current US Ordnan;e Explosion Temperature
Determination) 7) PATR 2700, Vol 6 (1973)
p E387-R (Explosion Temperature)
Fig 83. Apparatus for Determining the Tem-
perature of Ignition
Hot Extrusion of Shells. A modification of the
The’ copper bar (a) had a circular enlarge- Ugine-Sejournet hot extrusion process (using
ment atone end in which there were five glass as lubricant) is used by Scaife Company of
holes; the central one (F) contd mercury in Oakmont, Pennsylvania. In this process a com-
which the bulb of a thermometer was im- plete shell (such as 4.2 inch) can be produced
mersed; a small copper tube, contg O.lg of in one piece from a simple billet. Important
pulverized explosive to be tested, was placed features of the development are in the sub-
in each of the other holes. The bar was stitution of readily available billet stock for
supported on a stand and was heated by means seamless steel tubing, a critical material in times
of burners placed underneath it. The rate of of war. Another feature of this process is that
heating could be regulated by moving the it requires about 25% less steel
burners. The expl sample in tube (b) exploded Refs: ordnance, 38, 753 (1954) 2) Iron Age
first, then in (c) and (d) and finally (e). The (April 1954) pp 98-102
 H170

Hot Spots to 9 kbar in the PETN is ca 0.30- mm/microsec.

Introduction. A hot spot is a localized region of If all this Hugoniot energy (1/2 u;) goes into
higher-than-average temperature. In explosion heat (and it certainly does not) the max uniform
phenomena, the term “hot spot” is usually temp rise of the PETN ‘is only ca 36° which is
associated with the name .of Bowden, although clearly insufficient to even start slow decompo-
many other investigators have invoked the con- sition in the PETN, to say nothing of producing
cept and contributed to its understanding a detonation in the observed shock initiation
There is a great deal of evidence that most times which are of the order of 1 microsec. Ob-
explosive sensitivity phenomena are under- viously the shock energy must be concentrated in
standable in terms of the thermal decomposition hot spots
of the explosive involved. Some of the early work Hot Spot Generation Mechanisms. Although
on the interpretation of impact and friction there is general consensus on the existence of
sensitivity of explosives in terms of thermal hot spots, there is far less agreement on their
effects is excellently summarized by Bowden & means of generation or the mechanisms by which’
Yoffe (Ref 1). More recent studjes which also they initiate explosions. Some of the possible
include investigations of irradiation of explo- modes of hot spot generation are:
sives by nuclear particles and ionizing radiations a) an adiabatic heating of compressed gas
are also reviewed by these authors (Ref 2), and spaces (Refs 1 & 2)
by Bowden (Ref 7) b), a frictional hot spot on +he confining
Cook (Ref 3) summarizes the adiabatic de- surface or on a grit particle (Ref 1 & 2)
composition of explosives. Still more recently c) intercrystalline friction of the explosive
Bowden (Ref 7) reviewed energy localization itself (Ref 1 & 2)
effects in single crystals. (See Vol 4, pp D563- d) viscous heating of the explosive at high
69). All these reviews as well as more studies rates of shear (Ref 1)
(to be discussed below) emphasize the thermal e) heating of a sharp point when it is de-
nature of explosive initiation. Two simple examples formed plastically (Ref 2, p 76)
will reveal that the thermal energy to produce f) mutual reinforcement of relatively weak
initiation must be highly localized, ie unless the shock waves; probably at inhomogeneities
input energy, known to produce explosions, is in the shocked medium (Refs 7,8,10 & 16)
concentrated into hor spots no explosions can g) stagnation of particles spalled off a crystal-
occur lite by the incoming shock and then stopped
1) In the B of M impact machine small after flying across an air gap (the gap can
samples of RDX explode at around 30 cm drops be a void), by a neighboring crystallite
of a 2 kg weight. Assuming that all the drop (Ref 11)
energy goes into heating a 20 mg sample with h) Micro-Munro jets formed by shocking
no heat loss, then the maximum uniform bubbles, cavities or voids whose interface
temperature of the RDX is only ca 250°. At (between solid or liquid and the cavity)
250° the ignition lag for RDX is of the order is concave (Ref 7)
of 1 see, whereas it is found (Refs 1 & 3) that Modes a), b) & c) presumably operate in the
under impact’ measurement conditions the time usual impact and/or friction initiation of pressed
lags are only several hundred microseconds or solid explosives, and modes a) & b) in the ire-,
at least 1000-fold shorter. Clearly the impact pact and/or friction initiation of liquid ex-
energy must create hot spots that are at a con- plosives. Modes e), f), g) & h) operate in the
siderably higher temp than 250° shock initiation (and possibly the propagation)
2) For PETN compacts of about 90% of of detonation in solid explosive compacts or
crystal density, the 50% threshold for shock ini- explosive liquids containing inhomogeneities.
tiation is about 9 kbar. This threshold is very Mode d) is operative only at strong shock in-
nearly the same for large diameter plane-wave puts and may be the main mode of initiation
tests (Ref 18) and for small diameter, divergent and propagation in homogeneous explosive liquids
wave gap tests (Ref 17)., From, the Hugoniot data or defect-free explosive single crystals
in Ref 17, the particle velocity, up, corresponding Theoretical Development. The foregoing shows
 H 171

the complexity of the phenomena involved in

generating hot spots. The mechanism by which Absolute temperature
hot spots initiate explosions is even more com- Space coordinate
plicated since it involves: Time
Initial hot spot temperature
1) dissipation of the externally applied Medium temperature
energy leading to heat liberation in the Hot spot radius
materials during which the material is not Heat of reaction
heated uniformly, but at localized sites to Activation energy
form hot spots Pre-exponentialf actor
2) thermal explosion of the hot spot Specific heat
3) generation of a self-propagating process in Thermal conductivity coetlicient
. the material, resulting in explosion Density
Hot spot symmetry factor
As full theoretical discussion of this problem n = O ‘planar hot spot
involves enormous” difficulties, of both physical
and mathematical nature, the practice nowadays
is to make use of calculations based on an
( n= 1 cylindrical hot spot
n = 2 spherical hot spot
The exact solution of Eq 1 is unknown. Only
idealized picture of the phenomenon. These numerical or approximate analytical solutions are
idealizations are based on the following assump- available. Solutions are obtained in terms of
tions: dimensionless variables and parameters, eg: z &
a) during hot spot formation an insignificant .H ,[,4 $9
Variables:.
amount of chemical reaction takes place,
ie the first and the second steps are clearly
separated in time
b) the initial temperature profiie in the hot
7=$ —Q —E kOexp(-E/RTo)
spot is square wave cp Rr;
C) an exothermic first or zeroth order re-

action not accompanied by any phase trans- Parameters:

formation or other physiochemical
processes occurs in the hot spot and the
medium
The real picture is naturally much more
complicated. Some of the complications arising;
from the requirements of energy transfer from (Eq 2)
inhomogeneities to the explosive will be dis- by Merzhanov (Ref 14) and,
cussed in a “later section
The basic equation governing hot spot phenom-
ena is:
Parameters:
cp ~ =Qhexp(-E/RT)

(Eq 3)
where (Eq 1) by Friedman (Ref 15)
In terms of the first (Merzhanov) set of
O<x<ooandi>O dimensionless variables Eq 1 takes the form:
n W’
‘expo+x p+ _—
with conditions: ~
*=0 .T=T, x<r
T~ > T,
—
W
a?
1
(
ale
~ at )
:>(),
( T=Tl
%=(), g =0
x>r

.=(X+ .0
‘=0 (0=0
e=–eo
=lO.>O
(>1
ae
Tao ~=o g
‘0 ‘=m~ ‘0 (Eqs 4)
 H172

In Merzhanov’s treatment the hot spot problem, As an example of the usefulness of ap-
as well as ordinary problems of thermal explo- proximate solutions of Eq 1, let us consider
sion, involves a critical value of the parameter 6 how to compute the explosion time of a
which is a function of parameter 00, namely planar hot spot whose temperature and radius
an sf. (eO) are given. A rough, but as will be shown, not
(Eq 5) too bad an estimate is obtained from solutions
Merzhanov states that the results of numerical of the adiabatic explosion time equation:
calculations for spherical, cylindricrd and planar
hot spots fit the single empirical formula: T~=(Oi,)2exp(l /0’0)/uc2 (Eq 6)
&= d. (ln&Jm.
where a~=pRQkO r2 /AE, and the dimensionless
where dn & mn are (for 4< 0.<25): r; is then converted into actual time via Eq 3.
nzo ~= 2“66 t&=l:3 More accurately the explosion time, F, can be
n=l d,= 7.39 m,=O.83 obtained from Friedman’s results (Ref 15) namely:
?=2 4=12”1 m,=O.6
Numerical solutions can be invalid outside exp(– 1/4#)=7T1 n (fl~ –0’)/2(6~–O ~)(~’)’ n (Eq 7)
the computational range for which they are
made, and it is frequently cumbersome to use and 2(0’)2 (1 -2T;]–O’(20~ +1 )+6~0
them in establishing the functional dependence
of the solution on the variables of the process. where the average explosion time 7‘ is taken to
Thus even approximate analytical solutions are be 0.14. The following tabulation shows that
often more instructive than the more accurate Eq 7 underestimates 7’, but its values of #
numerical solutions. However considerable caution that are closer to the “exact” (numerical soln of
must be used in this approach, since some of Eq 1) at small O: than those obtained from
the approximations, employed to make the Eq 6. At large (lb the # from Eq 6 & 7 are
equations tractable, can lead to erroneous indistinguishable and a little smaller than the
answers. A number of approximate solution for exact #
the hot spot system (Eq 1) are reviewed by
Merzhanov and their shortcomings are pointed 0; 0.03 0.04 “0.06 0.08 0.10
out (Ref 14). More recently, Friedman (Ref 15) 0; 0.02 0.03 0.03 0.03 0.01
2
has developed approximate analytical solutions ‘C
2.28x10126 .00x108 4.36x10S I.20x104 1.73x1O
for a planar (semi-infinite slab) hot spot. These ~“ (“exact”) 0.114 0.179 0.141 0.150 0.138
were discussed in Sec 4 of Heat Effects on p H39-R ~’ (Eq 7) 0.107 0.161 0.128 0.143 0.124
of this Vol. To compare Friedman’s approximate ~’ (Eq 6) 0.150 0.200 0.143 0.144 0.124
solutions with the “exact” numerical solution of In contrast, ”the “exact” treatment of
Merzhanov we computed r, the hot spot half- Merzhanov (Ref 14) does not give even ap-
width, of a planar hot spot by both methods proximate explosion times unless Eqs 4 are
using the same thermal & kinetic parameters e~+d%?
solved numerically. ~
in both calculations. Over a wide range of input Heat jlow from a hot spot. One of the earliest
variables, the numerical solution gives values of recognized manifestations of hot spots was that I
r which are 33 to 43’ZOgreater than the r’s of of entrapped air or gas bubbles initiating ex- 1
the approximate solution. Thus it appears that plosion in an impacted liquid explosive (Ref 1).
the approximate solution, from whith the effect Originally Bowden’s school suggested that heat
of the process variables are much easier to dis- from the adiabatic compression of such gas
cern than from the numerical solution, gives bubbles initiated explosion in the surrounding
answers that differ from the exact numerical liquid. Johansson & coworkers (Ref 4), however,
solution by a nearly. constant factor pointed out that heat flow from a compressed
Other methods of making hot spot calculat- gas bubble to the surrounding liquid is much
ions are reviewed in Chap 10 of Ref 18. This too slow to account for the observed phenomena,
Ref gives generalized, non-dimensioned curves particularly at low impact energies. They have
for estimating hot spot temperatures and shown that to achieve explosion fine droplets
dimensions
 H 173

of liquid or the creation of foam are necessary the “temperature hot spot,” in which the
within the compressed gas bubble. They also density of the hot spot was the same as that
point out that too large a mass of droplets or , of the surroundimz nitromethane and the tem~-
foam within the bubble can result in too low erature was higher; and the “pressure hot spot,”
a temperature of this mass. This immediately in which the density was also increased. In the
suggests a critical condition for explosion, pressure hot spot, the density and temperature
namely, enough hot material within the com- chosen were values on the single shock Hugoniot.
pressed bubble to ignite the surrounding ex- In both cases, the temperature was chosen
plosive after this material undergoes thermal such that decomposition of the hot spot would
explosion; but not so much material that its occur almost immediately relative to the
temperature rise (due to heat flow from the surrounding nitromethane”
compressed gas) is, too low for its thermal Based on these calculations, hk conclusions
explosion. This criticality may account for the were:
wide spread of results usually observed in the “The hydrodynamic hot spot is successful
impact testing of explosives as a model for computing the critical sizes of
Hydrodynamic hot spots. For initiation via hot spots” in shocked nitromethane. The energy
impact, characteristic times are of the order of transfer in a hydrodynamic hot spot is effected
several hundred microseconds and explosion by shock and rarefaction waves. The computed
usually starts with a deflagration which can nitromethane hot spots, of reasonable size to
turn into a detonation (Refs 1 & 5). For this result from interactions of a shock with a bubble,
process the heat flow described above appears may initiate propagating detonation or not within
to be adequate. However, for initiation of the experimentally observed times of the order
detonation, in granular explosive compacts or of 0.1 psec. A hydro-dynamic hot spot may
explosive liquids containing inhomogeneities, via fail to explode if the rarefaction reaches the
shock the characteristic times are entirely too center of the hot spot before it can adiabatically
short for any appreciable heat flow from the hot explode. If the hot spot explodes, it sends a
spot to the surrounding explosive (Ref 6). shock wave into the undetonated explosive, which
Energy transfer from the hot spot to the heats the explosive. Whether or not it will
surround~gs is therefore presumed to occur initiate propagating detonation depends upon the
entirely by shock and rarefaction waves. initial strength of the shock wave and how rap-
Mader (Ref 7) called this hot spot model the idly the shock strength decreases at the interface”
hydrodynamic hot spot and the development More recently Mader developed computational
of this model is largely due to his work. In Ref procedures that enables him to examine 2-dimen-
7 Mader considered the shock initiation of sional hot spots (Ref 10). We quote his conclu-
nitromethane containing inhomogeneities such sion of that study:
as voids or grit particles. To quote Mader: “The basic processes in the shock initiation
“In these calculations, the hot spots were of inhomogeneous explosives have been investi-
idealized in initial geometry, since no method gated theoretically using the model of a cylinder
now exists for calculating the reactive dynamics of nitromethane containing a void or an aluminum
of the actual two-dimensional configuration. pellet. The interaction of a shock with the density
In order to retain one-dimensionality in the discontinuities, the” resulting formation of a hot
computations, the hot spot was assumed to be a spot, and the buildup to propagating detonation
spherical disturbed region whose density and were computed using two-dimensional numerical
temperature was uniform throughout. The sur- hydro-dynamics of the “PIC” type with chemical
rounding shocked nitromethane was likewise reaction and accurate equations of state. The
uniform in density and temperature. Initially, hot spots formed at aluminum pellets exhibit
the fluid was everywhere at rest relative to the failure or propagation of detonation in ap-
center of the hot spot, which was taken as the proximately the same manner as the one- dimen-
origin of the space coordinate sional, hydrodynamic hot spots studied pre-
Two types of hot spots were considered as viously. The failure of hot spots formed at
representing the extreme possibilities. These are voids could be studied only in those cases in
 H174

which the failure mechanism did not depend on sizes of crystals and above a critical impact
details of the structure of the reaction zone, as energy. Particles impacting below the critical
this structure could not be reproduced in the impact energy produced plastic indentations in
calculation” the crystals. On the basis of these results, it was
Mader then reprogrammed his computations. concluded that explosives” can be initiated as a result
for an Eulerian code and considered the inter- of rapid plastic J70w. It is believed that in many
actions of 4 cylindrical voids, rather than a single cases of impact and shock initiation plastic flow
void (Ref 16). He showed that shock interactions can’ allow the localization of impact energy re-
with four holes lead to much greater & faster quired for hot-spot formation” (Ref ,20)
computed nitromethane decomposition than the where ~*=r*/R; r*=distance from center of the
shock interaction with a single hole for the same anvil to the spot where explosion starts (deter-
initial conditions mined from the burning trace remaining on the
He concludes: anvil after an impact that produces ,explosion);
“The basic two-dimensional processes involved 7* is the observed time from impact to explosion;
in the shock initiation of heterogeneous ex- h is the test sample thickness; c & p have their
plosives have now been numerically described. usual meaning; u* is the critical impact velocity
The problem that remains is the study of the to produce explosion; T* is the hot spot temper-
interaction of a shock with a matrix of holes in ature. They obtain the following results with a
three-dimensional geometry. The basic two- 10 kg falling weight:
dimensional processes involved in the failure of Explosive u* @ t* T* Tad
detonation, the failure diameter of explosives, cm/sec psec “c
——
and the “sputtering “ initiation observed for
PETN 240 300 0.15 3T0 214
density discontinuities near the critical size have 15
RDx 310 210 0.22 470
been described. The three-dimensional study of
HMx 310 150 0.26 500
the interaction of numerous failures and re-
ignited detonations which is ,necessary for a We have added the last column, Tad, the time
complete numerical description of these problems lag for an adiabatic thermal explosion at T*. In
must await new computing hardware” our calculation T* is the temp of a hot spot ih
A novel method for estimating hot spot the condensed explosive. We used E=29.2 kcal/
temperatures. An interesting approach towards mole & k. =1.2x1012see-l for PETN (J. Roth,
estimating the hot spot temp during an impact Addendum to Bulletin of 6th Army-Navy Solid
test has been presented by Bobolev & Bolkhovi- Propellant Group, p 41, 1950) and E=41 kcal/
tinov(Ref 5). They suggest that in an impact mole & k. =3x1015see-i for RDX (Ref 3). It is
test in which the test sample is unconfined clear that ~*e~ad only for PETN. Why this is
some of the sample melts because of plastic so is uncertain at present. However the Bobolev
deformation and the whole sample then behaves & Bolkhovitinov approach merits further study
as a very viscous liquid.* After considering the As pointed out by Johansson (Ref 4) the
heat flow in this system, and taking into account temperature of a compressed gas bubble within
that the melting point of the sample is raised a condensed explosive is usually much higher
because the” pressure” iricreases during impact, than T*. This is emphasized by the Findings of
(they assume a linear increase with a coefficient Friedman (Ref 13) who used reflected shocks
a~0.02° /atm),
. . they arrive at the following eqn: in a shock tube to ignite explosive dusts and
sprays. Friedman claims that his results can
be interpreted to mean that ‘bubble hot spot
temperatures hot enough to ignite explosives
are between 500 & 800°C
A novel hot spot mechanism. Maycoc~ and
*Note.” According to R. E. Winter of Cavendish Grabenstein have observed a piezoelectric effect in
Labs, Cambridge: “Flat faces of Silver & Lead single crystal HMX (Ref 12). This effect increases
Azide crystals were initiated when impacted with linearly with static load up their max observed field
spherical metal particles, small compared with the strength of 10v/cm at a load of 400g on a sample
 H 175

area of 0.42cm2. With the extreme assumption Merzhanov, Ibid, 341 & CA 66, 47935 (1967)
that the piezoelectric effect continues to increase 15) M.H. Friedman, Ibid, 11, 239 (1967)
linearly to much higher pressures, and that shock 16) C.L. Mader, Proc 5th ONRSympDeton
loading, which constitutes dynamic loading, is no (1970) p 177 17) J. Roth, Ibid, p 227 18)
different from static loading, fields of 10s to D. Stine et al, JAP 41, 3324 (1970), 19)
106v/cm might be generated at shock loadings of Anon, “Principles of Explosive Behavior” AMCP
10 to 100 kbars which are pressures typical of 706-180 (1972) 20) R.E. SWnter, Expl Div
shock initiation processes. At such high field Newsletter PA July 1973
strengths electric breakdown and electron ava- Note: A brief description of “hot spots” was
lanching might be expected. This would create hot given urider the title Detonation, Spot or Hot
spots along the breakdown path. It is known Spot, Initiation of in Vol 4, pp D563-R to
(Ref 2) that Ag Azide breaks down and explodes D569-R, with 34 refs
at fields of 100 to 1000 v/cm, but breakdown
strengths of secondary explosives, such as HMX, Howard Powder. Same as Mercuric Fulminate
have not been measured
Use of high energy radtition to create hot spots. Howden Dynamite. A mixture compounded in
Attempts have been made to initiate explosives 1870 in San Francisco by J. Howden and
by ionizing radiation such a-particles, high speed consisting of: NC 75 absorbed in a mixture of
electrons, ~-rays, Plons etc (Refs 8 & 9). No sugar, magnesium carbonate and potassium
initiations were observed. Cerny & Kaufman nitrate. This Dynamite was stronger and better
(Ref 9) take this absence of initiation to indicate than Nobel’s Kieselguhr Dynamite ~,
failure of the hot spot model. However a crude Ref Blasters’ Handbook (1952), p 5; (1958)
preliminary calculation, based on the Friedman p5
model (Ref 15), suggests that the dimensions of
the Pion heated regions for Lead Azide (Fig 2 Howittite. A mixt of PA, K chlorate and Na
of Ref 9) and for RDX (Fig 3 of Ref 9) are nitrate, which proved to be very sensitive and
smaller than the critical hot spot dimension at unstable. It was not authorized in England
the corresponding temperatures Ref 1) Cundill (1889) in MP 6, 15 (1893)
Written by J. ROTH 2) Daniel (1902), 378
Refs: 1) Bowden.,& Yoffe (1952), Chapters II,
III & Iv 2) Bowden & Yoffe (1958), Chap- Howitzer. See under Cannon,. Gun, Howitzer,
ters IV, V & VII 3) Cook (1958), Chapter 8 Mortar, Rocket and Trench Mortar in Vol 2,
4) C.H. Johansson et al, ProcRoySoc A246, p C27-L
160 (1958) & CA 52, 21106 (1958) 5) V.K.
Bobolev & L.C. Bolhkovitinov, IzvAkadNauk, HOX. Code name for D1- or Bis (2,2 ,2-Trinitro-
SSSR (1960), 754 &CA 56, 10438 (1962) ethyl) nitramine (BTNEN) described under
6) J. Zinn, JChemPhys 36 (7) 1949 (1962) ‘ Diethylamine and Derivatives in Vol 5 of Encycl,
&CA 57,4921 (1963) 7) F.P. Bowden, pp D1224-R to D1225-L
Proc 9th InternatSymp on Combustion, p
499–515, Academic PreV (1963) 8) C.L. HS. Chemical warfare symbol (CWS) for
Mader, Phys Fluids 6 (3) 375 (1963) & CA “Mustard Gas”. See under H in VO1 2, p C 168-L
58, 8844 (1963) 9) J. Cerny & J.V.R. Kauf-
man, JChemPhys 40 (6), 1736 (1964) & CA Hs ( Henschel) Missiles. The following types were
60, 10467 (1964) 10) C.L. Mader, Phys Fluids developed in Germany before and during WW 11:
8 (10) 1811 (1965) & CA 63, 16120 (1965) Hs117 (Henschel 117), also known as Schmetter-
11) J.H. Blackburn & L.B. Seely, Trans Farad Iing (Butterfly), was a rocket, propelled, radio -
SOC61, 537 (1965) & CA 62, 8924 (1965) controlled missile for use against bomber for-
12) J.N. Maycock & D.E. Grabenstein, Science, mations. Some versions were for ground-to-
152, 508 (1966) & CA 65, 562 (1966) 13) air and some air-to-air. It used liq fuel called
M.H. Friedman, Combustion & Flame 10, 112 Tonka and an oxygen carrier called Salbei (qv)
(1966) & CA 65, 10416 (1966) 14) A.G. (Ref 1, pp 196–201 & Ref 2, p Ger 93-L)
 H 176

Hs 293 (Henschel 293) was a” radio’controlled 17 inches; Initiation, Sensitivity to–min~um

missile released and directed to the target from detonating chge is 0.30g LA; Power by Ballistic
an aircraft. The model fully developed and Mortar 120% TNT; Rifle Bullet Impact Test in
used was the ~s 293 A-1. Other models such as 3/1 6“ steel–90% explns and 10% burnings;
Hs 293 A-2> Hs 293 B, HS 293 C, HS 293 D, Ditto in 1/8” A1–50% expls and 50% umf-
etc were not fully developed (Ref 1, pp 201-03 fected; Sand Test–See Brisance by Sand Test;
& Ref 2, p Ger 91-L) Sensitivity to Impact–See Impact Sensitivity;
Hs 298 (Henschel 298) was a rocket-propelled, Sensitivity to Initiation-See Initiation, Sensiti-
radio-controlled missile designed primarily as an vityy to; Stability Test–See Vacuum Stability
air-to-air weapon to be carried on fighter air- Test; Vacuum Stability Test at 120”–O.37CC
craft as well as the bomber types. There were of gas evolved in 40 hrs from 1 g sample; Ve-
several versions but the basic type was called locity of Detonation–See Detonation Rate;
Hs 298 V-2. It used a solid propellant (Ref 1, Viscosity, Efflux-24.8 Saybolt Seconds
pp 203-05 & Ref 2, p Ger 91-L) Method of manuf of HTA–3 is similar to
Afote 1: Salbei was a code name for either that used for Torpex, namely: purified TNT is
99.5% nitric acid or its mixt with 5-10% melted by heating’ it to ca 100° in a steam-
coned sulfuric acid, added to suppress corrosion jacketed kettle, equipped with a stirrer. Water
(Ref 1, pp 216 & 231 & Ref 2, p Ger 170-R) wet HMX is added slowly to molten TNT,
Note 2: Tonka was a liquid rocket fuel, such while continuing to stir it and to heat, until
as a mixt of crude m-xylidine 57 and Triethyl- all the water is evapd. Aluminum powder is
amine 43%(Ref 1, p 216 & Ref 2, p Ger 199-R) added and the mixture continued to be stirred
Refs: 1) TM 9-1985-2 (1953) 2) PATR 2510 until uniform and then cooled, with stirring,
(1958) to obtain a slurry suitable for pouring into shells
or bombs to serve as their bursting charges
HSC (Propellant). Same as Cordite HSC. See Refs: 1) G. Silvestro & H. Will HI, PA Instru-
under CORDITE in Vol 3 of Encycl, p C535-L mentation Rept 1232–58 (1958) (Suitability
of HTA–3 as HE) 2) Anon, AMCP 706–177
‘HTA. Abbrn for German mixture consisting of (1967), pp 178-81 & 362 (Torpex); (1971),
Hexogen (RDX), Trotyl (TNT) and Al pp 178–81
(aluminum). One of such mixts contd RDX 40,
TNT 40 and Al 20% HTA–3, Analytical Procedures. Accdg to Pris-
Refs: 1) G. Romer, “Reports on Explosives tera (Ref), up to 0.35% of Ca silicate may be
(Germany)”, PBL Rept 85160 (1946), p 15 used as an additive. The analysis of HTA–3
2) PATR 2510 (1958), p Ger 93-R may be conducted as follows: TNT is ex-
tracted with CC14;HMX is extracted with ace-
HTA-3 (USA). Designation of expl mixt con- tone; the residue is Al. If Ca silicate is present,
sisting of HMX 49, TNT ,29 & Al 22% (Type I); the residue is treated with 10% NaOH sohr and
HTA–3, Type 11 contains HMX 49, TNT 28.65, washed with water, the remainder is Ca silicide
Al 22 & Ca silicate 0.35%; mw 91, OB to C02– Refl Frank Pristera (Picatinny Arsenal), “Ex-
21%; cast, sp gr 1.90; Brisance by Sand Test plosives”, in Vol 12, p 449 of “Encyclopedia
6 1.3g crushed in 200g Bomb; Detonation Rate of Industrial Chemical Analysis”, J. Wiley, NY
for cast unconfined 1.0 inch diam chge 7866 (1971)
m/see; Explosion Temperature ca 370° (flames
erratically at 5 sees); Friction Pendulum Test– HTA-3, US Military Specification’s Require-
unaffected by fiber or steel shoe; Gas Volume ments and Testsare described in Spec MIL-E-
Evolved on Explosion 680cc/g; Heat of Com- 46495 A(MU) (Nov 1964) with Amendment 1
bustion 3687cal/g; Heat of Explosion 1190 (April 1972), entitled “Explosive Composition
cal/g; Heat of Formation, no value reported; HTA-3”, superseding MIL-E-46495(Ord) (Feb
Heat, Specific 0.245 cal/g/°C; Impact Sensiti- 1961)
vityy, 2kg Wt: Bur Mines app for 20mg sample, 1. SCOPE
no value reported; PicArsn App for 25mg sample 1.1 This specification covers an explosive com-
 H 177

position having two types (Type I and Type II) accurately weighed portion of approx 2.5g in
designated as HTA-3 for use in the loading of a 200 ml beaker and add 75ml of benzene satu-
warheads and other ammunition items. rated with HMX. Cover the beaker with a watch
1.2 Classification – Explosive Composition glass and place beaker and contents on a steam
HTA-3 shall be of the following types as specified: bath. Break up the lumps with a glass stirring
Type I – See Table II and 3.3 to 3.5 rod and agitate the solution occasionally by swirl-
Type II – See Table 11 and 3.3 to 3.5 ing. Remove the beaker and contents from the .
3. REQUIREMENTS steam bath when all of the TNT has dissolved,
3.1 Material – The raw materials used in as evidenced by the settling out of the other in-
the manufacture of the composition shall be in gredients. Cool to RT and falter the solution
accordance with the applicable specification in quantitatively thru a tared medium porosity
Table I filtering crucible. Transfer any of the insoluble
matter remaining in the beaker into the crucible
TABLE 1.
by using an additional 150ml of benzene saturated
Material Specifications with HMX. Draw air thru the crucible until the
Octol MIL-O-45445 – Type I (See 6.4) odor of benzene is no longer detectable. Dry
HMx MIL-H-45444 – Type I, Class 2 & 3 the crucible and contents in an oven maintained
TNT MIL-T-248 – Grade I, Type I at 100*5 T for one hour. Cool the crucible and
Aluminum MIL-A-512 – Type III, Grade F, contents in a desiccator and weigh. Retain the
Class 7 crucible and contents for the determinations
Ca Silicate MIL-C-51 077 which follow
Calculate the TNT content of the sample as
3.2 Composition – The composition of ‘HTA-3,
follows:
Type I and Type 11 shall conform to the appli-
cable chemical requirements specified in Table II
when tested as specified in the applicable para-
Where: A = Weight of residue in crucible, g
graphs
W ‘ Weight of sample, g
TABLE II M = Percent moisture, expressed as a
Percent Applicable decimal (4.3.2)
Material Type I Type H Paragraph 4.3.1.2 “HMX – Code No 05001 – Place
— —
the crucible and contents retained from the TNT
TNT 29.0 *2.O 28.65 *2.O 4.3.1.1
determination on a filtering apparatus and wash
HMx 49.012.O 49.0*2.O 4.3.1.2
with ten 20ml portions of aceto”ne. Allow each
Aluminum 22.0*2.O 22.0*2.O 4.3.1.4
portion of the acetone to remain in contact
Ca Silicate – 0.35*0.05 4.3.1.3
with the residue in the crucible for one minute
3.3 Moisture content – The moisture content before applying suction. Aspirate the crucible
of Composition HTA-3, Type I and Type II shall and contents until the odor of acetone is no
be 0.10 percent maximum, when tested as speci- longer detectable. Dry the crucible and contents
fied in 4.3.2 in an oven maintained at 100 *5°C for one hour.
3.4 Viscosity – The vixcosity of Composition Cool in a desiccator and weigh. Wash the cru-
HTA-3, Type I and Type II, shall be 15 efflux cible and contents with an additional 20rnl
seconds, maximum, when tested as specified in portion of acetone, and dry and weigh again.
4.3.3. See 6.6 Repeat the washings and weighings until con-
3.5 Density – The density (specific gravity) stant weight is obtained. Retain the crucible
of HTA-3, Type I and Type 11shall be 1.85 grams and contents for the determinations which follow
per cubic centimeter minimum when tested as Calculate the HMX content of the sample as
specified in 4.3.4. See 6.6 follows:
4. QUALITY ASSURANCE PROVISIONS.
See in Specification Percent HMX = w
4.3 TEST METHODS AND PROCEDURES Where: A = Weight of residue in crucible. re-
4.3.1 Composition tained from 4.3.1.1, g
4.3.1.1 TNT – Code No 04001 – Place an
 H 178

B = Weight of residue in crucible, g NOTE: Use”a chunk of ‘the sample to make

W = Weight of sample, g this determination. See 6.6 ~
M = Percent moisture, expressed as a‘ 5. Preparation for Delivery. See Specifi-
decimal (4.3.2) cation
6. Notes:
4.3.1.3 Calcium Silicate – Code No 06001 ‘
6.3 Intended use of HTA-3. As a ftier for
(applicable to Type II only) – Place the crucible
warheads . ,
and contents retained from the HMX determi-
6.4 HTA-3 can be made from Octol and the
nation on a faltering apparatus ,and wash with ten
addn of TNT, Al~& Ca silicate to conform to
10n-d portions of the NaOH to remain in contact
the desired compn
with the residue in the crucible for one minute
6.5 Calculation of control limits. See spe-
before applying suction. Caution should be
cification
exercised “when performing this procedure to
6.6 The determination of density and vis-
preclude a too vigorous reaction between the
cosity is not necessary when the HTA-3 is
aluminum and the NaOH. Aspirate the crucible
manufd at the time of loading
and contents for a minimum of five minutes.
Washthe, crucible and contents with five 20ml
portions of distd water. Dry the crucible and HTP (High Test Peroxide). See under Hydrogen
contents in. an oven maintained at 100 ~5°C for Peroxide in this Vol
one hour or ,until constant weight is obtained.
Cool in a desiccator and weigh
Calculate the .Calcium Silicate content of the Hubner Powder. Smokeless powder prepd by
sample as follows: gelatinizing NC with a solution of potassium
100 c xanthogenate in alcoholic ether and adding 2-5%
‘ercent Ca ‘flfite = W–(MW) of nitronaphthol and nitromolasses or nitrosugar
-where: C = Weight of residue in crucible, g Refi Dariiel (1902), 378
W= Weight of sample, g
M= Percent moisture, expressed as a
decimal (4.3.2) Hudson Explosive. Explosive mixture intended
4.3.1.4 Aluminum - Code No 07001 for use as a bursting charge in shells and prepd
Calculate the aluminum content as follows: in the USA in 1889 by mixing NG with NC,
Percent Aluminum = 1OO–(A+B+C) previously dissolved in acetone, ethyl acetate or
Where: A = Percent TNT (4.3.1.1) ether-alcohol mixture
B = Percent HMX (4.3:1.2) Refi Daniel (1902) 378
C.= Percent Calcium Silicate (4.3.1 .3)
4.3.2 Determination of moisture content
4.3.2.1 Special solvent – The special sol- Hudson Maxim Explosive. An explosive patented
vent shall be equal volumes of anhydrous me- in the USA for loading HE shells. It was prepd
thanol and benzene thoroughly mixed. If by blending NC 30-40 with NG 70-60. After
necessary the s,olvents shall be dried by distil- the mass hardened it was pulverized and
lation thoroughly mixed with 3-4 parts of wet, finely
4.3.2.2 Method – Determine the moisture pulped Guncotton
content in accordance with Method No 101.4 Ref: Van Gelder & Schlatter (1927), 933
which is described in Specification MIL-STD-65 O,
using solvent indicated in 4.3.2.1
4.3.3 Viscosity – Determine the vlscosit y Huff-Duff (HFDF–High-frequency direction
(efflux) in accordance with Method No 212.1 finder). An electronic long-distance device
which is described in Specification MIL-STD- developed by Americans during WWH which
650. See 6.6 permitted spotting within a split second any ship
4.3.4 Density – Determine the .density in (such as submarine), or plane at distances much
accordance with Method No 203.1 described greater than radar’s capability
in Specification MIL-STD-650 Rejl Staff, ArmyOrdn 30, 280 (1956)

o
 H 179

Hugoniots, more properly called Rankine- The curve (c) is a plot of Eq (l); curve (b)
Hugoniots or R-H relations, are a series of is a plot of a combination of Eqs 2 & 3; and
equations and/or curves that describe conditions curve (a) is empirical, although, in a way, it
at a ihock front. These are best illustrated represents Eq 3, particularly for metals. Here
by reference to an idealized plane shock, such a. is the bulk sound velocity in the medium
as the one shown in ,Fig 1, and the following ahead of the shock
set of eqns that describe this shock: As indicated in Fig 2, curve (a) is useful in
correlating experimental data, curve (b) is es-
BEHIND AHEAD
sentially a stress-strain curve, although it has
PARTICiE VELOCITY u Uo. o other interesting features which will be dis-
I cussed later, and curve (c) is most useful in
PRESSURE P P.
considering shock and rarefaction effects
II
OENSITY P.lN u Po= lNO across boundaries of different media
d Examination of Eqs 1–3, reveals that the
lNITRNAL ENERGY E E. simultaneous measurement of any two shock
TEMPERATURE T 10
variables is sufficient to completely specify
the remaining variables, provided that initial
conditions in the unshocked medium are known.
No satisfactory methods of measuring V or p
PIANE SHOCK FRONTd are known for condensed media, therefore
Fig 1 Steady plane shock front measurements must be restricted to U, u & P.
propagating into undisturbed In Vol 4 of this Encyclopedia methods of
materials in laboratory coordinates measuring U, u & P are described on p D333,
p D446 & D485. Theoretical Hugoniot curves
P–Po=pouu (1) for detonation products are shown on pp
U* =v;(P–Po)/vo –v (2) D706 & 707. More recent methods are re-
U=(l –p. /p )U (3) viewed in Ref 21 & 22. A novel electro-
E–EO = l/2(Vo–V)(P+PO) (4) magnetic method for measuring u is described
by Jacobs & Edwards (Ref 20)
An excellent compendium of shock Hugoniot
Of these sets of equations it is Eq 4 that is data has been prepared by LRL (Ref 14). It
commonly called the Hugoniot equation. Graph- includes some of the earlier Hugoniot data for
ical representations of these equations (R-H explosives. These data as well as more recent
curves), taken from Ref 20, are shown in Fig 2 data are summarized in Table 1 in the form
of least square fits to the empirical equation
in Fig 2a
(a) (b) (c)
Most of the data in Table 1 is for granular
explosive compacts. It must be pointed out that
defining shock parameters for heterogeneous
pellets consisting of explosive granules and air
pockets present conceptual difficulties. At best
the shock Hugoniots for such materials are
useful only. for describing the gross hydro-
dynamic behavior of granular explosives. It can-
PARTICLS vrLocll-f. u SP. VOLMC V PARTICLS vELOCITY, u not be expected that the methods of continuum
(al u-u ml P-v (cl P-u hydrodynamios applied to discontinuous media
(CWRIMNTAL
DATA OISPLAVI
(STRESS-STRAIN
CURVEI
(WAVS INSIRACTION
SOLUTIONSI
will yield any information on the fine structure
of the state variables of the shocked explosive.
Fig 2 Alternative Hugoniot curves
 H 180

/u Table 1
“Unreacted” Hugoniot Data for Condensed Explosives

U = ao+ SU* Range of

u for
ao+ s+ exp data
HE (gacc) ~o:? (mmjusec). mm/usec)

AN 0.86 25 0.84 (a) 1.42 (a) 0.81-2.32

76/24 Baratol 2.63 “25 2.79 + 0.5 1.25 (a) 0.0-2.7
Comp B 1.70 25 3.0 +–0.4 1.73 (a) 0.0-1.5
II 1.68 25 2.71-2 0.05 1.86 + 0.07 0.0-0.9
1.78 25 2.45 + 0.04 1.89 ~0.06 0.0-1.2
H-6 1.76 25 2.83 + 0.07 1.70 + 0.08 0.0-1.1
H-6 1.76 25 2.65 ‘(a) 1.98 ‘(a) 0.0-2.0
HBX-1 1.75 25 2.93 f 0.08 1.65 ~ 0.10 0.0-1.0
HBX-3 1.85 25 3.13 ~0.02 1.61 ~0.02 0.0-1.0
HNS 1.38 25 0.61 + 0.21 2.77 + 1.09 0.0-0.5
HNS 1.57 25 1.00 T 0.05 3.21 ~0.10 0.0-0.7
HNS 1.46 260 ‘See Table 4 of-Ref 18
LX- 04 1.86 25 -2.7 (a)’ -1.9 (a) 0.0-0.6
1.86 2.36 (a) 2.5 (a) 0.0-0.4
NM 1.14 25 2.00 (a) 1.38 (a) 0.0-1.8
NM 1.14 25 -1.6 (a) 1.65 (a) ‘ 1.0-1.7
75/25 Octol 1.80 25 3.01 ~o.4 1.72 (a) 0.0-1.2
PBX 9404 1.84 25’ 2.45 + 0.21 2.48 + 0.11. 0.0-1.45
PBX 9404 1.84 25 2.31 ‘(b) 2.77 ‘(b) 0.0-2.00
PBX 9404 1.77 150 1.85 ~0.54 3.47 + 0.81 0.0-0.8
~O\50 Pentolite 1.67 25 2.83 ~0.4 1.91 (a) 0.0-”1.2
PETN 0.82 25 0.47 ‘(a) 1.73 (a) 0.76-3.50
PETN 1.0 25 ~0.76 (a) ‘0.66 (a) 0.28-0.42
PETN 1.59 25 1.33 + 0.08 2.18 + 0.27 0.03-0.37
PETN 1.60 25 1.32 ‘(a) 2.58 ‘(a) 0.2-0.4
PETN 1.72 25 1.83 (a) 3.45 (a) 0.2-0.6
PETN 1.55 110 -0.6 ~0.5 8.7 + 1.7 0.24-0.29
NIX 1.0 25 0.40 (a) 2.00 a 0.44-2.60
RDX 1.54 25 .0.7 (a) ‘3.2 Ia ) 0.25-0.6
RDx 1.58 180 0.71 + 0.24 4.22 + 0.42 0.25-0.32
RDx 1.64 25 0.70 ~0.18 4.11 +-0.37 0.35-0.47
RDx 1.80 25 2.87 ‘(a) 1.61 ‘(a) 0.75-1.6
RDx 1.64 25 1.93 + 0.05 0.666+ 0.168 0.11-0.35

RDX/EXON 94/6 1.60 25 1.33 (c) 1.99 (c) 0.35-0.93

TATB 1.85 25 2.34 ~0.07 2.32 ~0.Q8 0.3-1.4

(Continued)
 H 181

(Continuation)

Table 1
““Unreacted” Hugoniot Data for Condensed Explosives

* Range of
u = ao+ Su
u for
an+ s+ exp data
HE (9?CC) ( c’:; (mrn7psec). [rndusec)
Tetryl 25 0.35 (a) 1.35 (a) 0.76-2.80
Tetryl :20 25 2.16 (d) 1.438 0.499(d 0.3-1.1
Tetr~l 1.40 25 1.61 (d) 1.978 I 0.278(d 0.3-1.25

I
Tetryl 1.50 25 2.17 (dj 1.628 0.341(tl 0.3-1.0
Tetryl 1.60 25 2.36 (d) 1.538 0.255(d 0.3-1.25
Tetryl 1.70 25 2.48 (C) 1.42 (C) 0.4-1.2
TNB 1.64 25 2.32 ~0.07 2.03:0.12 0.0-0.75

TNT 1.0 25 See Ref 15

TNT 1.62 25 2.93 (a) 1.61 (a) 0.75-1.6
TNT 1.63 25 2.57 (a) 1.88 (a) 0.0-1.25
TNT 1.62 25 2.27 + 0.30 2.65 (a) 0.0-0.6
TNT 1.62 25 2.99 ‘(a) 1.36 (a) 1.0-1.5
TNT 1.61 25 2.39 + 0.03 2.05 + 0.03 0.0-1.4
TNT 1,64 25 2.08 ~0.13 2.3 ‘(a) 0.2-1.4
TNT 1.64 25 2.4 (a) 2.1 (a) 0.1-0.5

TNT (liq) 1.47 92 2.14 (a) 1.57 (a) 0.8-1.7

*u = shock velocity, aO = bulk sound velocity, u.= particle velocity in

the HE. S is a constant

t: terms are twice std deviation .

(a)std deviation not given in RefS
(b)based on widely divergent data
(c)although std deviations are not given, data points agree very closely
with this fit
(d) u = a: + SU’ - S“\U; thus “ao” column gives .ao’, & “S” colunm
gives S’ & S“

Moreover, chemical reaction in or near the A commonly encountered problem is that of

shock front can cause additional complications. a shock or rarefaction traveling from one
Nevertheless, the data in Table 1 can be very medium into another. To solve such problems
useful as will be shown below, even though, one converts the U-u data of Table 1 or Ref 14
aside from conceptual problems, there is some into P-u data via Eq 1. Then the problem is
inconsistency in the data for some of the readily solved by graphical means as illustrated
explosives. in Figs,3 &4 (taken from Ref21)
 H 182

MATERIAL L MATERIAL R
MATERIAL L MATERIAL R
‘1

-t‘JI ‘i —Po, uo”o

‘i
2 ‘1 PO,“0 l o I-INTERFACE
---l NIERFACE
(d PRESSURE-DISTANCE PROFILE BEFOREINTERACTION
[a) PRESSURE-OISTANCE PROFI LE BEFOREINTERACTION

i ! \/
HUCUNIOT FOR MATERIAL R

HU@NIOT FOR

a.
HUGONIOT FOR
L* MAIZRIAL R
&
2
CHARACTERISTIC
g
FOR MATERIALL

CHARACTERISTIC
FOR MATERI,AL L STATI O
PARTICII WLOCITY, U
STATEO
PARTICLE VELOCITY. U (b) GRAPHI CAL p-u SOLUTION
(b) GRAPHICAL P-u SOLUTION

‘1 U2 I ‘2 LPO, Uo=o
l-INTERFACE
(c) PRESSURE-DISTANCE PROFILE AFTER INTERACTION (cI PRESSURE-OISTANCEPROFILE AFiTR INTERACTION
Fig 3 Transmission of a plane shock wave Fig 4 Transmission of a plane shock wave
into a material of lower impedance into a material of higher impedance

Shock impedance is the product @U and

graphically it is represented by the slopes of
the broken lines in Figs 3 & 4. Note that in
Fig 3 the reflected wave is a rarefaction rather
than a shock. Figure 5 (also from Ref 21) is
a useful summary of shock effects in metals,
rocks, plastics etc in contact with some
common explosives
 H 183

0 CM Lo 1.5 2D 2.5 3.0 35 40

u. mm/pscc

Fig 5 Shock waves induced in various materials

by normally-incident plane detonation waves

Other interesting properties of Hugoniots are

best viewed in the P-V plane. Figure 6 (taken
from Ref 6) is an enlarged and more detailed
view of Fig 2b
( (PI’ ~1,~1) ~ Wasteheatprod.wd
in shock cycle
(= energy dissipated)
Fig 6 The Rankine-Hugoniot curve defines
states that can be induced in substance by shock \ ,,
compression in terms of pressure (p), specific c1 \
volume (V), and internal energy (E). Shock Rayleigh-Mikhel’son Line
“\\
compression from initial state B to shocked state T % #
C follows the R-H curve and dissipates energy ~ ,.’ ‘.x

\ -s\
~ i
shown by the hatched area. Thus shock com- i ~,’”.\
‘\\
pression is not a reversible process–unlike adia- ~ $%””1 “., Adiabac
batic compression, which is, at least ideally re- I \ ‘\\
versible ~ Rankine-Hugonlot
I
I
‘I!PO’VO’EO)
-,
I .. . . .
D’ A
volume ~
 H184

Quoting Duvall (Ref 6): “Figure 6 gives the thermodynamic consequences of shock Hugoniot
locus of all states (pI, u,, El , and so on) that data and what additional information is required
can be reached from an initial state @o, VO, EO) to specify an equation of state for the shocked
by shock compression. In an analogous way, the medium
ordinary adiabat or adiabatic curve may be de- Some very interesting information obtainable
fined as the locus of all states that can be reached from Hugoniot data is dramatically illustrated in
by adiabatic compression Fig 7 which is a plot of experimental P-V data
At the point B, which represents initial un- (taken from Ref 15) for lg/cc TNT
shocked conditions in the material (PO, VO,EO),
the R-H curve and the adiabat have the same
P
~bdi
slope and curvature, but only at that point:
at all higher pressures the R-H curve lies below
So
the adiabat, because unlike adiabatic compression,
shock compression dissipates energy, and is,
therefore, irreversible 4’0
As shown in Fig 6, the increase in internal
energy in a shock whose pressure amplitude is bo
PI is represented by area ABCD. Loss of energy
in a shock can be illustrated by comparing this
area thermodynamically with that associated with so
a weaker shock, area ABC’D~ for example. It
can also be shown by simple calculation that 40
just as the internal energy increases or decreases
as the shock is stronger or weaker, so the
entropy of the final shocked state also increases 30
with the shock strength. Although such cal-
culations are valuable in computing the entropy .!0
of the shocked state, they are insufficient for
calculating the total energy dissipation resulting
from passage of the shock wave. “However, re- {0 /
ferring again to Fig 6, the hatched area–bounded /
below by the Rankine-Hugoniot curve and above / v Cclg
by the Rayleigh-Mikhel’ son line, a straight line
I& 1 1
0,S + 0,? 0,% 0,9
connecting the initial, unshocked point B with
the final shocked state C – is a fair approxima- Fig 7 P-V Hugoniot for 1 g/cc TNT
tion to the energy dissipated in the shock cycle.
But specifically this area is the waste heat of the Here the TNT sample is compressed at very
cycle, not the energy dissipated. It is difficult low pressures from V=l cc/g to V~.62 cc/g
to determine an exact expression for energy (crystal density). Further compression (increase
dissipated because thermal. stresses are left in pressure) then causes the sample to expand~
behind in the material, even after the shock This can only mean that some heat effect is
pressure has been relieved. Therefore, a precise overcoming this compression. Since it can be
calcu~ation of the true energy dissipation in a shown that uniform shock heating at pressures
decaying shock must account for hard-to-evaluate of the order of a few kbars is very small, this
effects of thermally induced after-flow in the heat effect must be produced by exothermic
material. In practice we settle for the waste chemical reaction at or very near the shock
heat approximation” front. Thus shock Hugoniots for reactive materials
Duvall (Ref 5) also provides further discussion can provide information on the presence or
of P-V Hugoniot curves, eg the manifestations of absence of chemical reaction at the shock front
multiple shocks, phase transitions, elastic limits
etc. Cowperthwaite (Ref 11) considers the Written by J. ROTH
 H 185

See also Hugoniot in Vol 4, pp D278-R to Hulls, Nitrated. Kriiger studied the action of
D281-R and pp D604-L to D60:7-R concd(d 1.52) nitric acid on a variety of plant
Refs: 1) W.B. Garn, JChemPhys 32, 653 (1960) hulls, such as those of chestnuts, walnuts, plum-
& CA 54, 14687 (1960) 2) V.S. Ilyukhin pits, etc, After 12 hours at -10° in the acid
et al, DoklAkadNauk, SSSR, 131 (4), 793 a considerable portion of the hulls dissolved
(1960) & CA not, found 3) A.W. Campbell leaving a residue (40-60% of the original weight)
et al, PhysFluids 4 (4), 498 (1961) & CA not that contained 11- 1270N primarily in the form
found also B. G. Craig, LASL Rept GMX-8- of nitrate esters. When water was added the
M2-62-4 (1962) 4) G.E. Seay et al, JAppl dissolved material, a slimy precipitate was
Phys 32 (6), 1092 (1961) & CA 55, 25254 formed. It also contained N but less than the
(1961) 5) G.E. Duvall, Bull Seism Soc of residue. Moreover this N was only partly in the
America 52 (4), 869 (1962) & CA not found form of nitrates
6) G.E. Duvall, Science & Technology (April Rejl W. Kriiger Ber 73B, 493 (1940) & CA 34,
1963) & CA not found 7) R.J. Wasley et al, 6580 (1940)
Preprints 4th Deton Symp (Ott 1965) p B-109
8) J.B. Ramsay et al, Proc 4th Deton Symp Humidification and Humidity. The amount of
(Ott 1965) ONR, ACR-126, p 233 9) V.M. water vapor in air is referred to as the humidity
Boyle et al, Ibid, 241 10) N.L. Coleburn et al, of air. The controlled increase in humidity is
JChemPhys 44 (5), 1929 (1966) & CA 64, called humidification. The actual moisture con-
11019 (1966) 11) M. Cowperthwaite, AmJPhys tent in air is called absolute humidity, and the
34 (1 1), 1025 (1966) & CA 66, 22443 (1967) ratio of the weight of water vapor to the
12) I. E.Lindstrom, JApplPhys 37 (13), 4873 weight of water vapor in moisture-saturated air at
(1966) & CA 66, 39481 (1967) 13) the same temp (expressed in %) is called
Anon, SRI Prog Rept 66-2 “Sensitivity Funda- relative humidity (RH)
mentals,” 39 (1966) 14) M. Van Thiel Humidity can affect explosives and propellants
UCRL 50108 “Compendium of Shock Wave both adversely and beneficently. If the humidity
Data” (1966) & CA 69, 99685 (1968) is very high, an explosive can pick up enough
15) L.C. Bolkhovitinov, 12th Combstn Symp, moisture to cause it to ‘deteriorate or mal-
(1969) & CA 74, 143971 (1971) 16) I.E. function. A prime example of this is Ammonium
Lindstrom, JApplPhys 41, 337 (1970) & CA Nitrate which must be stored and handled in
72, 80972 (1970) 17) D. Stirpe et al, special dehumidified areas to prevent caking. The
JApplPhys 41, 3384 (1970) & CA 73, 89722 humidity above which a substance deliquesces,
(1970) 18) J. Roth, Proc 5th Deton Symp or below which it ceases to be hydroscopic is
(Aug 1970) ONR, ACR-1 84, pp 221-23 called the critical relative htimidity (CRH).
19) V.M. Boyle et al, Ibid, pp 254-56 20) It is equal to the humidity in equilibrium with
S.J. Jacobs et al, Ibid, pp 413--26 21) O.E. a saturated solution of the substance at a given
Jones, Proc 12th Annual Symp on Behavior temperature
& Utilization of Explosive in Engineering Design On the other hand, humidification can pre-
(March 1972); pp 130-138 22) J.P. Sumner, vent buildup of dangerous electrostatic charges.
Ibid, pp 225-34 23) Anon AMCP 706-180 This is especially important in the handling
“Principles of Explosive Behavior” (April 1972) of such primary explosives as Pb Azide or
Styphnate. General references on humidity con-
Huile de Nobel. Fr for NC trol & humidification are Refs 2, 4, 5 & 6
CRHS can be used to determine whether a
Huile ditonante, ou Huile explosive. Fr for one material will deliquescedor if it has a tendency to
of the names for Nitroglycerin. cake. Thus if the RH>CRH the substance will
pick up ‘moisture from the air (deliquesced) until
Hull. The outer covering or husk of any seed or
the vapor pressure of water in the deliquescing
fruit. Some of these substances, for instance, material equals the partial pressure of water in
walnut or cocoanut hulls (shells) can be ni- the surrounding air. Conversely, if RH< CRH
trated and probably would produce explosives any moisture in the material will tend to escape
resembling NC or NS
 H 186

# Critical Relative Humidities for Some Explosives and

‘\
\ for Ingredients of Explosive and Pyrotechnic Compositions

v’ Temperature “C
/ Substance 10 20 30 40 Other temperatures
Ammonium chloride, N% Cl 75.3 69.8 59.4 52.5 48.4 at 50°
,, bichromate (NH4)2Cr207 98. l(c)
,> nitrate, NHq N03 75.0 66 60 53 48.6 at 50”
>, oxalate, (NH4 )2 Cz Oq – 98.9(h)
>> perchlorate, NH4C 10Q 95.6(c)
,9 permanganate, (NHQ)Z Mn04 ,99.1 (c)
?> sulfate, (NW )2 S04 79.4 80 81 79 75 at 108.2°
Barium chloride, BaClz .2H20 — 88.O(g)
>, nitrate, Ba(N03 )2 —
98.8 97.7 –
Calcium chloride, CaC12.6HZ O 38.0 32.3 – —,
,> nitrate, Ca(N03)2 .4H *O 66 56 51 46
,, sulfate, CaSOo .5H20 — —
98 –
Cobalt chloride, COC12.6H2 O 72.5(d) 67.3 61.9 56.6 49 at 55°

Copper nitrate, CU(N03 )2 — 75(d)

Hexose, C6H12 06 .l/2H20 57(b) 56(f) 55(i)
Lead nitrate, Pb(N03 )2 99 98 96.5 95.5 88.4 at 103.5°
Magnesium chloride, MgC12.6H2 O 34.7 33.1 31.7 31.3 28 at 71°
,, nitrate, Mg(N03 )2. 6HZ O 56(e)
Mercuric Fulminate, Hg(ONC)2 99.9(b)
Oxalic acid, Hz Cz OQ.2H2 O — 76.0
Potassium chlorate, KC 103 98.O(h)
,7
chloride, KC1 87.4 86.3 84.5 82.8 74.7 at 100°
,, chromate, Kz CrOo — —
88 –
,> bichromate, K.@207 — —
97.8 –
,, nitrate, KN03 95.1 94.2 92.5 89.4 61.2at 110°
,, perchlorate, KC1 Oa 99.8(c)
“ sodium tartrate, KNa~ ~ O ~ .4H20 87~5” – 87.1 86
,. sulfate, KZSOQ 98.2 97.1 96.6 96.1 93 at 102.1°
>, sulfocyanate, KCNS — 47.0 – —
,> tartrate, Kz CqHq 06. %Hz O – 75(c) – 73
Sodium chlorate, NaC103 98.8(b) – – —
>, chloride, NaCl 76.9 75.8 75.1 74.4 73.7 at 100°
,? bichromate, Na2C~207 — 52 – —
,7 nitrate, NaN03 77.7 77.5 73.2 70.5 62at71°
,, sulfate, Na2SOa —
93(j) – –
,, tartrate, Na2~ ~ 06. Hz O – 92.5 91.1 90.7
Strontium nitrate, Sr(N03 )2 — 86 – —
Sugar, Cl~H2201 ~ — 85.O(h) – —
Urea, NH2 .C0.NH2 81.5 80.5 73.3 68.7 62.7 at 50°
Zinc chloride, ZnC12.xH2 O 10.O(b) – – —
“ nitrate, Zn(N03 )2. 6H2 O — 42.0 – —
“ sulfate, ZnS04. 7H2 O 94.7(a) 90 88.5(h) 84
a-at5° f-at 20°
b -at 12° g -at 24.5°
c-at 15° h -at 25°
d-at 18° i - at 35°
e-at 18.5° j -at room temp
 H 187

until equilibrium is established., Such evaporation Hunting Powders. See Sporting Powders
can produce caking. Obviously caking will be
strongly influenced by the original moisture Hurst. Patented in 1898 in the USA. The use of
content of the material NC in frozen form as bursting charge for pro-
The foregoing table (taken from Ref 1) giveS , jectiles
CRH for some explosives and ingredients of #d ,~%” Refi Daniel (1902) 379
explosive and pyrotechnicompositions - ~~
Practical measures for controlling explosive Hybalines. A family of novel metal hydride
dusts by humidification are discussed in Ref 3 coordination compds, both liq & solid, trade
Ignition lag times of pyrophoric substances name of Union Carbide Corp, New York. The
such as Al(BHa )3, AlMe3, BEt3, etc were found company’s R & D program at its South
to increase (except for BEt3 ) with decreasing Charleston, West Virginia technical center sug-
humidity. In fact, A1(BHQ)3 is not pyrophoric in gests Hybalines may find use as high-energy
dry air (Ref 4) liq fuels and as additives in high-energy solid
Suppression of firedamp and coal dust ex- proplnts
plosions, in high humidity coal mines, by stone Carbide is proposing a new concept of
dusting is affected by humidity. Agglomeration solid proplnt grain construction. The process
of moisture content of the dusting material uses std ingredients, yet the grain burns more
influenced its effectiveness as explosion suppressor. efficiently and can be fabricated faster than
Salt dusts become ineffective above 80% relative with convential methods. There also exists
humidity because they dissolve (Ref 7) a group of binders trademarked Carbitron
Refs: 1) Cmelin (8th Ed, 1936) p 122 2) which may find use in solid proplnts because
Unit Operations Rev “Absorption and Humidi- of their superior physical & ballistic props
fication” IEC (1947-1960) 3) H. R. Brown, Refs: 1) Staff, C&EN 40 (26), p 24 (25 June
Safety Engineer 94 14, 32 (1947) & CA 41, 1962) 2) Staff, “Physical & Chemical Studies
7119 (1947) 4) M. Guinet, Rech Aeronaut of Hybaline A5 Fuel,” Progress Rept No. 2,
(Paris) 76, 25 (1960) & CA 54, 25826 (1960) RTD-TDR-63-1021, Air Force Systems Corn
5) F. A. Holland, BritChemEng 9, 678 (1964) mand, Res & Technology Div (March 1963)
& CA 61, 15691 (1964) 6) E. J. Amdur (Ed) (Conf, not used as a source of info)
“Humidity and Moisture: Control in Science and
Industry,” Reinhold, NY (1965) & CA 63, 1501 Hybrid Rocket Propellants. A special proplnt
(1965) 7) A. K. Ghosh & M. L. Mahato, combination of unlike materials, particularly
JMineMetals Fuels 14 (11) 351 (1967) of unlike physical characteristics. Typical hybrid
proplnt combinations are a solid fuel (or
Hummel (Bumble Bee). Nickname for a self- oxidizer) in combination with a liquid
propelled mount consisting of’ 150mm Medium oxidizer (or fuel) in that order. Sometimes a
Howitzer on the chassis of a PzKpfw HI/IV tank. grain of solid fuel is encased in the com-
(See also under Panzer) bustion chamber of a rocket engine and
Rejl PATR 2510 (1958), p Ger 93-L burned in combination with liq oxygen. Sim-
ilarly, a liq fuel may be injected into a com-
Humus. Decayed products of plant life, such as bustion chamber in contact with a solid
Ieafmolds, rotten wood, rotten straw, etc. It has oxidizer. Another example is the use of
been used as an ingredient of some explosive concentrated hydrogen peroxide and a hydro-
mixtures, as for instance of Bracket Sporting carbon fuel. In this case, the hydrogen
powder, manufactured in the USA, and which peroxide is converted by decompn into a
contained 18.9% of humus, according to the hot gas contg oxygen. The fuel is injected
analysis by Munroe downstream of the first reaction, mixed with
Rejl Daniel (1902) 82 the hot oxidizer-rich gas, and burns (Ref 1)
Hybrid rocket proplnts & hybrid technology
Hungarian Ammunition, Explosives and Weapons. provide a number of propulsion-system capa-
We have no information on post WWll Hun- bilities in combinations not readily achievable
garian ammunition, expls & weapons with all-solid or all-liq systems. Foremost among
 + H 188
\
$

capabilities are throttling, safety, smokelessness, (pH 5). Can be prepd either by nitrating hy~
~ and low development cost (Ref 7) dantoin with mixed nitric-acetic acid or by dis-
Refs: 1) Rocket Encycl (1959), p 209 2) solving hydantoin (15g) in white nitric (50ml),
North American Aviation Inc, Rocketdyne Div, followed by evaporation of the soln to dryness
“Research in Hybrid Combustion,” Summary on a steam bath
Rept R-3446 (Dee 1960 thru Nov 1961) It is a mild expl of satisfactory thermal
[Contract Nonr 3016(00)] 3) Hybrid Pro- stability and with sensitivity to impact com-
pulsion Systems Symposium. Presentations held parable to that of TNT. Its heat of combstn
at Washington, DC (4-5 October 1961). Spon- is 295kcal/mol
sored by the Bureau of Naval Weapons. Pub- Refs: 1) Beil 24, 259 2) A.P.N. Franchimont
lished by the Liquid Propellant Information & E.A. Klobbie, Rec 7, 236 (1888) 3) E.C.
Agency, Applied Physics Laboratory (Conf) Wanger & J.K. Simons, JChemEducn 13, 266
4) Thiokol Chemical Corp, Reaction Motors (1936) 4) R.Adams & C.S. Marvel, OSRD 86 “
Div, “Study of Reverse Hybrid Propulsion (1941), pp 1, 7–8 & 20–22
System,” Rept R MD 5021, QTSR-1 (Ott to No Azido- or Polynitro-derivs of Hydantoin are
Dec 1962) [Contract N600(19)-59314] (Conf) found in Beil or CA thru 1971
5) North American Aviation Inc, Rocketdyne
Div, “Research in Hybrid Combustion,” Final Hydral-cellulose, (~ H,0 O ~) ~“H20, mw 666.58. “
Rept R-5179 (Dee 1961 thru Jan 1963). May be prepd by digesting cellulose, such as filter
[Contract 301 6(00)] 6) United Aircraft Corp, paper, with a solution of H ~0 ~ until completely
United Technology Center, “Investigation of disintegrated. On evaporation, a white substance
Fundamental Phenomena in Hybrid Propulsion,” is obtained which resembles “oxycellulose” in its
Rept UTC-2007-QT7 (Dee 1962 thru Feb 1963) properties. When treat ed with 10% aqueous NaOH,
(Contract NOW 61-1 OOO-C) 7) D. D. Ordahl, 33% of it dissolves, leaving a residue resembling
57 (318), 448-49 (1973) (Hybrid Rocket cellulose
Proplnts) When cellulose is treated with concentrated
Hz 02 (60%) the resulting mixture is explosive I
(see Hydrogen Peroxide Explosives)
Hydantoin and Derivatives Refs: 1) Marshall 1 (1917), 154 2) A.W.
Hydantoin, Glycolylurea or Imidazoledione Schorger, “The Chemistry of Cellulose and
(called Lactam der Ureido-essigitiure in Ger), Wood”, McGraw-Hill (1926), pp 269, 270&
HN.CH2 .CO.NH.CO; mw 100.08, N 27.99%; ‘ 276 3) Marsh & Wood, Cellulose (1945),
colorless, odorless trysts, sp gr %, mp 220–21°, 253
bp ?; sol in hot w & alk; S1sol in ale; nearly in- Hydra Programs. HYDRA is a US Navy code
sol in eth. Was first prepd by Franchimont & “ name for all its studies & tests of sea-launched
Klobbie (Refs 1 & 2). Wagner & Simmons (Ref missile concepts & systems. To simulate nuclear
3) prepd it by two-step process from glycine, explns, Hydra programs have used them HEs
H2N.CH2 .H. Used as intermediate in manuf of (Pentolite) which form noncondensable gas I
pharmaceuticals, synthetic resins, lubricants, etc, bubbles. In an effort to more accurately simu-
Gives on nitration an expl late nuclear detonations, which form steam
Refs: 1) Beil 24, 242, (287) & [127] bubbles, two steam producing expls were
2) A.P.N. Franchimont & E.A. Klobbie, Rec 7, developed. These were an equal mixt by wt of
12 (1888) 3) E.C. Wagner & J.K. Simons, RDX & alum [AIN~ (SOq)2. 12HZO] and a
JChemEducn 13, 266 (1936) 4) CondChem- pressurized stoichiometric mixt of hydrogen &
Diet (1961), 582-R (Hydantoin); (1971), 450-L oxygen. Using Friedman’s formula for the
N-Nitrohydantoin or N-Nitroglycolylurea, bubble oscillation period and the experimentally
02 N.N.CH2 .CO.NH.CO; mw 145.08, N 28.96%, determined bubble periods from Hydra studies,
OB to C02 –38.6%; colorless, S1hydroscopic the energy partition (ie, fraction of chge
plates; sp gr ?, mp 170–710 (dec), bp–puffs energy left for bubble oscillation after shock
off and sometimes ignites at 225°, but does not passage) of the three expls were found to be:
explode. Dissolves in w giving an acidic soln
 H 189

Explosive r Refs: 1) Marshall 1 (1917), pp 153–54

Pentolite 0.45 f0.12 2) Marsh & Wood, Cellulose (1945), p 152
RDX + alum o.’5oto.l4
2H2 + 02 o.41to.11 Hydrated Explosives. Permissible explosives (ie
Since the min error variation in energy partition permissible for use in gassy mines) in which
is much greater than the variation due to type salts containing water of crystallization, such as
of expl, it makes little difference which expl MgSOa .7H20 with 51.22% HZO, Kz ~(SOo)a
is used to simulate the nuclear case (Ref 6) .24H20 with 45.57% Hz O, A12(SOQ)3. 18H20
See also Refs 1, 2, 3, 4, 5 & 7 for further with 48.81 % Hz O, CaS04 .2HZ O with 20.92%
details Hz O etc, are characteristic ingredients. Explo-
Refs: 1) W.G. Neall, “Radiological Safety Re- sives of this class are somewhat similar in com-
port. Hydra 1 at David Taylor Model Basin, position to the ordinary low-grade Dynamites
Washington, DC;’ Naval Radiological Defense (all of which contain NC as the principle
Lab Rept USN RDL-TR-423 (May 1960) 2) explosive ingredient and many contain Ammonium
J. W. Hendricks & D.L. Smith, “Above-and- Nitrate), except that one or more salts containing
Below-Si_rrface Effects of One-Pound Underwater water of crystallization are added to reduce
Explosions Hydra 1j“ Ibid, USNRDL-TR-480 flame temperature. These explosives are usually
(Ott 1960) 3) J. S. Hedge, “Hydra Program, easily detonated, produce only small quantities
Determination of the Total Thermal Radiant of poisonous gases and generally can be used
Energy Emitted by an Underwater Exploding successfully in damp working places. A typical
Wire;’ USNRDL-TR-612 (Jan 1963) 4) R, R. hydrated explosive has the following composition:
Buntzenj “Hydra Program. TIN NRDL Low- NG42, hydrated Mg or Na sulfate 46, wood-
Yleld Underwater Explosion Tank and Associated meal 12Y0. Its strength compared to blasting
Instrumentation,” USNRDL-TR-623 (Feb 1963) gelatin: 200ml lead block expansion and 1 lmm
5) K. W. Kaulum, “Hydra Program–Hydra HB crushing compared to 560CCand 24mm for
Series-Investigation by Water Sampling of the 92/8 blasting gelatin
Internal Structure of Columns Resulting from See also Permissible Dynamites in Vol 5,
Small Shallow Underwater Explosions,” Ibid, p D1604-Rff
USN RDL-TR-706 (Sept 1963) 6) M. Kaltwasser, Refs: 1) C. Hall & S. Howell, “Tests of
“Hydra Program–Theoretical and Experimental Permissible Explosives;’ USBur of Mines Bull
Determination of Energy Partition of Selected 66, Washington (1913), p 19 2) C. G. Storm,
Underwater Explosives,” USNRDL-TR-702 Analysis of Permissible Explosives, US Bur of
(Ott 1963) 7) W. W. Perkins, “Hydra Program. M Bull 96, Washington (1916), pp 5,6 3)
Hydra HA Series-The Above-Surface Phenomena Marshall 2 (1917), 605 4) Naorlm, NG
Created by 10000-Pound Underwater Detonat- (1928), 399
ions~’ DASA-1443 (Ott 1963) (Conf) (Not used
as a source of info) Hydraulic Coal Bursters are devices ining com-
pressed water for breaking down the coal. Some
Hydrated Cellulose, C12 Hzo 010 “Hz O, mw 342.30; of these devices are described in the book of
name proposed by Cross and Bevan for substances J. Taylor and P.F. Gay, “British Coal Mining
recovered from cellulose that has been mercerized Explosives”, G. Newnes Ltd, London (1958),
(by treatment with aqueous NaOH) and then pp 134–137
washed out, or that which has been converted
into viscose and then regenerated Hydrazide is a deriv of Hydrazine (qv) of general
The name “hydrated cellulose” is now con- formula MHN.NH2, where M means metal. One
sidered to be obsolete, and the term “dispersed” such compd, Sodium Hydrazide, NaHN.NH2, mw
cellulose has become more general (Refs 1 & 2). 54.04, N 5 1.85%, is extremely explosive. It
Hydrated cellulose gives off 1 mol of water at can be prepd by the action of Na on anhydrous
120-125° while hydrocellulose retains it hydrazine or from NaNH2 and hydrazine
obstinately (Ref 2). See also Amyloid in Vol 1, Refs: 1) Gmelins Handbuch, 8th ed (1936),
p A398-L Syst 23, p 537 2) C .C. Clark, “Hydrazine”,
Mathieson Chem Corp, Baltimore, Md (1953), p 4
 H 190

Hydrazides are compounds of the, type of combustion to water Iiq is 148.635 kcal/mole
RCONHNH2. It is claimed that during recovery (Ref 9). Sol in polar liquids such as water, al-
of pure anhydrous hydrazine from its mixtures cohol, ammonia & amines; insol in nonpolar
with NHq Cl & NH3, by treating the mixture with liquids such as ether, chlf, hydrocarbons and
a stoichiometric excess of alkali or alkaline earth halogenated hydrocarbons. It is strong reducing
metals in dil Iiq ammonia, a large excess of the agent and diacid base. Its vapor is explosive and
metal is to be avoided to prevent formation of toxic and especially dangerous to the eye (Refs
explosive hydrazides 18a, 27c and 32a) (See also under Toxicity)
Refs: 1) F. T. Neth USP 2,735,752 (1956) & Preparation.
CA. 50 8148 (1958) 2) No further refs to Anhydrous hydrazine was first prepd in 1894
explosive hydrazides was found in CA 1957-71 by Lobry de Bruyn, but its salts and derivs
were prepd beghming in 1875 by Emil Fischer,
Hydrazidicarboxylic Acid, Mercuric Ester. who coined the name “hydrazin”. The “hydra-
CG HIO 0aN2Hg; this powder is claimed to explode zine hydrate” was first prepd by Th. Curtius
on heating (total abstract) in 1887 (Ref 14a, p 1)
Refi R. Stoll~ Ber 45,273 (1912),& CA 6, 1005 Accdg to Clark (Ref 14a), only a small scale
(1912) operation was producing hydrazine prior to WWII
In WWII the Germans discovered that N2H4
Hydrazidioxalic Acid-Diazide(called Hydrazidi- was an excellerit rocket fuel when used with
oxalsable–diazid in Ger) N3 COCONHNHCOCON3 , hydrogen peroxide, oxygen or fuming nitric
mw 226.12, N 49.56%, OB –35.4; wh powd (from acid. They used hydrazine as the proplnt of
eth). Prepd by treating hydrazidioxalicacid-dihy dra- their first rocket plane
zide with nitric acid. Explodes on heating The synthesis developed in 1907 by Raschig
Refl Beil 2, (244) is the only preparative method that is now
used commercially to produce Nz ~ (Refs 3,
4 & 5). Sodium hypochlorite and NH3 are
Hydrazinate of Diammoniodecaborane or
first reacted to form chloramine according to:
Diammoniodecaborane (1,2) hydrazinate.
NH3,(BIOH12)NH3 -N2 ~; was prepd (Ref 1) by NaOCl + NH3 + NH2 Cl + NaOH
adding hydrazine to a suspension of Blo H12” 2MeCN Then hydrazine is formed by the action of
in benzene and refluxing the mixt. The benzene excess ammonia upon chloramine:
layer was decanted, the Nz ~ layer was heated,
NH2 Cl + NH3 + NaOH + Nz Hq + NaCl, + Hz O
EtOH was added & the mixt was cooled to
0° to ppt the salt. A suggested use is as a The Raschig synthesis yields a crude solution
propellant component. No properties given containing about 2$?0N2 Hq. After evaporating
Refi M.F. Hawthorne & A.R. Pitochelli, to precipitate sodium chloride, the purified
USP 3453092 (1969) & CA 71, 103742p hydrozine hydrate solution is distilled to yield
(1969) an azeotrope containing 58.5 mole% N2 Hq.
Commercial anhydrous hydrazine is produced
by an azetropic distillation using aniline
HYDRAZINE, ITS SALTS AND DERIVATIVES process (Ref 18). In the US, Mathieson Chem
Hydrazine, Anhydrous (Diamidogen or Diamide), Co began in 1947 research on the production
H2N.NH2; mw 32.05, N 87.43%, OB to C02 of anhyd hydrazine with emphasis directed to
– 100%; colorless, corrosive, fuming hydroscopic its use as a rocket fuel. After constructing a
liquid; sp gr 1.011 at 15°/4~Lange) or 1.004 at pilot plant, an installation for commercial pro-
25°/40 (Ref 18a); fr p 2.0°, bp 113.5°, fl p duction of hydrazine and its derivs was erected
(open cup) 126”F; RefrIndex 1.46979 at 22.3°. at Lake Charles, Louisiana
Vapor pressure can be calcd by the equation A modification of the Raschig synthesis
given in Ref 11; viscosity by the eqn given in uses urea in place of ammonia to synthesize
Ref 8, thermodynamic data is in Ref 12, heat N2 I& according to (Ref 12):
capacity of liquid is in Ref 2, heat capacity of NHZCONHZ + NaOCl + 2NaOH + Nz Hq. H20 +
gas is in Ref 11 and entropy is in Ref 11. Heat
NaCl + Naz COS
 H 191

Audrieth summarizes many other lab prepn Hydrazine demand is rising continuously.
methods based upon hyponitrous acid (H2N202 ), Apart from being a constituent of rocket fuels,
nitramide (NH2 N02 ), nitrosohydroxylamine it is used to remove oxygen from boiler water
[NH(NO)OH] derivatives, nitrosoamine (NH2NO) to prevent the corrosion of the vessels. If, as
derivatives, nitrosoketones, azo compounds, some believe, hydrazine-based fuel cells eventually
hydrazoic acid and azides, nitrogen and the come into commercial useYdemand will be enor-
decomposition of NH3 (Ref 12). In more recent mous. Hydrazine hydrate production in non-
work Anderson converted NH3 to N2 Hq by communist countries now stands at about
passing NH3 through a discharge tube using 25000 metric tons per year, of whicli 17000
high frequency radio waves (Ref 17). Yields in metric tons are used by the US with about
terms of energy input are discouragingly low. 7000 metric tons taken by the space programs.
Aerojet General has also studied a process US hydrazine capacity will be greatly increased
based upon thermal decomposition of NH3 in by the end of 1975 when Mobay’s 1000Omt/yr
a nuclear reactor but without achieving com- unit constructed at Baytown, Texas will be ready
mercial production (Ref 26) The reaction of the PCUK process is de-
Accdg to Ref 38, although the classical scribed more fully by Dr Schirmam on p 19-L
Raschig Process was improved by West Germany’s of Ref 38, while the additional advantages of
Bayer, many of its drawbacks still exist. These the process are listed by Dr S. Delavarenne on
include the environmental problem of disposing p 19-M
of the ahge quantity of by-product chloride, the Toxicology
current tight chlorine situation and sizable con- If spilled on the skin or in the eyes liquid
sumption of primary energy N2 ~ can cause severe local damage or burns
Now chemists at the Central Research Labo- and can cause dermatitis. In addition it can
ratories of Produits Chimiques Ugine Kuhlmann penetrate skin to cause systemic effects similar
(PCUK) at Lyons,, France, developed begiming to those produced when the compound is
in 1970, under the direction of Dr F. Weiss, a swallowed or inhaled. Inhalation of the vapor
novel continuous process for manufg hydrazine. causes local irritation of the respiratory tract
The process is based on the discovery that am- and eyes. On short exposure systemic effects
monia, hydrogen peroxide, and a carbonyl compd, involve the central nervous system. Resultant
such as methyl ethyl ketone, react in presence symptoms include tremors &, on exposure to
of an amide and catalytic quantities of a phos- higher concentrations, convulsions and possibly
phate to form an azine intermediate. This in- death follow. Repeated exposures may cause
termediate hydrolyzes quantitatively to hydrazine toxic damage to the liver (fatty liver) and
and to carbonyl compd which is recycled. The kidney (interstitial nephritis), as well as anemia.
yield is claimed to be better than 75% The threshold limit value of hydrazine is
The reaction proceeds as follows: 1 ppm (1.3 mg/m3 ) (Ref 20) (See also Refs
27c and 33a)
Uses
Ketone Ammonia Amino alcohol Imine 0xa2rane The use of N2 IL as a hyperbolic propellant

H2N~)c.N_&
Hydrazine Azine \
‘=0 ;&H2
Ketone Hydrazone
fuel for rocket propulsion is discussed in detail
in this Vol under Hyperbolic Propellants. It has
also been used extensively as a monopropellant
e fuel or in combination with hydrazine nitrate
Accdg to PCUK’S Dr J.P. Schirmann, the new
and/or water as a thruster for maneuvering space
method in addn to having a decided economic
vehicles (Ref 31)
edge over existing methods, has the important
Applications using hydrazine as a gas generator
advantage that chlorine compds are not involved
include tank pressurization, inflating pneumatic-
in the reaction
power engine starters, turbines and positive dis-
Encouraged by the operating success so far
placement drives. The development of many of
of a pilot plant in Lyons, PCUK is building a
these uses was brought about by the introduction
small-scale commercial unit there due on stream
of decomposition catalysts discussed below in
in 1975.. A full scale plant is planned for 1977
t the section on combustion properties
 H 192

Hydrazine is used for the preparation of Anhydrous Nz ~ is a thermodynamically un-

hydrazoic acid according to: stable compound and tends to undergo decomp-
N2~ +HNOZ+HN3 +2H20 osition to Nz, H2 and NH3 spontaneously. This
is also true in aqueous solutions and is enhanced
or for the preparation of sodium azide (Ref by the presence of catalytically active metals
14). Hydrazine is used also as a scavenger for
oxygen in preventing corrosion in boilers (Ref, and oxides, such as Cu, Zn, Fe203 etc
16) and as an oxygen scavenger to prevent (Ref 7)
external corrosion of oilwell casings (Ref 21). Generally hydrazine reactions are similar to
It has been found to be an excellent fuel for those of ammonia and amines except that as a
diamine, further reaction takes place. The re-
fuel cells (Refs 23, 25 & 27). Hydrazine is
action of N2 ~ with CO at 20-50”C and high
also used in a family of liquid expls developed
pressure produces semicarbazide (Ref 1). At
& marketed under the trade name “Astrolite”
higher temperatures and pressures the products
by the Explosive Corporation of America,
are 4-amino- 1,2,4-triazol-3-one and 4-amino-
Issaguah, Wash (Refs 27b, 33a & 37)
1,2,4-triazole. With cyanamide, hydrazine forms
Analytical aminoguanidine which is treated with nitrous
The water and ammonia content of anhydrous acid to form tetracene, a primary explosive
N2~ are determined by a gas chromatography (Ref 15, 19). Carboxylic acids are neutralized
(Refs 37 & 38) method, and the analysis of the by hydrazine to form salts which decompose
aniline in the mixture by ultraviolet spectro- upon heating to give mono- or diacylohydrazides
scopy. The total N2~ content can be then (Ref 2). The hydrazine salts of oxidizing acids,
determined by difference. C)ther methods are suc~ as nitric acid or perchloric acid, are sen-
given at the end of section on Hydrazine sitive to shock and decompose violently. Hydra-
Chemisoy zinium Selenate, N2 H5 HSe04, is also explosive,
Nz ~ has been characterized by Audrieth in fact a very sensitive explosive (Ref 27a).
(Ref 7) as a saturated hydronitrogen belonging Salts of very powerful oxidizing acids (eg
to the type given by the formula NnHn+2. The chromic or permanganic) are unknown, and are
members of this series of compounds are as unlikely to exist. Hydrazonium iodate may exist
follows: in solution at low temp (Ref 27a). Alkali metals, I
NH3 ammonia NH3 amides and hydrides react with hydrazine to
Nz ~ hydrazine Hz N–NHz give the corresponding alkali hydrazide. Sodium
N3 H5 triazane H2 N–N–NH2 hydrazide explodes violently in the presence of
A Oz or when heated above 100°C–a typical be-
havior of the alkali hydrazides. For other
Nq Hc tetrazane H 0
reactions, see Ref 24
H2–N–~– –NH2
x Explosive and Combustion hoperties
Hydrazine may be looked upon as the nitro- Liquid anhydrous Nz ~ is a non-explosive
gen analog of hydrogen peroxide. It is a powerful even though it is thermodynamically unstable.
reducing agent which makes it an attractive fuel In the absence of decomposition catalysts, it
for reaction with oxidizers such as Hz Oz, 02, and has been heated above 500° F with very little
fuming nitric acids and nitrogen tetroxide. Aqueous decomposition. It is completely insensitive to
solutions of Nz I-& have been employed to reduce shock, friction or electrical discharge. Hydrazine
vapor has a lower limit of inflammability of (
various metallic ions such as copper, silver, gold
and the platinum metals to the metallic state. It 4.67% by volume in air. The upper limit is
also reduces strong oxidizing agents such as 100% since the vapor may be exploded with-
permanganate, iodate, hypoiodate, iodine, cerate out the addition of air (Ref 10)
and the like. Many of these reactions have been The use of Nz ~ as a hyperbolic rocket
used for the quantitative determination of fuel is described under the topic Hypergo/ic
hydrazine but side reactions giving off NH3 and I%opellants in this Vol. Another major research .,
in some instances hydrazoic acid may present effort has seen the development of hydrazine
problems thruster rockets based upon the catalytic de-
 H 193

composition of hydrazine. Typical thruster Hydrazine forms numerous salts and deriva-
rockets give thrusts ranging from 0.1 ft-lb to tives, some of which are expl or used as ingre-
5 ft-lb with positive thrust pulses ranging to dients of expls or for their prepn. Several of
1 million cycles (Refs 13 & 35). Catalysts them are described below
studied for the heterogeneous decomposition Refs: 1) V. Meyer & M.T. Lecco, ChemBer 16,
of Nz ~ include ruthenium, iridium and 2976 (1883) 2) Th. Curtius & H. Franzen,
rhodium. Decomposition kinetics are detailed ChemBer 35, 3239 (1902) 3) F. Raschig,
for ruthenium (Ref 34) and rhodium (Ref 36) ZAngewChem 20, 2065:2067 (1907) 4) F.
Due to the relatively high freezing point of Raschig, ChemZtg 31, 926 (1907) 5) F.
pure anhydrous Nz I-&, simple binary and Raschig, Schwefel -und Steckstoffstudien, Ver-
ternary solutions of Nz F& with water, ammonia lag Chemie G mbh, Leipzig, Berlin (1924) 6)
and hydrazine nitrate form low freezing eutectics International Critical Tables, McGraw-Hill, NY
which provide a wide range of exhaust gas (1928), 1st Ed, vol 3, pp 228-229 7) L.F.
temperatures and compositions when used in Audrieth, JChemEducation 7, 2055-2062 (1930)
gas generators. Typical examples are given in 8) P. Walden & H. Hilgert, ZPhysikChem 165A,
Ref 31. Ternary diagrams for the system 241-271 (1933) 8a) “Gmelins Handbuch
Nz ~ –Nz H5 N03 –Hz O give mixture freezing
der anorganischen Chemie”, 8th Edn, Verlag
points, detonable limits and vacuum specific Chemie, Berlin (1936), Syst 4, pp 315-16 and
impulse for 20’%, 40~0 and 60’% NH3 in the 9) A.M. Hugher et al, JAm-
Syst 23, p 547-48
equilibrium mixture
ChemSoc 61,2639-2642 (1939) 10) F.E. Scott
Explosive Compositions et al, “Explosive Properties of Hydrazine”, RI
Mixtures of hydrazine and other compounds 4460, Bureau of Mines, (May 1949) 11) D.W.
form liquid explosives which have been described. Scott et al, JACS 71,2293-2297 (1949)
A study of the detonability of binary and ternary 12) L.F. Audrieth & Betty A. Ogg, “The Chemistry
mixtures of nitromethane–hy drazine–methanol of Hydrazine”, John Wiley& Sons, NY (195 1),
showed that Nz ~ sensitizes nitromethane and pp 99ff 12a) E.F. Wiebke, AnalChem 23, No 6,
nitromethane-methanol mixtures to detonation 922 (1951) &CA 45.7469 (195.1) 13) B.W.
(Ref 29). From 2-10% N,~ and 90-98% lower Schmitz & W.W. Wilson, “Long Life Mono-
molecular weight nitioparaffins are claimed to propellant Hydrazine Engine Development
be a water insoluble liquid explosive (Ref 22). Program, .Final Rept~’ Rocket Research, RRC-
Mixtures of hydrazine, ammonium nitrate and 71-R-257 (Sept 1951) (Available NTIS-AD-
aluminum have been patented as explosive comp- 731287) 14) Ullmann, 6, 206, Encyklop;die
ositions with high air blast effects (Ref 32). der Technischen Chemie (1951) 14a) Ch.C.
High performance explosive mixtures with Clark, “Hydrazine”, Mathieson Chem Corp,
densities Z 1.4 have been obtained with a Baltimore, Md (1952), pp 1–3, 19–29, 83–4
sensitizer containing an oxidizing acid and a & 92–113 (Numerous references) 15) S.H.
base such as hydrazine (Ref 30). High detonation Patenkin, et al, JAmChemSoc 77, 562 (1955)
rate, low freezing point, low viscosity and low 16) Anon, “Hydrazine and Water Treatment ,“
impact sensitivity are provided by mixture of Whiffen & Sons, Ltd, London (1958) 17) W.
N2H5 N03 (and its mixtures with NzH5–CIOq in H. Anderson et al, IEC 51, 527 (1959) & CA
a 4:1 ratio for increased sensitivity) and inclu- 53, 14432 (1959) 18) B.H. Nicolaisen et al,
ding up to 25% of metal salts such as Na, K, “Commercial Production of Hydrazine,” K.A.
Ca and Al nitrates and perchlorates, 6- 15?I0 Kobe & J.J. McKetter, Jr, eds; Advances In
Nz ~ and 2-15% NH3 and water (Ref 28). Petroleum Chemistry & Refining, vol 2, Inter-
The water content is varied to control the science Publishers, Inc, NY (1959), chap 9
detonation velocity. For example a solution 18a) CondChemDict (1961), p 584-L
containing Nz H5 N03 70Y0,N2 HQ 7% and NH3 19)” F. Kurzer & L.E.A. Godfrey, ChemInd,
14% has a density of 1.31, detonation rate London (1962) 1584 20) Anon, The Handling
8100 m/see, fp -8°F and a viscosity of 12 cp. & Storage of Liquid Propellants, Office of the
Variable amounts of perchlorates give impact Director of Defense Research & Engineering,
sensitivities of 45-85 Kg/cm (nitroglycerin = Wash, DC (Jan 1963) 20a) D.M. Kuwada,
2 Kg/cm on the particular impact machine JGenChem (March 1963) p 11 & CA 59, 3320
used)
 H 194

(1963) 21) F.W. Schremp, OilGasJ 61 (25), Liquid Hydrazine on a Supported Rhodium
96 (1963) & CA 59, 9076 (1963) 22) Aero- Catalyst,” Rocket Propulsion Establishment,
jet General Corp (no author), BelgP 627768 Westcott. (England), Rept No RPE-TR-7 1/16-
& CA 60, 13091 (1963) 23) S.S. Tomter PT-4; BR-3 1012, Available NTIS (N73-19177)
& A.P. Anthony, “The Hydrazine Fuel Cell (NOV 1972) 37) S. Levmore, “Physical
System,” in “Fuel Cells,” HIChE, NY (1963) Characteristics of the Gelled Slurry Explosive
pp 22-31 24) Th. Kauffmann, “AngewChemIntern- Astrolite A-l-5”, PATR 4650 (May 1974)
Ed (Engl) 3, 342 (1964); AngewChem 76, 206 38) Staff, “Hydrazine Process Offers Advan-
(1964) & CA 60, 10489 (1964) 25) R.J. tages”, C&EN 52, No 37, pp 18–19 (16
Jasinski & T.G. Kirkland, MechEng 86, (3), 51 Sept 1974)
(1964) & CA 60, 14117 (1964) 26) J.H.
Cusack et al, “Continuously Circulating Fissio- Hydrazine and Derivatives, Analytical Procedures.
chemical Process Development Applicable to See at the end of this section
Hydrazine Synthesis, vol I–Program Survey,
Processing & Mater ials,” AFML-TR-65-98, Hydrazine Azide, Hydrazine Azoimide or
Final Rept (Jan 1965) Aerojet General Nucleon- Hydrazonium Azide. See list of Irrorganic
ics, San Ramon, Ca, Availabie DDC 27) R. Azides in” Voi 1, pp A536-537, and additional
Jasinski, ElectrochemTechnol 3 (1965) 129 & information below
CA 64, 6084g (1966) 27a) A.A. Shidlovskii, Apin et al (Ref 4), in a calorimetric inves-
ZhFizKhim 39 (9), 2163 (1965) & CA 64, 516 tigation of mixtures of Hydrazine Azide with
(1966) 27b) S. Levmore & S.J. Lowell, several metallic elements found that an explo-
“Principal Characteristics of the Liquid Expl~ sion resulted with the formation of NH3. The
sive Astrolite G“, PATR 3633 (Aug 1967) amount of NH3 depended on the explosion
27c) Sax (1968), p 819-R 28) M. Maes, conditions. The limiting conditions were either
USP 3419443 &CA 70, 69763 (1969) N2m “HN3 + 2%H2 + 2%NZ or+ 1 2/3NH3 + 1 2/3N2
29) D.R. Forshey et al, “Detonability of LMciurn Azide Hydrazinates. Ca(N3 )L. Nz Ho and
the Nitromethane-Hy drazine-Methanol Sys- Ca(N3)2“2N2 HQ; the addn of alc to a soln of
tem”, Explosivstoffe (1969), 17 (6), 125-9 & Ca(N3 )2 in anhyd Nz Hq, or evapn of such a
CA 71; 103735 (1969) 30) C. Dinglinson & W. soln in a vacuum desiccator over sulfuric acid
Lyerly, USP 3431155 & CA 70, 116778 (1969) leads to the formation of a 2-hydrazinate. This
31) Anon, Monopropellant Hydrazine Design solvate dissociates rapidly under reduced *
Data, Rocket Research Corp, Seattle, Wash pressure and/or at higher temps to give the
(1969) 32) R.M. Bridgforth et al, USP l-hydrazinate, Ca(N3)z “Nz Hq (Ref 1)
3523047 & CA 74, 14701 (1971) 33) Cond- Rejl: 1) A.L, Dresser & A.N. Brown, JACS
ChemDict (1971), p 55 I-L 33a) Staff, Bio- 53, 4235 (1931) & CA 26, 666 (1932) 2)
netics Res Labs, Bethesda, Md, “Acute Toxico- A.L. Dresser et al, JACS 55, 1963 (1933) &
logy Studies on Astrolite A-l-5”, Rept submitted 3) L.F. Audrieth &
CA 27, 3417 (1933)
to Explosives Corporation of America (Feb 1971)
Betty A. Ogg, “The Chemistry of Hydrazine”,
34) C.F. Sayer, “The Heterogeneous Decom- 4) A,Ya. Apin et al,
J. Wiley, NY (1951)
position of Hydrazine, Part 5: The Kinetics
ZhFizKhim 32, 819 (195kl) & CA 52, 21108
of the Decomposition of Liquid Hydrazine
(1958)
on a Supported Ruthenium Catalyst”,
Rocket Propulsion Establishment, Westcott (Eng- Hydrazine Chlorate, Hydrazinium Chlorate.
land) Rept No RPE-TR-72/ 1-PT-5; (BR-29320)
N2W. HC103 or NZH5C103; mw 116.51, N
Available NTIS (N73-14122) (Jan 1972) 35) 24.05%, OB to Clz and Hz O +6.9%; crys~als;
P.I. Moynihan, “Minimum Impulse Tests of mp 80°; v sol in I-IzO, cliff SOI in ale, insoi in
0.45-N Liquid Hydrazine Catalytic Thrusters,”
ether, benzene and chloroform; hydroscopic;
JPL Quarterly Tech Rev, vol 2, No 1 (April
may be prepd by mixing eq solns of N2 H4
1972) pp 107-112 36) C.F. Sayer, “The
and HC103 and evap at room temp; a power-
Heterogeneous Decomposition of Nz ~, Part
ful oxidizing agent and a very powerful explo-
4: “The Kinetics of the Decomposition of
sive. Its power, as detd by Trauzl test is
 H 195

about 278% of Mercury Fulminate or 100% 2) Clark, Hydrazine (1953), 12–13 3) Lange
TNT. It is less stable than Hydrazine Perchlo- (1961), 256 4) CondChemDict (19’71), 451-R
rate. It has been proposed for use in primary
and initiating mixtures (Ref 1) Hydrazine Dihydrochloride. See Hydrazine Di-
Refs: 1) R. Salvadori, GazzChimItrd 37 (2), chloride
32 (1907)&CA 2, 182 (1908) 2) Gmelins
Hdb (1936), Syst 33, p 555. 3) Blatt, OSRD Hydrazine Dinitrate. See under HYDRAZINE
2014 (1944) 4) ADL, PureExplCompds NITRATES
(1947), p 72, Compd 140 5) Ullrnann 6,
206 (1951) 6) L. Audrieth & B.A. Ogg, Hydrazine (or Hydrazinium) Hydrate,
“The Chemistry of Hydrazine”, Wiley, NY NH2NH2 .H20; mw 50.06, N 55.97%; exists
(1951) 7) Ch.C. Clark, “Hydrazine”, Ma- only in the solid state, contains 64% N2~,
thieson Chem Corp, Baltimore (1953) p 13 bp 118.5° at 739.5mm (Ref 2a, p 100); fr p
–51 .~C; density 25 ~ 1.031g/ml; fl p (open
Hydrazine Chlorate and Perchlorate Complexes. cup 163°F; refractive index 1.4284 at 200
See Hydrazine Perchlorate and Chlorate Complexes” (Ref 4); vapor pressure for the hydrate given
in Ref 1. Mist with w & ale; insol in eth &
Hydrazine (or Hydrazinium Chloride (or Mono- chlfi strong reducing agent, weak base. Its
chloride) (or Hydrochloride), mw
N2H4.HCl; aq soln was first prepd in 1887 by Th. Curtius.
68.52, N 40.89%; colorless trysts, mp 92.6°, In the Raschig process (prior to 1924), NaOH,
decomp at 240°; v sol in w; diffc sol in absol chlorine and ammonia react in aq soln to form
ale; easily sol in liq NHa – Forms a number of dil soln of hydrazine, with Na chloride as a
double salts. Can be prepd by treating hydrazine by-product; also by oxidation of urea by Na
hydrate with 1 mole of HC1 hypochlorite. For its purification can be used:
Rej3: 1) Gmelins Hdb (1936), Syst 23, pp fractional distillation, flash distillation or con-
552–53 2) Clark, Hydrazine (1953), p 12 version to the slightly sol sulfate, followed by
3) Lange (1961), 256 4) CondChemDict treatment of the latter with coned NaOH soln.
(1961), 584 (Hydrazine Monochloride; (1971), Its vapor is expl and toxic; especially dangerous
451-R to the eyes
Analytical. Hydrazine content in aqueous, solu-
Hydrazine (or Hydrazinium) Chlorite, N2 H4 .HC102; tions is determined by reacting with picryl chloride
mw 100.52, N 27.8870, rep-ignites spontaneously to form the yellow hexanitro hydrazobenzene,
when dry. Was prepd in small arnts from hydra- which, with alkali forms red or violet salts that
zine hydrosulfate (N ~H ~HS04 ), Ba hydroxide can be measured calorimetrically (Ref 3). More
and Ba chlorite [Ba(C102) ~] concentrated solution of hydrazine can be
Refs: 1) Gmelins Hdb (1936), Syst 33, p 555 titrated with either standard iodine or iodate
2) Clark, Hydrazine (1953), p 13 solutions according to the following equations
(Ref 4):
Hydrazine (or Hydrazonium)-N,N‘-dicarbonic
NH2NH2 + 212 + 4NaHC03 + 4NaI + Nz + 4HZ O +
Acid Diazide. See under HYDRAZINE SALTS
OF ORGANIC ACIDS 4CO*
or
Hydrazine (or Hydrazinium) Dichloride (or NH2NH2 + K103 + 2HC1 + KC1 + IC1 + N2 + 3HZ O
Dihydrochloride), N2E& .2,HC1, mw 69.53, N Heat of formation –10.3kcal/mole; heat of
40.30%; wh trysts, sp gr 1.4226 at 200/4 ~ mp combustion + 146.94kcal/mole with water
198° with dissociation; detonates on ignition, liq (Ref 2a, p 28)
or when heated rapidly; hydroscopic; v sol in Thermal, Combustion and Explosion &operties. lgn
w; almost insol in hot absol ale. Can be prepd temperatures of 85% hydrazine hydrate in
from hydrazine hydrate and excess of HC1 or pyrex and air was found to be 292°C. Oxygen
from hydrazine hydrosulfate and Ba chloride lowered the ignition point to 2 18°C. On plat-
Refs: 1) Gmelin’s Hdb (1936), Syst 23, p 553 inum foil an air atmosphere gave an ignition
 H 196

temperature of 338°C and oxygen gave 132°C Hydrazine (or Hydrazinium) Hydrochloride.
.
(Ref 1). The hydrate was not found to be See Hydrazine Chloride
sensitive to the impact of a 5kg weight dropped
from a height of 1 frreter. No explosion, burning Hydrazine (or Hydrazinium) Hydrosulfate
or local reaction occurred when the 8570 hydrate (Hydrazinium Acid Sulfate – so called by Clark
was subjected to the standard friction sensitivity (Ref 2) and its formula is given as NzH5.HS04 ).:
test in the pendulum-friction machine. No explo- The same compd is called Hydrazine Sulfate in
sion was obtained when hydrazine hydrate was Lange (Ref 3) and in CondChemDict (Ref 4),
subjected to a detonator in the ballistic mortar. where its formula is given as N2~ .H2S04,
No noticeable decomposition was observed in which amounts to the same mw for both for-
unconfined samples when a static spark of mulas equal to 130.13 and the same props:
12.5 joules was discharged through the liquid wh trysts, sp gr 1.378, mp 254° (with evolution
(Ref 1) of gas); stable in storage, but contact with
Used for prepn of anhydrous hydrazine and alkalies and oxidizing agents must be avoided;
for the same purposes as listed under Hydrazine, explodes with NaNH z; v sol in hot w; diffc
Anhydrous. Also used as gas absorbent (Ref 2a, sol in cold w; insol in ale. Can be prepd by
p 100) mixing hydrazine hydrate soln with sulfuric
Explosive Compositions. See hydrazine for acid. It is a strong reducing agent. Used for
explosive compositions containing water prepn of other hydrazine salts and derivs; also
Refs: 1) F.E. Scott et al, “Explosive Properties in analysis of minerals and ores; in tests of blood;
of Hydrazine”, Bureau of Mines, RI 4460 for separation of polonium from tellurium; as
(May 1949) 2) L.F. Audrieth & Betty A, fungicide & germicide; and in adhesives
Ogg, “The Chemistry of Hydrazine”, John Refs: 1) Gmelins Hdb (1936), Syst 23, pp
Wiley, NY (1951) 2a) Ch.C. Clark, “Hydra- 559–565 2) Clark, Hydrazine (1953), 10–11
zine”, Mathieson Chem Corp, Baltimore, Md 3) Lange (1961), 256 4) CondChemDict
(1953), pp 2, 8,28, 100& 112 3) A.I. (1961), 584-R and (1971), p 451-R
Cherkesov & L.M. Kul’berg, ZhurAnalitKhim
11, 89–90 (1956) & CA 50, 9236 (1956) Hydrazine Mononitrate. See under HYDRA-
4) Kirk & Othmer, “Encyclopedia of Chemical ZINE NITRATES
Technology”, 11 (1966),p 166 5) CondChem-
Dict (1971), 451-R Hydrazine (or Hydrazinium) Nitrite. N2~ .HN02;
mw 79.06, N 53.15~o; decompor explodes on
Hydrazine Hydrate and Hydrazine Reactions rapid heating; colorless to yellowish hygr solid;
with Explosive Violence. sol in w & ale; insol in eth; may be prepd by
The following reactions with inorganic sub- mixing solns of barium nitrite and neutral
stances are taken from the book of Clark, hydrazine, sulfate, as described in Mellor (Ref
Hydrazine (1953), pp 4 to 18: Potassium re- 1). Explodes violently on impact and less so
acts with N 2H4 expl violently (p 4); Mercuric when rapidly heated. When heated slowly it
oxide reacts with N2~ .H20 with expl violence decomposes according to the equation:
(p 5); Chlorine, bromine and iodine react vio- N2~ .HN02 + NH3 + NZO + H20 and this
lently (p 8) with N 2H4 and spontaneous igni- decompn is greatly accelerated by nitrous acid
tion of Nz ~ takes place in a chlorine atm. Refs: 1) Mellor 8, 472–3 (1946) 2) F.
Explns of N2H4 and iodine have been reported Sommer, ZAnorgChem 83119 (1913)
(p 12) 3) Clark, Hydrazine (1953), p 6
In Chap III of Clark’s book entitled “Organic
Chemistry of Hydrazine”, it is stated on pp
83–4, that all indications are that anhydrous HYDRAZINE (OR HYDRAZINIUM) NITRATES
hydrazine reacts so vigorously with org sub- Hydrazine Mononitrate, HN, HzN, hydrazinium
stances that products will not be the same as nitrate. N2~ .HN03 or N2H5N03; mw 95.07;
with hydrazine hydrate or the salts. Anhyd N 44:20%, OB to Nz and H20 +8.4%; white
N H is not used for making ‘erg hydrazides monoclinic tablets and rods existing in 2 forms,
because it attacks other groups
 H 197

a’ & (?. (1 form is unstable, mp 62°; cx form, of ignition was 307° (Ref 21). Whittaker and Y
stable, mp 70°; crystal axial ratio a:b: c = Barham (Ref 15), using high-speed photography,
0.957: 1.0:0.492; interracial angle (polar) measured average surface temp and melting - )
88026’; crystal angle 90° (Ref 12); d 1,661. point for NH4N03: 303° * 12° and 166° *
Ib16dard(Ref 8) determined density at va- 10°; for HN: 19$ * 9° and 74° * 5°; and for
rious pressures as follows: pressure in kg/ an NH4NOS–HN eutectic: 307° * 11° and 39°
sq cm, density: 34, 1.08; 88, 1.18; 136, ~6°. Equilibrium flame temp of HN detonations
1.28; 204, 1.43; 306, 1.49; 425, 1.58; have been reported to be 2400°C (Ref21)
680, 1.61; 1020, 1.635; 1700+, 1.64. If In the open air, HN supports combustion,
a coned aq soln is cooled from 100°, silky but the flame was extinguished upon removal
needles of ~-form separate, but they undergo of the ignition source. To achieve stable
monotropic transition to a-form with evo- burning Shidlovskii (Ref 14) found that addi-
lution of heat at room temp. Soly in g/100g tion of 10 wt–% of KzCr207 was necessary.
H20 at 10°, 174.9; 20°, 266.3; 30°, 402.2; HN ignites with permanganate, chromate,or
40°, 607.2; 50°, 1034.0; 60°, 2127.0 (Ref 6) peroxides. At slightly above its mp it will
l%ermodynamic data. AH combustion (const ignite with metallic Zn, or Cu, or their oxides,
vol) 112.1 kcal/kg; AH comb (const press) sulfides, nitrides or carbides (Ref 9)
111.1 kcal/kg; A% (const VOI) 56.7 kcal/kg; Sensitivity to initiation: non-compressed HN
AH; (const press) 59.8 kcal/kg (Ref 10); with 0.5% moisture content, detonated with a
AH transition f3 to ~ “form 2.0 kcal/mole; cap contg 0.25g Mercury Fulminate; compressed
AHsoln (Hz O) -8.72 kcal/mole; AHsoln (N2 Hq ) to d 1.60, 1.5g MF was required for detonation
+3.7 ~cal/mole (Ref 21). Refractive ind at (Ref 8)
5983A & 25”C, ct 1.605+0.004 and 1.620i0.005, Sensitivity to impact: values of 175 kg/cm
fl 1.458t0.003 (Ref 12). Density and viscosity and 200 to 150 kg/cm for 50% probability
curves of HN solns with hydrazine and water are reported for the “Bruceton up-and-down”
are given in Ref 21 method; values of 32 kg/cm and 50 kg/cm
are reported for the ERL type 12 tool test
Preparations. Add HN03 “by drops (to anhyd (Ref 21)
Nz ~ dissolved in MeOH) to pH of 5.5. HN Card gdp sensitivity: 6.25 cm; brisance 82
ppts and is fiitered off (Ref 10). May also be (TNT = 100); Trauzl lead’block test 120.4 t
prepared from hydrazine carbonate and HN03, 0.5 (picric acid = 100); TNT equivalence =
from Nz H~ OH and HN03 or from Nz H5 HS04 1:42
and Ba(N03 )2 (Ref 6). Weiss (Ref 16) re- Detonation velocity: Bureau of Mines detd
acted Nz ~ and Nz 04 at -133°, forming HN det velocity of molten HN at 75° in thin-
Toxicology. Similar to hydrazine (Ref 24) “ frlm expts to be 8500 m/see (Ref 21)
Jacobs (Ref 4), with a rotating mirror camera,
Analytical. Infrared absorption and x-ray dif-
measured a detonation velocity of 5200 m/s
fraction spectra are given in Ref 21
with a 1“ diam cartridge, 5600 m/s with a
Thermal, combustion and explosion properties. 1 5/8” diam cartridge, and 8500 m/s with a
Decomposes on heating at 1 atm to 200-300° 2~’ ‘diam cartridge (d of 1.6 for pressed
as follows: 4N2H~N03 +2N0 + 5N z+ 10H 20 material)
(Ref 9). Medard (Ref 8) measured wt loss on M6dard (Ref 8) using a 30mm diam and
heating at 100° as compared with Ammonium 170mm long cartridge found a maximum ve-
Nitrate: HN lost 0.005%/hr of its weight at a locity of 5640 m/see at a d of 1.25 g/cm3.
const rate as compared to 0.016% for AN. Price et al ‘(Ref 17) reported a det velocity of
Shidlovskii et al (Ref 14) in studying thermal 8510 m/see at d 1.59 g/cm3 for a 6.3 cm
decomp of function of temp found the de- diam charge of pressed HN. Price and co-
composition started at 180°; increased rapidly workers found, that the infinite charge diam
above 240°, at 270° became explosive. The detonation velocity, D (in m/see) for HN
ignition temp detd by the “Bruceton up-and- can be expressed as D = 5390 (PHN-1OO)
down” method which gave a 50% probability in which pHN is the d of HN in g/cm3.
 H 198

Kurbangalina et al (Ref 22) found that crit- (1953) & CA 49, 11284 (1955) 11) L.F.
ical diam increases with increasing water Audrieth, USP 2704706 (1955) & CA 50,
content, and that molten HN & its aq solns 8208 (1956) 12) R.J. Robinson & W.C.
can detonate with different velocities (2-8 McCrone, AnalChem 30, 1014 (1958) & CA
km/se). Low-velocity detonations are less 52, 10681 (1958) 13) T.A. ,Erikson, Am-
dependent on critical diam than high-velocity RocketSocJ 30, 190 (1960) & CA 54, 13661
detonations (1960) 14) A.A. Shidlovskii et al, ZhPriklad-
Explosive compositions. Audrieth (Ref 11) Khim 33, 1411 (1960) & CA 54, 22132 (1960)
15) A.G. Whittaker & D.C. Barham, JPhysChem
patented an explosive compn of NHQN03
86 (l), 196 (1964) & CA 60, 6693 (1964)
78.5 - 83.5%, HN 5-10%, TNT 7.5%; Al
16) H. Weiss, Western States Comb Inst Paper’
dust 0.5%; coal 3% and chalk 0.5%. Increasing
WSCI 65-20 (1965) & CA 64, 11019 (1966)
HN content to 10% increases sensitivity and
17) D. Price et al, The Detonation behavior of
detonation rate. Bridgeforth et al (Ref, 20)
hydrazine mononitrate, NOLTR 66-31, Naval
patented explosive compns with high detonation
Ordn Lab (15 April 1966) AD 634602 18)
rate and high air blasts (up to 2-fold TNT)
D. Price, SympComb 11, 693 (1966) & CA 67,
which contain N2 Ho and HN with or without 101557 (1967) 19) P. Breisacher et al,
NH3 + N~ N03 + finely divided ~ and a
CombustFlame 14 (3), 397 (1970) 20) R.M.
thickening agent. These compns have good ,
Bridgeforth et al, USP 3523047 (1970) & CA
cratering performance, comparable to TNT. 74, 14701 (1971) 21) H.K. James et al, Physi-
M6dard (Ref 8) examined properties of HN cal and Explosion Characteristics of Hydrazine
mixtures with NH4N@. Guanidine Nitrate,. Nitrate, US B of M Info Circular 8452 (March
Nitroguanidine, and Ethylenediamine Nitrate. 1970) 22) A. Kh. Kurbangalina & N.N. Tinok-
Also examined (Ref 8). was a mixt of 6% HN hin, FizGoreniyaVzryva, 6 (4), 515 (1970) &
in a commercial explosive of NHq N03 87.5% CA 75, 89717 (1971) 23) A.R. Gregory et al,
and 12.5% wood flour. The original tit of ProcWestPharmacolSoc 14, 117 (197 1) & CA
d = 0.80 required 0.80g MF for complete 75, 46981 (1971) 24) Sax (1968) p 819
detonation, while the one with HN, d = 0.90
required only 0.30g MF for detonation. The Hydrazine (or Hydrazinium) Dinitrate.
gap test was 1.3cm for orig mixt and 4cm NzI-LI.2.HN03,mw 158.08, N 35.45%, OB
for mixt contg 6% HN. Incorporation of HN to N2 ‘and Hz O 30.4%; crystals, mp 103–
renders NHQN03 explosives less hydroscopic. 104° when heated rapidly. When slowly
Thermal stability of HN at temps 100-200° is heated it decomp at 80-85° without melting,
satisfactory and it can be incorporated in ex- yielding among other decomp products hydro-
plosives loaded by casting. The low mp of HN gen.azide. Even in a desiccator over sulf acid
lowers the casting temp of NH4 N03 mixtures and at ord temp it decomp with evolution of
(Ref 8) . hydrogen azide, leaving a residue of Nz ~. HN03
Refs: 1) Gmelin’s Hdb (1936), Syst 23, p 551 and NH4 N03. Readily sol in w, but aq solns .
2) W.R.E. Hodgkinson, JSCI 32, 519 (1913) & contg more than 30% decomp on heating,
33, 815 (1914) &CA 9, 571 (1915) 3) Gmelins d 1.64. Prepd by treating 1 mole of hydrazine
Handbuch der anorganische Chemie, VerlagChemie, hydrate with 2 moles of nitric acid. It was
Berlin (1936), p 551 4) S.J. Jacobs, US Naval examined in US during WWH and found to
Ordn Lab Memorandum 10068 (1949) 5) A. be a more powerful explosive than Tetryl but
LeRoux, MP 32, 121 (1950) & CA 47, 9014 less powerful than PETN. It is slightly less
(1953) 6) L.F. Audrieth & Betty A. Ogg, sensitive to impact than Tetryl
“The Chemistry of Hydrazine”, J. Wiley, NY Refi 1) Sabannejeff, ZAnorgChem 20, 21
(1951) 7) L. M6dard, MP 33, 323 (1951)
(1899); not in CA 2) W.R.E. Hodgkinson,
& CA 47, 10227 (1953) 8) L. M6dard, JSocChemInd 32, 519 (191 3); not in CA 3)
MP 34, 147 (1952) & CA 48, 6125 (1954)
F. Sommer, ZAnorgChem 86, 71 (1914) & CA
9) Ch.C. Clark, Hydrazine, Mathieson Che-
8, 1932 (1914) 3a) Gmelins Hdb (1936),
mical Corp, Baltimore, Md (1953), p 6
Syst 23, p 551 3b) Blatt, OSRD 2014
10) L. M6dard & M. Thomas, MP 35, 160
(1944) 4) Mellor 8, 327 (1946) 4a) ADL,
 H 199

PureExplCompds (1947), p 65, Compd 142 Note: During the investigation of various
5) J. Barlot & S. Marsaule, Compte rend 226, methods of preparation, it was observed by
1981 (1948) & CA 42, 8058 (1948) 6) .L.F. Barlot (Ref 2) that if solns of equimolecular
Audrieth & Betty A. Ogg, “The Chemistry of amounts of nickel nitrate and hydrazine nitrate
Hydrazine”, J. Wiley, NY (1951) 7) Ch.C. are mixed no precipitation is observed. If,
Clark, “Hydrazine”, Mathieson Chem Corp, however, some hydrazine, or ammonia is added,
Baltimore, Md (1953), p 6 an immediate precipitation of pink complex
is observed
Hydrazine Nitrate Complexes. Salts of bivalent Cadmium Nitrohydrazinate. Cd(N~ ~ o3N2~.
metals (Ni, Co, Zn, Cd and Mn) of complex Calcd: Cd 33.7% and N2~ 28.9; found: Cd
hydrazine nitrates may be represented by the 33.1’% and N2 I& 28.5%. White tryst powder,
following formulas: [M(N ~H4)2 ] (N03 )2, or explodes on strong impact (such as of 2kg wt
by [M(N2N)31 (NOS)2. In these complexes, falling from the height of 3m) or on rapid
called nitrohydrazinates, each N2 ~ group heating to ca 245°; when spread in a thin layer
plays the same role as two NH3 groups in the it burns while melting and evolving brown fumes
corresponding ammonium complexes (Ref 3)
For Cu and Hg the only known nitrohydra- Cobalt Nitrohydrazinate. CO(N03)2 “3N2 ~.
zinates contained one Nz ~ group Calcd: Cd 2 1.0% and Nz ~ 34.5%; found: Co
Most of these complexes are stable @ the 22.1% and Nz ~ 32.5%. Brownish. (bister
dry state and remain so on heating to tem- color) microcryst powder; explodes violently
peratures of at least 110°. At higher tempera- on impact (such as of 2kg wt falling from the
tures the complexes explode, some of them height of 1.75m) or on heating to ca 210°.
violently. They are nearly insol in water but Addp of 25% water decreases sensitivity
are more or less hydrolyzed by it to drop test. Explodes also on contact with
The complex of Ni was first prepd by coned acid. It is unstable and decomposes
Franzen and Mayer (Ref 1) and the formula slowly even in the presence of traces of
[Ni(N, ~ )3 ] (N03)2 was assigned to it. The “ water changing to a greenish color (Ref 3)
same investigators prepd the nitrohydrazinates
of Cd, Cu and Co Manganese Nitrohydrazinate. Mn(N03)2“2N2 Hq.
Most of these complexes were prepd by Calcd: Mn 22.8% and N2HQ 33.6%; found:” Mn
the action of aqueous soln of hydrazine on 23.6% and N2~ 33.5%. Reddish (ochre)
ammoniacal complexes of the nitrates of colored hexagonal crystals; ignites easily ca
Co, Ni, etc (contg six NH3 groups). M6dard 150°, produces copious fumes of Mn ofide; is
and Barlot (Ref 3) proposed the following insensitive to shock (Ref 3) ‘
procedure: Nickel Nitrohydrazinate. Ni(N03 )2” 3N2 ~.
A soln of 20-30pts of a nitrate in 10Opts Calcd: Ni 21 .0% and N2HQ 34.5%; found: Ni
of water (or preferably in ethanol) was gradually 21.3% and Nz ~ 34.0%. Rose-violet colored
added to a mechanically agitated soln of 50pts microcrystals; explodes violently on impact
of hydrazine hydrate in 100pts of ethanol, (such as of 2kg wt falling from the height of
cooled to ca 10°. The amount of reagents 1.50m) or on heating to ca 2 15°; the explosion
should be calculated in such a manner that is accompanied by a loud noise and a brilliant
the final mixture contains 4 to 5% of excess flash. Addn of 25% water decreases sensitivity
of hydrazine to drop test. Power in the French lead Mock
As soon as all the nitrate was added the test (CUp) ca 85 (PA 100) which is higher
mixture was poured into a Btichner funnel than for MF or LA. In cellophane tubes
connected to a suction flask. The resulting 200mm long at d = 0.62 (MF detonator),
precipitate was washed with methanol or the velocity of detonation by the Dautriche
ethanol until the elimination of hydrazine was method for various tube diams were: 2600
complete and dried first in air and then in a m/see at 6mm diam; 2900 and 3100 at 8mm; -
steam oven at 100° 2700 at 10mm; 2900 at 12mm; and 3500
at 15mm (Ref 3)
 H 200

Ellern and Olander (Ref 4) report a ignitable initiating compound, such as Lead
spontaneous explosion of a thoroughly washed Styphnate
and dried nickel nitrohydrazinate [Ni(N2Ho)3- d) The complex Styphnate of Ni hydra-
(N03)Z] after exposure totheatmforlOmiri zinate also deflagrated & did not detonate
Barlot and Medard (Refs 2 & 3) describe an Refi 1) H. Franzen & O.V. Mayer, ZAnorg-
analytical procedure for nickel nitrohydrazinate: Chem 60, 266 (1908) 2) J. Barlot, Deriv6s
decompose the complex cautiously (to avoid an complexes de l’hydrazine et de quelaues
explosion) by means of coned Hz SOq and de- nitrates m~talliques, 24e Congr& de chimie
termine Ni content by means of dimethylgly- industrielle, Paris (1951) 3) L. M6dard &
oxime. Determine the hydrazine content by J. Barlot, MP 34, 159-166 (1952) & CA 48,
means of an iodate soln 6125 (1954) 4) H. Ellern, & D. Olander,
Uses: The possibility of using Ni nitrohydra- JChemEd 32, 24 (1955) & CA 49, 6607
zinate in commercial detonators was investigated (1955) i
by loading Cu caps of 5mm diam with 2.5g of
Ni complex and trying to detonate them by Hydrazine (or Hydrazinium) Perchlorate,
means of a fuse, or an electric igniter. No ‘ Hydrazinium Perchlorate, N ~H4.HC104 or
detonations were produced unless the substance ~H5C104; rnW 132.51; N 21.13%, OB to
was primed by ca 1.5g of Black Powder Clz and H20 +18.1%; orthorhombic crys-
In attempts to increase the detonability of tals; for a study of crystal structure see
N1 hydrazinate, it was mixed with equal parts Conant and Rooj (Ref 16); mp 131–132°;
of an easily ignitable initiating substance, such d 1.939 (diperchlorate d 2.21, mp 1910);
as Pb- styphnate or Pb- picrate, and then ignited. soly in Hz O: temp, g/ 10Og satd soln: 0°, 23.68; I
The best that could be obtained was a deflag- 40°, 68.9; 60°, 87.4; 75°, 93.1 (Ref 3). Carleton
ration but no detonation. Mixtures of the Ni & Lewis (Ref 11) studied the phase equilibria
complex with RDX deflagrated ~and only in of Hydrazine Perchlorate–water system and
one case detonated (Ref 3) observed: the limiting melting temp of the salt,
142.4°; the occurrence of a solid hydrate decompg
Zinc Nitrohydrazinate. Zn(N03 )2 o3N2 ~. at 64° with a entectic point at -4.10 and 80% I
Calcd: Zn 22.8% and Nz I& 33.6%; found Zn Hz O; hydrate identified as N ~HqC104 *%H~O;
23.0% and Nz ~ 33.5%. White crystalline quadruple pt 64° and 88mm Hg. AH of addn
powder (apparently hexagonal); explodes of N2@ to HC104 = -44.4 kcal/mole; AH of
occasionally under very strong impact (less addn of HCIOQ to Nz ~ .HCIOQ = -18.8 kcal/
sensitive than any of the above complexes with mole; AH! = 40.69 * 0.36 kcal/mole(Ref 15)
the exception of Mn); ignites with crackling and or 42.9 t 0.2 kcal/mole (Ref 5); AHO for I
greenish sparks on heating to ca 310° (Ref 3) diperchlorate = -70.1 f 1.0 (Ref 7); i Hsoln =
Conclusions. The following conclusions about 33.11 kcal/mole; AH diln 1:1000 = +9.77 kcal/ ,
the explosive properties of complex metallic mole 1
nitrohydrazinates were drawn by M6dard and Preps: May be prepd by addn of coned HCIOq
Barlot (Ref 3): to aq soln of Nz ~ neutralizing and cooling to
a) the complexes of Ni, Co and Cd possess 0° (Ref 3). Byrne (Ref 14) prepd anhyd per-
properties similar to primary and initiating chlorate by metathesis of a hydrazine salt with
compounds, such as Mercury Fulminate an inorg perchlorate dissolved in a lower
b) they are much less sensitive to shock aliphatic alcohol. Stern (Ref 6) prepd the hemi-
than Mercury Fulminate or Lead Azide and hydrate by adding Nz I& to an aq soln of
are more powerful NHq C104, heating to remove Hz O and NH3,
c) they are much more difficult to ignite and cooling below transition temp to crystallize
by means of a fuse, or an electrical igniter,
Analytical: Jacobs & Russell-Jones (Ref 12)
than Mercury Fulminate and even when
detd the IR spectrum and assigned absorption ,
ignited they do not detonate but only defla-
bonds
grate. This is also true, in a lesser degree,
for mixtures of above complexes with more Toxicolo~: Unknown. Probably toxjc (Ref 18)
., ‘>
(
 H 201

Use: Rocket propellant (Ref 17) as 11370PA, while ADL (Ref lc) gives 122%
Thermal, combustion and explosion properties: TNT. Impact sensitivity FI 12% PA (Ref lb).
Barlot and Marsoule (Ref 3) reported the salt In air it forms a semi-hydrate, mp 85°, which
melting to a colorless liquid at 137-8°, with is insensitive to impact (Ref lb)
decompn beginning at 145°, becoming complete Refs: 1) R. Salvadori, GazzChimItal 37 (2)
at 230°. Grelechi and Cruice (Ref 9) using a 32 (1907)&CA 2, 182 (1908) 1a) Gmelins
manometric technique to study thermal decompn, Hdb (1936), Syst 23, p 556 lb) Blatt, OSRD
found the reaction rate to be proportional to 2014 (1944) 1c) ADL, Synthesis HE’s,
the amt of free HCIOO present. Shidlovskii et al Ist Rept (1949), p 69, Compd 43 2) Ullmann
(Ref 5) detd the rate of thermal decompn at 6, p 206 (1951) 3) J. Barlot & S. Marsoule,
different temps. They rdso measured the vol of Compt rend 228, 1497 (1949) & CA 43, 8934
gases evolved in decompn to be 864 l/kg. (1949) 4) C.C. Clark, Hydrazine, Mathieson
Jacobs and Russell-Jones (Ref 12) studied the Chem Corp, Baltimore (1953) p 14 5) A.A.
thermal decompn of the hemihydrate. In vacuo Shidlovskii et al, ZhPrikKhim 35, 756 (1962)
it will partially dehydrate even at room temp; & CA 57, 5285 (1962) 6) D.R. Stern, USP
when heated, the remainder of the O.5 mole 3131997 (1964) & CA 61, 9198 (1964) 7)
Hz O is lost at 610. At low temps, decompn R. Caruso et al, JPhysChem 69, 1716 (1965)
is represented by the equation: & CA 63, 71 (1965) 8) R. Friedman & J.B.
2N2H5C100“0.5H20 +-0.8 N~C104 + 0.702 Levy, AD 351940 (1966) & CA 66, 97033
+ 1.6N2 + 0.6C12 + 4.4H2 O, but at high temp (1967) 9) C.S. Grelechi & W. Cruice, Advan
the rate of decompn of ~ C104 formed be- ChemSer 54, 73 (1965) & CA 65, 4992 (1966);
comes appreciable. When ignited, hydrazine ACS Div FuelChem Preprints 9, 80 (1965) &
perchlorate burns without exploding. The flame CA 65, 18415 (1966) 10) J.B. Levy et al,
temp is 2200° AdvanChemSer 54, 55 (1965) & CA 65, 5294
Friedman and Levy (Ref 8) and Levy et al (1966) 11) L.T. Carleton & R.E. Lewis,
(Ref 13) investigated deflagration behavior. JChemEngData 11 (2), 165 (1966) & CA 65,
Levy et al (Ref 10) studied deflagration of 86 (1966) 12) P.W.M. Jacobs & A. Russell-
hydrazine perchlorate both pure and with fuel Jones, CanJChem 44 (20), 2435 (1966) & CA
and catalyst additives (Cu chromite, KzCr207 65, 16482 (1966) 13) J.B. Levy et al, US
and MgO). Deflagration rates were measured DeptCommerce AD 628035 (1967) & CA 66,
photographically from 0.26 to 7.7 atm. 77925 (1967) 14) J. Byrne (Monsanto) USP
Shidlovskii et al (Ref 5) studied ignition 3537924 (1967) & CA 67, 71 (1967) 15)
behavior. Ignition temp, 277-80°, was lowered V. Ya. Rosolonskii et al, ZhNeorgKhim 13
to 254-9° by addn of 5% Mn02, and addn (3), 681 (1968) &CA 69, 13538 (1968) 16)
of 5% CUC12 resulted in explosion at 170°. J.W. Conant & R.B. Rooj Jr, ActaCrystallogr
In 1.05cm diam tubes hydrazine perchlorate Sept B 26 (12), 1928 (1970) & CA 74, 46614
did not ignite, but with 5% Mn02, COO or (197 1) 17) CondChemDict,. Van Nostrand, NY
CU2C12 it maintained self combustion at room (1971) p 451 18) Sax (1968) p 820
temp. The rate of burning in the presence of
additives decreased in the order CU2Clz > COO Hydrazine Perchlorate and ,Chlorate ,Complexes.
> Mnoz. Self combustion was not maintained, Srdts of hydrazine chlorate and perchlorate
in the presence of 570 CUC12.2HZ O, but in the complexes, such as [CO(N2~ )2 ] (C103 )2,
presence of 2.5% CUC12“2H20 + 2.5% CUC12 yellow tryst, and [CO(N2 I-&)2] (CIOa )2, were
about 2/3 of the perchlorate burned out before first prepd by Salvadori (Ref 1). Friederich
the residue exploded. The rate of burning of and Vervoorst (Ref 2) describe a number of
the perchlorate was 2-3 times as high as that complexes (Cn, Cd, Ni, Co & Zn) prepd by
of NH4 C103. Hydrazine perchlorate is an ex- adding a soln of hydrazine hydrate in Hz () or
plosive comparable in power to the’ chlorate EtOH to a soln of a metallic chlorate or
but is more stable. Srdvadori (Ref 1) proposed perchlorate with cooling and agitation, and
using it in primary and initiating mixtures. washing and drying the ppt at low temperatures.
Blatt (Ref lb) gives its power by TrauzI Test For example, [Ni(Nz ~ )3 ] (C103)2, also Cd

..\
 H 202

and Cu chlorates and perchlorates, were prepd Refs: 1) Gmelins Hdb (1928), Syst 21, p 260
and their explosive characteristics were studied. 2) T.W.B. Welsh, JACS 37, 497–508 (1915)
They were, found to be powerful and sensitive 3) Clark, Hydrazine (1953), p 4
explosives, claimed to compare favorably with
standard initiating explosives. Violent decompn
occurs, presumably in accordance with the HYDRAZINE SALTS OF ORGANIC ACIDS
following hypothetical equations: Hydrazine-N,N’dicarbonic Acid Diazide
[Me(Nz W )2] (C103 )2 + MeC12 + 2N2 + 4H2 O + 02 (Hydrazin-N,N’-dicarbonsaure, in Ger)
[Me(N~MI)31 (C1O, ), + MeClz + 3Nz + 6H, O N3$.HN.NH.$.N3; mw 170.10, N 65.88, OB
/[Me(NZN)21 (clOiI)2+ MeClz + 2N, + 4H2 O + 202 o 0
[Me(NzH4)31 (CI04 ), + MeC12 + 3N2 + 6H, O + 02 to CO* –28.2%; trysts, mp 150–52 (decomp)
The chlorates are more sensitive than the perchlor- and explodes if heated rapidly. Was obt d,.in
ates (Ref 2); the Cu-chlorate complex detonates 20% yield as by-product of the action of nitrous
even on drying at room temperature. Maissen & acid on the hydrazide of dicarbonic acid. It
Schwarzenbach (Ref 3) attempted to prepare is primary type expl more sensitive to impact
[Ni(N,~ ), ] (C104), by mixing Ni(CIOd ), and than Lead or Silver. Azides. One g of TNT can
Nz ~ in water. After 5 days a blue ppt formed. be initiated by 0.25g of this expl
When a glass stirring rod was introduced into Refs: 1) Beil 3, (60) & [102] 2) w.
the suspension, a violent explosion resulted Kesting, Ber 57, 1321 (1924) 3) Blatt,
Refs: 1) R. Salvadori, Gazz 40, II, 9 (1910) & OSRD 2014 (1944) 4) ADL, Pure Expl
CA 5, 1568 (1911); Gazz 42, 448 (1912); JCS Compds, Part 1 (1947), p 5 l; Compd 141
98, II, 959 (1910) 2) W. Fnederich & P.
Vervoorst, SS 21, 49 (1926) & CA 21, 1184 Hydrazine picrate, N2 J& “C6 Hz (N02 )3 OH;
(1927) 3) B. Maissen & G. Schwarzenbach, mw 261.2, N 26.8%; OB -52.0%; soly detd by
HelvChimActa 34, 2084 (1951) & CA 46, 3280 Gilbert & Huffman (Ref 1) in EtOH–Hz O
(1952) mixtures. Soly curve showed maxima & minima
but no evidence of a stable alcoholate. Water of
Hydrazine Picrate. See under HYDRAZINE hydration was retained even in 99.8% EtOH.
SALTS OF ORGANIC ACID Forth (Ref 3) studied thermal stability of amine
salts of ficric Acid; and rated, in order of in-
HYDRAZINE, REACTIONS WITH METALS creasing stability the following salts: Hydrazine
AND THEIR SALTS. Picrate; Arninoguanidine Picrate; N-Methyl-
Lithium dissolves slowly in anhydrous hydra- guanidine Picrate; Guanylurea Picrate; N-
zine with evolution of hydrogen and nitrogen. Ethylguanidine Picrate; and Guanidine Picrate.
In the presence of N2H ~.HS04 the reduction Christensen & Gilbert (Ref 2) plotted the vapor
is much more rapid” pressure curve of the hydrated picrate, Nz ~. -
Refi Clark, Hydrazine (1953), p 4 CbHz (N02 )3 OHC?4HzO; up to its melting point
Mercuric Oxide. Explosive action betw HgO and found no break in the curve. It holds the
and hydrazine hydrate was observed by Curtius water of hydration very tenaciously and begins
& Schrader to have an appreciable vapor pressure only at
Refs: 1) Th. Curtius & F. Schrader, JPrakt- temps around 100°; calculated AH of dehy-
Chem [2] 50, 320(1894) 2) Clark, Hydra- dration is 16.855 kcal/mole and calculated
zine (1953), p 5 ‘F~98.1 is 2705 cal. No explosive props
Potassium reacts with anhydrous hydrazine with mentioned, but is evidently explosive
explosive violence
Refs: 1) E.C. Gilbert & E.H. Huffman, JPhys-
Refs: 1) T.W.B. Welsh & H.J. Broderson, JACS Chem 36, 2789 (1932) & CA 27, 459 (1933)
37, 816–24 (1915) 2) Clark, Hydrazine 2) B.E. Christensen & E.C. Gilbert, JACS 56,
(1953), p 4 1897 (1934) & CA 28, 6615 (1934) 3) M.I.
Sodium reacts with aqueous or anhydrous hy-
Fauth, AnalChem 32, 655 (1960) & CA 54,
drazine with formation of NaNH.NH2. When 1594 (1960)
dry the salt is extremely explosive
 H 203

Hydrazine Styphnate and Hydrazine Styphnate d 0.871 at 26°, heat of formation +12.7 kcal/
complex. Fauth (Ref 2) examined relative mole, heat of combstn–311 .7kcrd/mole, explo-
stability in terms of the temp of explosion sive limits in air 2.5 to 98%, vapor pressure
of amine salts of styphnic acid, and rated, 49.63mm Hg at 25°, viscosity 19.Ocps at –55°.
in order of increasing stability, the following For other props see below. May be prepd by
salts: Hydrazine Styphnate; N-Methylguanidine the alkylation of hydrazine:
Styphnate; N-Ethylguanidine Styphnate; CH3C1 + 2N2~ + CH3 NHNH2 + N2~ oHC1 or
Guanidine Styphnate; Guanylurea Styphnate; by reaction of NH2 Cl with methylamine (Ref
and Aminoguanidine Styphnate. The impact 3). Liquid MMH is not sensitive to impact or
sensitivity of the styphnates as indicated by friction. It is hyperbolic with some oxidants
the 5kg drop test, in order of increasing such as Hz 02, Nz 04, fluorine and nitric acih.
sensitivity was: Aminoguanidine Styphnate; When a fdm of MMH comes into contact with
Guanidine Styphnate; N-Ethylguanidine Styph- metallic oxides, such as those of iron, copper,
nate; N-Methylguanidine Styphnate; Guanylurea lead and manganese, it may ignite owing to
Styph!_rate and Hydrazine Styphnate the chemical heat of decomposition (Ref. 5)
Medard & Barlot (Ref 1) prepd a small
quantity of a Hydrazine Styphnate complex “
of Ni (no formula given) by dissolving freshly
pptd Ni hydroxide in an aq soln of styphnic
acid and treating the soln with aq hydrazine. Unsymmetrical Dimethylhydrazine, UDMH,
The resulting ppt was dried and tested for (CH3)Zm2; mw 60.10; N 46.62%, density
following properties: Flammability: the com- 0.784 at 25°; fr p –57’O; bp 63°; Refr Index
plex, either alone or in mixts with, RDX, was 1.4058 at ca 25°; fl p (Tag CC) 34°F; vap
just as difficult to ignite by means of a fuse, press 157mm at 25°; viscosity 0.51cPs at 25°;
or an electrical igniter as was the corresponding flammability limits– 150 to ca 60°; spontane-
complex Ni-nitrohydrazinate., When ignited, the ous ignition in air 250°; heat of forrnn (endo-
complex styphnate did not detonate and for thermic) 12.74kcal/mole at 25°; heat of combstn–
this reason is considered to be unsuitable for 474.1 lkcal/mole; impact sensitivity–not de-
use in detonators. Sensitivityy to impact: explo- tonable by 100g Tetryl chgq
sions’ were obtained 20% of the time on drop- may be j.repd by reduction of nitrosodimethyla-
ping a 2kg hammer from the height of 1.5m, mine (Ref 3). Korablina et al (Ref 6) prepd the
and 40% of the time from a height of 2.5m perchlorate salt of UDMH by reacting the base
lle~s:l) L. M~dard & J. Barlot, MP 34, 165 with HC104 at 50-60°, cooling or evapg to
(1952) & CA 48, 6125 (1954) 2) M.L. Fauth, deposit crystals. Resulting salt is sol in H2 O and
AnalChem 32, 655 (1960) & CA 54, 1594 detonates easily
(1960) UDMH is known to be miscible with the
following: water, benzene, triethyl benzene,
toluene, kerosene, ethyl alcohol, isobut yl al-
HYDRAZINE SUBSTITUTED DERIVATIVES: cohol, n-butyl ether, n-amyl ether, n-hexyl ,
ether, diethyl ether, petroleum ether, petroleum
Alkyl Substituted Hydrazines & Derivs naphtha, n-heptane, n-hexane, n-octane, n-decane,
Of the many alkyl substituted hydrazines, n-dodecane, n-hexadecane, cyclohexane, 1,2-
only two are used as rocket fuels now: mono- dimethyl cyclohexane, phenyl cyclohexane, n-
methyl hydrazine (MMH), CH3 NHNH2, and tetradecane, trichloroethylene, dichloroethylene,
unsymmetrical dimethylhydrazine (UDMH), perchloroethylene, 1,1,1-trichloroethane, tri-
(CH3 )2 NNH2. (See Hyperbolic Fuels in this ethyl amine, ethylenediarnine, diethylene
Vol for combustion properties” as rocket triamine, acetonitrile, aniline, cumene, tetra-
fuels). Their physical properties are summa- hydronaphthalene, tetraethylene pentamine,
rized below ethylene glycol and hydrazine (Ref 4)
kfonorrzethyl hydrazine, MMH, CH3 NHNH2 ,’ UDMH should always be handled under
mw 46.07; N 59,7%; fp –52.4°, bp 87.$’, a blanket of N (Ref 4)
 H 204

Other alkyl hydrazines. Picard & Boivin (Ref Rejk: C.F.H. Allen, Org Syntheses 13, 36 (1933)
2) studied the action of 100% HN03, mixed & CA 27, 3921 (1933) 2) J.J. Blansma &
at -30° with acetic anhydride, on various M. Ii. Wackers, RevTravChim 55, 661 (1936)
symmetrical disubstituted hydrazines. Westphal & CA 30, 7105 (1936) 3) J.P. Picard &
& Euhen (Ref 1) studied in great detail the J.L. Boivin, CanadJChem 29, 223 (1951) &
properties and thermal disscn of various tetra- CA 45, 9469 (1951) 4) L. M~dard & M.
alkylhydrazines Thomas, M6mPoudr 36, 97 (1956) & CA 50,
Refs: 1) O. Westphal & M. Euhen, Ber, 76B, 3763 (1,956)
1137 (1943) & CA 38, 4916 (1944) 2) J.P.
Picard & J.L. Boivin, CanJChem 29, 223 (1951) Hydrazine (or Hydrazinium) Sulfate. The name
& CA 45, 9469 (1951) 3) Jet Propulsion, p given in Clark (Ref 4) to the compd which is
399 (April 1957) 4) J. Heriches et al, US actually Dihydrazinium Sulfate (N2H ~) 2S04 .H ~0.
B of M RI 5635 (1960) 5) The Handling & It is prepd either by neutralization of hydra-
Storage of Liquid Propellants, Office of the zine hydrate soln by sulfuric acid or by neu-
Director of Defense Research & Engineering tralization of hydrazine hydrosulfate, followed
(Jan 1963) 6) L.S. Korablina et al, by evaporation of soln at 60° to obtain trysts
IzvVysshikhUcheb Zaved, Khim i Khim Tekhnol of D,fiydrazinium Sulfate, Monohydrate, melting
9 (3) 351 (1966) & CA 66, 2147 (1967) at 118.9°. Anhydrous salt can be obtd on
slow cooling but in contact with soln it is stable
Hydrazine Substituted AryI Derivatives only above the transition point, 47.3°; storage
NJV’’initro-N,Nt-dibenzoylhydrazine. PhCON(N02 )- over P *OS gives anhydrous srdt. The mono-
N(NOZ)COF%, hydrate is hydroscopic but insol in ale. Moist
mp 10 1.5°; may be prepd by reaction of nitric trysts have neutral pH. Can be used for prepn
a~id-acetic ahhydride mixtures with N, N’- of other hydrazines [See also Hydrazine (or
dibenzoylhydrazine; reacts with coned Hz SOq, Hydrazinium) Hydrosulfate]
giving off nitrogen oxides (Ref 3) Refs: 1) Gmelins Hdb (1936), Syst 23, p 560
2,4-dinitrophenylhydrazine. 2,4-(NOQ)ZPhNHNH2, 2) F. Summer & K. Weise, ZAnorgChem 94,
51–91 (1916) &CA 10, 1139–4 (1916)
may be prepd by reaction of 2,4-(N02 )2 PhCl, 3) B.E. Christensen & E.C. Gilbert, JACS 56,
AcOK and Nz ~ .Hz SOq (Ref 1); AHcomb, 1897099 (1934) 4) Clark, Hydrazine (1953), 10
395o cal/g at const press, A% 9.2 kcal/mole
at const press (Ref 4) Hydrazine and Derivatives, Analytical Procedures.
The following procedures are described in the
2,6-dinitrophenylhydrizine. 2,6-(NOZ )ZPhNHNHz,
book of Clark, Hydrazine (Ref 5): p 114–
Direct Iodate Method Using Solvent, originally
may be prepd from 2,6-(N02 )ZPhCl, AcOK
described in Ref 4
and Nz ~. Hz SOq (Ref 1)
pp 114-15–Direct Iodate Method with Internal
2,4,6-trinitrophenylhydrazine. 2,4,6-(NOZ )3 - Indicator, originally described in Ref 4
PhNHNH2 , p 115–Sulfate in Hydrazine by the method de-
may be prepd from picryl chloride, AcOK veloped by Mathieson Chem Corp
and ‘z ‘Q .Hz ’04 (Ref 1); ‘Hcomb 3070 pp 115-16–Ammonia in Hydrazine by the
cal/g at const press, -AH~ 5.8 kcal/rnole (Ref 4) method developed by Mathieson Chem Corp
a -(2 ,4,6- tn”nitrophenyl)-u -methylhydrazine. pp 116-17–Iron in Hydr@e. Calorimetric
2,4,6-(NOZ )3 PhN(CH3 )NH2; method with a,&’-Dypyridyl, earlier described
crystals; mp 170°; may be in Refs l&2
prepd by reacting MeNHNH2. H2 S04 with pp 117-19–Sulfides in Hydrazine, earlier de-
NaOH, faltering, ti”d reacting fdtrate with scribed in Refs 2 & 3
picryl chloride (Ref 2) p 119–Chloride in Hydrazine by the “method
developed by the Mathieson Chem Corp
~tten in collaboration with E. L. CApENER The method for estimation of hydrazine
R. M. WRIGHT content in unknown materials is described in
 H 205

Std Methods Chem Analysis (Ref 6). The method 3.3 Filter. A filter with a 10-micron nominal
consists of titration with O.lM K103 soln, stan- and 40 absolute rating shall be installed between
dardized against pure N ~H4.H2S0 ~ the manufacturer’s plant system and the container
Refs: 1) F.D. Snell & C.T. Snell, “Calorimetric to be ftied for delivery
Methods of Analysis”, VanNostrand, NY, Vol 3.4 Qualitative. The propellant shall be a
1 (1936), p 310 2) W.W. Scott, “Standard colorless, homogeneous liquid when examined
Methods of Chemical Analysis”, Van Nostrand, visually by transmitted light
NY, Vol 1, (1939), p 914 3) H.H. Willard 4. QUALITY ASSURANCE PROVISIONS.
& H. Diel, “Advanced Quantitative Analysis”, See in Specification
Van Nostrand, NY (1943), p 194 4) R.A. 4.5 Test Methods
Penneman & L.F. Audrieth, AnalChem 20, 4.5.1 Examination of product. The propel-
1058–61 (1948) 5) Ch.C. Clark, “Hydrazine”, lant shall be visrially examined while performing
Mathieson Chem Corp, Baltimore, Md (1953), test specified in 4.5.3 to determine compliance
pp 114–19, 6) R.H. Pierson, Edit, “Standard with the requirement as specified herein. Exa-
Methods of Chemical Analysis”, Vol.2 Part B, mination to ensure that the material conforms
Van Nostrand, Princeton, NJ (1963), p 1317 to 3.4 shall be conducted after the sample has
been transferred to the 500-rnl calibrated cy-
Hydrazine, Propellant, US Military Specifications linder
Requirements and Tests given in MIL-P-
are 4.5.2 Hydrazine assay and water. The pro-
26536C (May 1963), superseding MIL-P-26536B pellant and water content of the sample shall
(March 1964) be determined by the following method
1. SCOPE 4.5.2.1 Gas chromatographic method
1.1 This specification covers the require- 4.5.2.1.1 Suggested column preparation.
ments for hydrazine (N 2H4) propellant Weigh 10 grams of polyethylene glycol 400 and
3. REQUIREMENTS 20 grams of Anakrom B support material into
3.1 Chemical and physical properties. The separate beakers. Dissolve the polyethylene
chemical and physical properties of the pro- glycol 400 in reagent grade methylene chloride
pellant shall conform to those listed in table I (dichloromethane). The final volume of the
when tested in accordance. with the applicable solution should be approximately that of the
test methods support material. Pour the support materird
Table I Chemical a d Physical Properties into the polyethylene glycol 400 (stationary
Test phase) solution with gentle stirring. Evaporate
Properties Limits Paragraph the solvent by spreading the mixture in a tray.
Occasionally turn the mixture gently during
Hydrazine assay 98 min 4.5.2 the drying process. The column packing mate-
(percent by weight) rial is dry when it becomes a free-flowing powder.
Water (percent by 1.5 max 4.5.2 Fill a 1/4 inch x 1 meter (39.4 inches) stainless
weight steel tube by pouring the prepared material thru
Particulate 10max 4.5.3 a small funnel attached to one end. The bottom
(milligrams per liter of the tubing is plugged ‘with a small wad of
glass wool. Tap gently or use a mechanical
3.2 Limiting values. The following applies to vibrator to facilitate packing. When the column
all specified limits in this specification. For pur- is full, plug the inlet with glass wool and bend
poses of determining conformance with these the tubing to the configuration required by
requirements, an observed value or a calculated the chromatography oven
value shall be rounded “off “to the nearest unit” 4.5.2.1.2 Procedure. Install the prepared
in the last righthand place of figures\ used in column into the gas chromatography but do not
expressing the limitation value, in acc~rdance connect the column to the detector inlet. Con-
with the rounding-off method of the Recom- dition the column for at least 4 hours by heat-
mended Practices for Designating Significant ing at 302°F (150°C) with the carrier gas
Places in Specified Limiting Values (ASTM (helium) flow set at. approximately 50 milli-
Designation: E-29)
 H 206

liters per minute. After conditioning the column, a thermal conductivity detector
set the column oven temperature at 230°F ‘“ (2) Recorder: potentiometric strip
(1 10“C) and connect the column to the detector chart, O– 1 millivolt, 1 second F.S.
inlet. Adjust the carrier gas flow to 80– 120 ‘ response, with ‘integrator
milliliters per minute. If the gas chromat o-” (3) Tubing: stainless steel, 1/4 inch
graph is equipped with separate injector ahd de- O.D. x”1 meter (39.4 inches).
tector temperature controls, set the detector (4) Hypodermic syringe: 10 microliter,
f~ed needle
at 302° F (150°C) and the injector at 230”F
(5) Regulator: helium, to fit the
(110”C). Saturate the column by injecting two
cylinder
or three 10-microliter samples of propellant.
(b) Reagents
Saturate the column prior to each series of
(1) Anakrom B: 90/100 mesh,
analyses. When more than 30 minutes elapse
Analabs, Inc, 9 Hobson Ave,
between the elution of the hydrazine and the
Hamden, CT 06518, or equivalent
injection of a new. sample, resaturate the column
(2) Polyethylene glycol 400: Carbo-
with one 10-microliter injection of propellant
wax 400, or equivalent
sample. Use a clean, dry 10-microliter hypo-
dermic syringe and draw up 8 microliters of (3) Methylene chloride: ACS reagent
sample. Invert the syringe and expel the gas grade
bubbles. Carefully set the syrtige plunger to the (4) Helium gas: conforming to
3-microliter mark and wipe the tip with a piece MIL-P-27407
of tissue without touc~g the open end of the 4.5.3 Particulate. The propellant sample shall
needle. Quickly inject the sample into the in- be tested for contamination in accordance with
strument injection port and” then withdraw the ASTM Designation D-2276 -65T, Method A, with
syringe immediately. Measure the areas of all the following exceptions
peaks in the chromatogram. The analyst may 4.5.3.1 Mix the sample thoroughly by shaking
vary the temperature, flow” rate, column sti”e, the sample container. Immediately pour 500ml
and sample size to optimize the analysis ~ of the &urrple into a clean 500-ml graduated
4.5.2.1.3 Calculations cylinder. Use this 500ml of propellant for the
particulate analysis’
A 4.5.3.2 Use a solvent resistant falter disc
%N2~ =* x 100
i made from such materials as Millipore LSWP
04700, (Mitex-Teflon), Millipore URWP 04700,
., A (Solvinert), or Gelman VF-6, (Fluoride-Metricel),
%H20 ‘~ X 100 plain, white, 1@3 microns, 47rnm diameter in-
1 ,,
where: ‘ stead of the filter specified in Method 2276-65T
A NzH4 = the measured area of”the N2H4 peak 4.5.3.3 The drying oven temperature shall
multiplied by its signal attenuation be 158°F (70° C) instead of the 194% (90”C)
factor ‘ specified in Method 2276-65T
A H20 = the measured area of the H20 peak 4.5.3.4 Filtered isopropyl alcohol shall be
multiplied by its signal attenuation used for rinsing the sample bottle and filter
factor holder instead of petroleum ether specified in
ZAi = the sum ,of all the measured peak Method 2276-65T
areas in the signal attenuation 6. Notes
factors 6.1 Intended use of proplnt described in
this specification is as a fuel in rocket engines
Assumption: The thermal conductivities of all
6.2 Particulate is the undissolved solid re-
components in the sample are equal tained on a 10-micron falter membrane
4.5.2.1.4 Equipment and reagents. The fol- 6.3 Density. For informational purposes,
lowing equipment and reagents shall apply as the range of density for material conforming to .
test conditions of 4.5.2 “ this Spec is 1.002–1 .008g/ml at 25° (77°F)
(a) Equipment
(1) Gas chromatography: incorporating
 H 207

Hydrazinobenzene and Derivatives Refs: 1) Beil 15,489, (146)& [215] 2) Beil

Hydrazinobenzene or Phenylhydrazine (called 15,(146) & [219] Borsche & D.
3) W.
Hydrazino-benzol in Ger), C6H5 .HN.NH2; mw Rantscheff, AM 379,,171 (1911) 4)A.G.
108.14, N 25.91%; pale-yel monoclinic trysts Green & F.M. Rowe, JCS 101,2448 (1912)
or oily liq, mp 19.5°, bp 243.5° (with ,decompn), 4a) M. Giua, Gazz 52 (I), 346–49 (1922)
flash p 192°F (CC), auto ign temp 345”F, d 5) A.H. Blatt, Ed,Organic Syntheses Coil Vol
1.0978; sol in ale, eth, chlf, benz, w and dil 2 (1943), pp 228–29 (C.F.H. Allen) 6) Clark,
acids. Can be prepd by reduction of diazo- Hydrazine (1953), p 32 (Prepn), 32,92 & 97
tized aniline, followed by reaction with NaOH. (Uses)
Hydrazinobenzene is highly toxic by inhalation, ”
ingestion & skin absorption. It forms a hydrate N-Nitroso-N-[2,4dinitrophenyl]-hydrazine, ‘
with 0.5 water. Used in anal them as reagent (02 N)2C6H3.N(NO)NH2; mw 227.14, N
for aldehydes & sugars, and in org syntheses. 30.84%; yel lflts or prisms (from eth), mp 72°,
Also as fuel additive and gm absorbent bp–deflagrates; was prepd from 2,4-dinitrophenyl-
Refs: 1) Beil 15,67, (23), [44] 2) H. Gilman, hydrazine & NaN02 in a soln of HC1, water &
Org Syntheses Coil Vol 1 (1932), p 442 (G.H. alc (Refs 1 & 2)
Coleman) 3) Clark, Hydrazine (1953), p 33 Refs: 1) Beil 15, 493 2) T. Curtius & (?)
(Prepn), pp 39, 97,99& 100 (Uses) 4) Sax Dedichen, JPrktChem [2] 50, 263 (1894)
(1968), 1013 5) CondChemDict (1971), 681
Hydrazinotrinitrobenzene;2,4,6-Trinitrophenyl-
Hydrazinomononitrobenzene or Mononitro- hydrezine or Picrylhydrazine,
phenylhydrazine, O 2N.C ~H4.NH.NH z; mw (02 N)3C6H2NH.NH2; mw 243.14, N 28.81%;
153.14, N 27.44%. Three isomers are known: red-brn prisms; nearly insol in w, eth, chlf,
2-Nitro-,, brick-red ndls (from benz), mp 90° cold alc or benz; S1sol in hot ale; sol in acetic
(Ref 1) acid; was prepd from picrylchloride & hydra-
3-Nitro-, yel-orn ndls (from ale), mp 93° zine hydrate or acetate in ale. This compd is
(Ref 2) an expl less powerful & less brisant than PA
4-Nitro-, orn-red lfts or ndls (from boiling ale), Refs: 1) Beil 15,493, (147) & [221]
mp 157° (dec) (Ref 3) 2) A. Purgotti, Gazz 24 I, 113 (1894)
Other props & methods of prepn are found ‘ 3) W. Borsche, Ber 54, 1287 (1921); JCS
in Bed 66 I, 372 (1894) 4) A.H. Blatt, Ed, Organic
Refs: 1) Beil 15,454, (127)& [177] Syntheses, Coil Vol Z Wiley, NY (1943), 229
2) Beil 15,460, (129) & [182] 3) Beil
15,468, (130) & [183] Hydrazinebenzene or Phenylhydrazine Reactions.
Several investigators have studied the reaction
Hydrazinodinitrobenzene or Dinitrophenyl- betwn Phenylhydrazine and various aromatic &
hydrazine, (02 N)2C6H3 .NH.NH2; mw 198.14, aliphatic compds. The following Refs should
N 28.28%; OB to C02 –88.8%. Two isomers be of interest
are known: Refs: 1) F. Kehrmann & J. Messinger, Ber 25,
2,4-Dinitrophenylhydrazine, blah-red trysts 899 (1892) (Studies of reactions betwn Phenyl-
(from ale), mp 194°, dec at 198°; insol in w; hydrazine & dinitrochlorobenzene) 2) M.
sol in alc & ethyl acetate, SI sol in ether, benz & Giua, AttiAccadLincei 27 I, 379–82 & 247–52
chlfi was prepd in 1894 by Purgotti and in 1912 (1918) &CA 13, 1450, 1586 (1919); GazzChem-
by Green& Rowe by heating on a w bath 4- Ital 49 H, 146–54 (1919)&CA 14, 1530
Chloro-1 ,3-dinitrobenzene with freshIy prepd alc (1920) (Reactions betwn Phenylhydrazine and
hydrazine hydrate. Some of its salts are expl some aromatic nitrocompds contg a labile N02
(Refs 1,4,5 & 6) group, such as TNT’s, Trinitrobenzoic Acid,
2, 6-Dinitrop?renylhydnrzine, orn-red ndk (from Trinitroxylene, Trinitrocresol & Trinitroanisole
ale), mp 145°; insol in w; sol in hot w; S1sol in were studied. In most cases the ‘formation of
eth, benz & chlf; was prepd from 2-chloro-l ,3- nitrohydrazo compds was observed). 3) R.C.
dinitrobenzene & hydrazine hydrate in @ alc Elderfield, “Explosives from Hydroxy and Amino
(Refs2, 3,5 & 6)
 H 208

Compounds”, OSRD 158 (Ott 1941), pp 24–25 Hydrazinodicarbonic Acid Diazide or Hydrazo-
[a) On condensing Phenylhydrazine with 2,4- dicarbonazide,N3.0C.HN.NH.C0.N3; (called
dinitrochlorobenzene, instead of the expected Hydrazindicarbons&.rrediazid Ger); mw 170.10,
in
dinitrohydrazobenzene, 2-phenyl-5’-nitrobenzo- N 65.88%, OB to C02 and N2 –28.2%; ndls
triazole, (from eth), mp” 150–52° with evolution of gas
HC = CH – ~ = ‘\N.C6H5 (when heated slowly); explodes without melting,
(02N)~ = CH - C = NZ , was obtd. when heated rapidly. May be prepd from
hydrazidicarbonhydrazide hydrochloride,
When nitrated, this compd yielded an expl,
H2 NNHCONHNHCONHNH2 .2HC1, and an
aqueous solution of NaN02. ,Dfficultly sol in
cold w & bz; insol in chlf & ligroin; sol in
called 2(2’’,4’’-Dinitrophenyl} 1‘,5 ‘-dinitrobenzo- acetone, alcohol & hot ethylene bromide; very
triazole. b) Also on condensing Phenylhydrazine sol in eth
with 2 ,4-dinit rochlorobenzene, followed b y re- It is a primary explosive and is slightly more
fluxing in glacial acetic acid, 2-phenyl-(5’-nitro- sensitive to impact than Lead and Siiver Azides.
benzotriazole)-l -oxide, It would require 0.25g of this explosive to deto-
nate lg of TNT
?
Refs: 1) Beil 3, (60) & [102] 2) ‘R. Stolh$ Ber,
43, 2468 (19 10) (Prepn of hydrazidicarbon-
hydrazide) 3) W. Kesting, Ber, 57, 1321 (1924)
When this compd was nitrated, an expl compd ‘&CA 19,245 (1925) 4) Clift & Fedoroff,
2-(2’’,4’’-Dinitrophenyl)-l ‘,5 ‘-dinitrobenzotri- Manual for Expls Labs, Lefax, Phila, Pa, Vol
azole- 1-oxide, 2 (1943), p H9
9
H =C(N02)–~=fi
Y
(02N)C = CH — C=N~
‘N.C6H3(N02)2, Hydrazinoethane. See Ethyl I-Iydrazine in
Vol 6, p E300-R
was obtd]

Hydrazino compounds, Analytical Methods for Hydrazinoethane; 2,2-Dinitro. See 2,2-Dinitro-

Three.potentiometric methods of analysis of ethyl Hydrazine in Vol 6, p E300R
hydrazine compounds are described:

1) Dissolve sample in Hz O, add coned HC1, cool Hydrazinohydroxyazobenzene and Derivatives

& titrate until equilibrium is established between Hydrazinohydroxyazobenzene,
700 & 800 mv. This. takes place when the IO; is H0.C6H4.N:N.C6H4 .HN.NH2; mw 228.25, N
reduced to ICI, losing 4 meq 2) Dissolve in H20- 24.55%; may be considered as parent compd of
H2 SO & titrate to the formation of 1° 3) Dis- its dinitro deriv, although not used to prep it
solve in boiling H 20 & keep under nitrogen while Refi Bed, not found
cooling. To cold soln add NaOH & titrate to I-
end pt. The 3rd method gives low results but 4,6-Dinitro-3’-hydrazino-4-hydroxyazobenzene
is the only possible method for some hydrazino (called Phenol-(4azo3) - [4,6-dinitrophenylhy-
compounds drazin] or 4,6-Dinitro-3’-hy drazino-4-oxy-
Ret W. R. McBride et al, AnalChem 23, 890 azobenzol in Ger).
(1951) & CA 45, 7463 (1951) Ho.CbH~.N:N.CbH’(NO’) zNH.NHz; mw
318.25, N 26.41%; red-brown crystals; S1sol
Hydrazinodicarbonic Acid and Derivatives in boiling ale; sol in boiling nitro-benzene.
IYydrazinodicarborzic Acid, HOOC.HN.NH.COOH; Prepd by reacting 5’-chloro-2’ ,4’-dinitro-4-
mw 88.07, N 31.8170; may be considered as a hydroxy-azobenzene & hydrazine hydrate in
parent compd of its deriv, although not used to hot alcohol. Decomposes 178–80°
prep it Refs: 1) Beil 16, [262] 2) W. Borsche,
Ber 54,684 (1921) ,.
 H 209

Hydrazinomethane or Methyl Hydrazine, Hydrazinopyridine and Derivatives

CH3.HN.NH2; mw 46.07, N 60.81%; hygr Hydrazinopyndine, H2N.NH.C5 H4N, mw 109.13,
flammable liq, sp gr 0.874 at 25°; fr p <80° N 38.51%. Exists as 2-, 3- & 4-hydrazino isomers
(Lange), –52.4° (CondChemDict). It can be (Refs 1 & 2). Maybe considered as parent compd
prepd by method of Thiele (Refs 1 & 2) con- of nitrated derivs, although they were not prepd
sisting of condensing hydrazine with benzalde- from it
hyde to give azine, C6H5 .CH:N.NH2, which is Rej3: 1) Beil 2? (688) & [487] 2) Beil
treated with dimethyl sulfate followed by 22, [488]
water:
(CH3)2S04 Hydrazinopyridine Azide, C5HCNC, not found in
C6H5 .CH:N.NH2 ~ Beil

C6H5.CH:N.NH.CH3 + H20 +
Nitrohydrazinopyridine, C5H6N402; mw 154.13,
C6H .CHO + H2N.NH.CH3 N 36.35%. Two isomers are known:
S-Nitro-2-hydrazinopyndine,
It is used in missile proplnts and as a solvent “02N
and intermediate (Ref )
o N NH.NH~;
Refs: 1) Beil 4, 546, (560), [957] & { 1726)
2) J. Thiele, Ann 376, 239–68 (1910) trysts, mp 204–06° (dec); diffc sol in common
3) Clark, Hydrazine (1953), 35 4) CondChem- SOIVS;sol in alkalies; tin be prepd by treating
Dict (1961), 742-L and (1971), 575-R 6-chloro-3-nitropyridine with hydrazine hydrate
or alcoholic hydrazine soln under cooling (Ref
1); from 5-nitro-2-pyridine, solfonic acid & the
Hydrazinophenol and Derivatives appropriate amine (Ref 3), or by boiling 2-
4-Hydmzinophenol, C6H4(OH).HN.NH ~; mw metroxy-5-nitropy ridine with hydrazine (Ref 4)
124.14, N 22.57%; trysts, rep-unstable. It 3-Nitro-4-hydrazinopyridin e, NH.NH2
can be prepd as hydrochloride salt by heating o~
N- [4-hydroxyphenyl) -hydrazine-N ‘-sulfonic acid o N;
K with alc & HC1; forms other salts red ndls (from ale), mp 200°; insol in eth &
Refs: 1) Beil 15, 596 2) ? Altschul, Jprakt.
benz; S1sol in w & ale; v sol in acids giving a
Chem [2], 57, 202(1 898) yel colored soln; was prepd by treating hydrazine
hydrate with 4-chloro-3-nitropyridine in a little
Hydrazinophenol Azide, N~ .C6H3(OH).HN.NH2;
alc heated on a water bath (Ref 2)
not found in Beil 2) Beil 22, [489]
Refs: 1) Beil 22, [487]
3) A. Mangini & M. Collona, Gazz 73, 313
4,6-Dinitro-3-hydrazinophenol or 4,6-Dinitro-3-
(1943) &CA 41, 1225 (1947) 4) M. Collona
hydroxyphenylhydrazine, (02 N)2C6H2(OH).NH.NH2;
& D. Dal Monte Casoni, BollSciFacoltaChimInd-
mw 214.14, N 26.17%, OB –74.6%; fine egg-
UnivBologna 5, 35 (1944–47) &CA 44, 3494
yellow flocks, resembling yellow HgO when dry;
(1950)
mp 197° (decomp); sol in hot alc (with separation
of red-brown spherical granules); sol in warm aq
Dinitro, C5H5 N504, and Trinitrohydrazino-
HC1; decomposed by dil NaOH with vigorous
pyridine, C5H4N6 06, were not found in Beil
foaming. Prepd by heating 2,5-Dinitro-4-
chlorophenol in alcohol with hydrazine hydrate
& then acidifying with dil nitric acid
5-Hydrazino-tetrazole (Tetrazyl-5-hydrazine)
Refs: 1) Beil 15, [274] 2) W. Borsche, Ber
([Tetrazolyl-(5)] -hydrazin, Tetrazolonhydrazon
54B, 676 (1921)&CA 15, 2844 (1921)
in German);
H2N.NH–C–NH-N or H2N.N=C.NH.N ‘
Trinitrohydrazinophenol, C6H5 N~ 07,, not found
in Beil II II I II
N—N NH-N;
 H 210

mw 100.09, N 83.97%; trysts (from w), mp 199° in Beil:

(dec), bp–decomp explosively on heating above 3,5-Dinitro-2-hydrazinotoluene, orn ndls (from
mp; S1sol in cold w; sol in alkalies & ammonia; ale), rnp 169° (dec); v S1sol in ale; was prepd
~insol in ale, eth & benz. It was first prepd by from 2,3,5 -Trinitrotoluene & hydrazine hydrate
Thiele et al (Refs 1 & 2) by reduction of tetra- in alc (Refs 1 & 7)
zolediazonium chloride with stannous chloride 2,4-Dinitro-3-hydrazinotoluene, red prisms (from
in the presence of HC1: Other methods of prepn ZIC or benz), mp l~O”; sol :in warm 10% HC1;
are given in Refs 1, 2 & 5 was prepd by wafiing 2,3,4-Trinitrotoluene
Refs: 1) Beil 26, 405 2) J. Thiele et al, Ann with hydrazine hydrate in dil alc and cooling
273, 155 (1893); 287, 235 (1895) and 303, 62 the soln (Refs 2 & 7)
(1898) 3) E. Lieber & G.B .L. Smith, Cher-n- 2, 6-Dinitro-3-hydrazinotoluene, solid, rep-not
Revs 25, 240 (1939) 4) F.R. Benson, Chem- reported; was prepd by warming 3-chloro-2,6-
Revs 41, 8 (1947) 5) F.L. Scott et al, JAppl- dinitrotoluene with hydrazine hydrate in dil
Chem 2, 369 (1952) &CA 46, 3354 (1954) alc on a water bath (Refs 3 & 7)
6) No more recent refs found in CA 4, 6-Dinitro-3-hydrazinotoluene, yel-red trysts
(from ale), mp 194–95° (dec); sol in ale, benz
& chlf; was prepd by treating 2,4,5 -Trinitroto1-
Hydrazinotoluene and Derivatives uene with hydrazine hydrate in alc (Refs 4 & 6)
Hydrazinotoluene or Tolylkydrazine, 3,5-Dinitro-4-hydrazirwtoluene, copper-colored
H3C.C6H4.HN.NH2; ITiW 122.17, N 22.93%. tablets (from ale), mp 139°; was prepd by
There are three isomers, ortho-, meta-, and para- heating an alcoholic soln of 3,4,5 -Tririitrotoluene
tolylhydrazines with alc hydrazine hydrate soln (Refs 5 & 7)
Refs: 1) Beil 151496, (147) & [222] (ortho) Other props are given in Refs
2) Beil 15, 506, (152) & [229] (meta) , Refs: 1) Beil 15, [229] 2) Beil 15, [231]
~ 3) Beil 15, 510, (153) & [233] (para) - 3) Beil 15;”(152) 4) Beil 15, (1 15), [232] &
{676} 5) Beil 15, [244] 6) M. Giua,
Hydrazinotoluene Azide, C7H9N~, not found in Gazz 49, H, ’171 (1919); 53, 849 (1923)
Beil 7) O.L. Brady & J.H. Bowman, JChemSoc
119, 896, 899 & 900 (1921)
Mononitrohydrazinotoluene, C TH9N’30Z; mw
167.17, N 25.14%. Two isomers are found 2,4,6-Trinitro-3-hydrazinotoluene,
in Beil:
5-Nitro-2-hydmzinotolpene, lt golden-yel or
.,,
O,
*N
CH s
N02
orn-yel ndls with a violet ,tinge (from ale),
mp 179–80°; diffc sol in hot alc & .xylene;
was prepd by heating the K salt of N- [4-
n V NH.NH,
Nitro-2-methyl-phenyl] -hydrazine-N,N ‘-disul- N02 :
fonic acid with coned HC1 (Refs 1 & 3) mw 257.17, N 27.2470; golden-yel pltlts (from
3-Nitro-4-hydrazinotoluene, dk-red ndls (from ale), mp 176° (dec); sol in ale, benz, chlf & acet;
eth), mp llO–llO; v sol in acet; sol in eth, sol in alkalies giving a red-brn soln; S1sol in
chlf & benz; d sol in petr eth; was prepd by petr eth;’”was prepd by treating 2,4,6-Trinitro-3-
diazotizing 2-nitro4-methylaniline with Zn methoxytoluene” with hydrazine hydrate in alc
.,
chloride & HC1, Its Hydrochloride salt, (Refs 1 &2)
C7H9N302+HC1, orn-red ndls or plates (from Refs: 1) Beil 15, (153) 2) M. Giua, Gazz
w) dec at 190–910 (Refs 2 & 4) 49 II, 174 (1919)
Refs: 1) Be~ 15, 505 2) Beil 15, 530
3) Bamberger, Ber 30, 516 (1893) 4) Pope
& Hird, JChemSoc 79, 1142 (1901) 3-Hydrazine-1,2,4-triazole,
HN–NH-C=N.NH ~ or HN-N=C-NH.NH2
Dinitrohydrazinotoluene, C7HSN404; mw II
212.17, N 26.41%. Five isomers are described
 H 211

mw 99.10, N 70.68%; ’no props given; was prepd Refs: 1) Beil 15,493 & (147) 2) M. Giua
by reduction of S-nitrosimino-l ,2,4-triazolin- &F. Cherchi, GazzChimItal 49 (2), 152 (1919)
3-carboxylic acid with Zn chloride & HC1 at &CA 14, 1532 (1920) 3) R. Andrisano &
–3°. Its Hydrochloride ~lt, C2H5 N5 +HC1, D. Dal Monte Casoni, BollSciFacoltaChimInd
ndls, dec at 224°. Also form a Picrate w“lt, Bologna (1) (1943) &CA 41,723 (1947)
CzHSNS+CGHsN@T, lt-yel ndls (from w), mp 4) No further refs were found in CA thru 1971
165° (Refs 1 & 2)
Refs: 1) Beil 26, 138 2) W. Manchot & Hydrazobisformamidine or Hydrazodicarbon-
? Nell, Ann 343, 18 (1905) amidine. See Biguanidine in Vol 2, p BI 15-L

5,5’-Hydrazo-bis-1H-Tetrazole. See Bis (5-Tetra-

Hydrazobenzene See N,N’-Di-
and Derivatives. zole)-hydrazine in Vol 2 of Encycl, p B 157-R
phenylhydrazine and Derivatives in Vol 5 of and the following addrd refs
Encycl, pp D1462-R to D1463-L and the fol- Refs”, 1) F.R. Benson, ChemRevs 41, 8 (1947)
lowing derivs not described: 2) O.E. Sheffield, “Long Range Basic Research
2,4,2’-Trinitrohydrazobenzene, Leading to the Development of Ideal Propellants.
(02N)ZC6Hd.NH.M.CGH~(NO~); mw 319.23, Compounds of High Nitrogen Content in Propel-
N 21.94%; pale yellow needles (from HAc), lant Powders,” PATR 1694 (May 1948) 3)
mp 220°, puffs off on strong heating; sol in W.S. McEwan & M.W. Rigg, JACS 73, 4725
acetone, chlf, ligroin & Et acetate. Prepd from (1951) & CA 46, 4350 (1951) (’give AH;)
2-nitrophenylhydrazine & 4-chloro- 1,3-dinitro-
benzene Hydrazodicarbonazide. See Hydrazinodicar-
Refs: 1) Beil 15, 490 2) A. Werner & bonic Acid Diazide
? Stiasny, Ber 32, 3281 (1899)
2,4,3’-Trinitrohydrazobenzene, Hydrazoic Acid. See under Azides in Vol 1,
(02 N)zCGHS.NH.NH.C GH4(NOZ); no props p A537-42
given; was prepd by heating 3-nitrophenyl-
benzene (2 mols) with 4-chloro- 1,3-dinitro- Hydrazotates. See tides
benzene at 1.00–105°
Refs: 1) Beil 15, 490 2) A. Werner & 5,5'-Hydrazotetrazole. Compd investigated for use
? Stiasny, Ber 32, 3280 (1899) as a primary explosive. Impact sensitivityy was
2,4,4’-Trinitrohydrazobenzene, found unsatisfactory. Some pertinent properties:
(O ZN)2CGH3.NH.NH.C 6H4(N02); lt-yel ndls Impact sensitivity 32 ems, Vac Stab, 1.7 MI of
(from Nitrobenz), mp 21 2–13°; sol in glac acet gas/48 hrs/lOO°C, Hot Bar Ign temp 239°C
ac & acet; S1sol in hot ale; almost insol in benz Ref Francis Taylor, NAVORD Rept 2800,
& chlfi insol in petr eth; was prepd by heating Primary Explosives Research, Naval Ord Lab,
2 mols 4-nitrophenylhydrazine with 1 mol White Oaks, Md (1953)
4-chloro- 1,3-dinitrobenzene at 100–05° (Refs NOTE: See also 5,5’-Hydrazo-bis-tetrazole in
1&2) Vol 2 of Encycl, p B 157-R
Refs: 1) Beil 1.5, 490 2) A. Werner &
? Stiasny, Ber 32, 3266, 3277 (1899) Hydrazulmin. C6H6N6, mw 162.16, N 51.83%, soot-
2,4,6-Trinitrohydrazobenzene (called N-Phenyl- black shiny leaflets. Prepd from cyanogen & dry
N’ [2,4,6-trinitrophenyl] -hydrazin h Ger). ammonia. Decomposes on heating to give paracyano-
C6H5NH.NH.C6H2(N02)3; mw 319.2, N 21.9%; gen; decomp in water
dark red prisms (from HAc or acetone); mp Ret Beil 2, 553
181°; decomp on rapid heating & puffs off
in a flame; S1sol in alc or chl~ somewhat sol Hydrides. Both ionic & covalent compounds of
in acetone. Prepd from phenylhydrazine & H with another element usually metallic. These
picrylchloride (Refs 1 & 3) or trinitroanisole will generally be described under the “other”
& phenylhydraztie in abs EtOH (Ref 2). It element eg Al-hydride in Vol 1, p A145 & B-
may be considered to be a mild explosive hydrides in Vol 2, pp B253-56. However certain
 H 212

props common to the hydrides follow below: 31, 2334 (1953 )& CA47, 8371 (1953) 3)
Toxicity: Variable. The hydrides of phospho- Sax, 3rd edit (1968), p 820
rus, arsenic, sulfur, selenium, tellurium and boron
which are highly toxic, produce local irritation Hydrin is the reaction product of a polyhydric
and destroy red blood cells. They are particularly alcohol and an inorganic acid, eg ~ chlorhydrin
dangerous because of their volatility and ease of is formed from HOCH *CH(OH)CH20H + HC1=
entry into the body. The hydrides of the alkali HOCHZ CH(OH)CH2 Cl + Hz O
metals, alkaline earths, aluminum, zirconium and Ref Hackh’s (1944), p 418-L
titanium react with moisture to evolve hydrogen
and leave behind th; hydroxide of the metallic Hydrinwestfalite. A German explosive containing
element. This hydroxide is usually caustic. See DNT
also sodium hydroxide Rej Colver (1918), p 167
Hydrides, metallic, primary type:
This group includes the hydrides of calcium, Hydrobel. Brit Expls used for Pulsed Infusion
lithium, magnesium, potassium, sodium and . Shot firings: NG+NGc 37.9-40.9, NC 1.O-3.0,
strontium. In the presence of moisture they are woodmeal 0.6-1.6, AN 19.0-21.0, NaCl 26.1-
readily converted to hydroxides which are highly 28.1, Bar!ytes 8.7-10.7, chalk 0.1-1.0, diammonium
irritating to the skin by caustic and thermal phosphate 0.1-0.8, Acid Magenta 0.001-0.05,
action. Similar effects can occur on contact with AS No, 2 (optional) 0.001-0.01%; d 1.7; vel of
eyes and respiratory” mucous membranes deton 5000 m/see; temp of expln–not given. To
Fire Hazard: The volatile hydrides are flam- initiate hydrobel chges under high hydrostatic
mable, some spontaneously so in air. All hydrides pressure, it is necessary to use a specially de-
react violently on contact with powerful oxidiz- signed Cu tube & submarine electric detonators
ing agents. When heated or on contact with Ref. McAdam & Westwater “Mining Explosives,”
moisture or acids an exothermic reaction evolving Oliver & Boyd, Edinbtirgh (1958), p 109
hydrogen occurs. Often enough heat is evolved NOTE: The compn of AS No 2 is not reported
to cause ignition. Hydrides require special hahd-
ling instructions which should be obtained from Hydrocarbon. C20 HX; mw 264.39, crystals, mp
the manufacturers 38°, bp 330°. Was prepd by Puranen & Ehrn-
Explosion Hazard: The volatile hydrides (such as rooth from cymene by treating it at low temp-
hydrides of boron, arsenic, phosphorus, selenium, erature with a solution of nitrosylsulfuric acid
tellurium) form explosive mixtures with air. in coned Hz S04, who proposed it as a starting
The nonvolatile hydrides (such as sodium, lithium, material for preparation of various explosives
calcium) readily liberate hydrogen when heated Refi N. Puranen & E. Ehrnrooth, GerP 611461
or on contact with moisture or acids. Further- (1935) & CA 29; 4020 (1935)
more, hydrides form dust clouds which can
explode due to contact with flames, sparks, heat Hydrocarbons. Compounds consisting of carbon
or oxidizers and hydrogen, The number of such compounds is
Disaster Hazard: Highly dangerous; when heated, immense and they may be classified into:
they can ignite at once or liberate hydrogen: “aliphatic” (alicyclic) and “aromatic” (cyclic)
they react with moisture or acids to evolve heat compounds. In the former class, the principal
and hydrogen; on contact with powerful carbon atoms are arranged in chains, while in the
oxidizers violent reactions can occur. (Ref 2) latter class they are arranged in one or several
Metal hydrides (Al, Li, LiAljetc) in Me ether rings. Hydrocarbons may also be divided into
solns should not be evaporated because of the “saturated’’-in which all four valences of C are
danger of explosions (Ref 1). Similarly the use satisfied, and “unsaturated’’-in which there are one
of LiA1-hydride is not recommended for drying or more double or triple bonds between carbon
Me ethers (Ref 2) atoms
Refs: 1) G. Barbaras et al JACS 70,877 (1948) & Many hydrocarbons furnish explosive. nitrates
CA 42,3572 (1948) 2) R. M. Adams C & EN or nitrocompounds on nitration. (See under
individual compounds)
 H 213

The literature on hydrocarbons is overwhelm- (Ref 7), who gives (Qf)v = 1400 cal/g &
ingly voluminous. Only three standard references (Qf)p = 1428 cal/g
are listed below:
Refs: 1) Beil original, & 1st, 2nd, 3rd & 4th Hydrocellulose Nitrate or Nitrohydrocellulose.
Supplements 2) G. Egloff “Physical Constants A substance resembling NC in its properties (but
of Hydrocarbons;’ Reinhold, NY (1939-47) in slightly more sensitive to shock), was prepd
five volumes & ACS Monograph 78 3) F. D. by Cross and Bevan and Beadle by. nitration of
Rossini et al “Hydrocarbons from Petroleum” 1 part of dry hydrocellulose by means of 3
Reinhold, NY (1953) ACS Monograph 121 parts of nitric acid and 9 parts of sulfuric acid
Hydrocarbons As Rocket Fuels or Explosives. (Refs 1, p 25, & 2, p 556); products correspond-
Liquid methane other hydrocarbons are con-
& ing to hexa- and heptanitrohydrocelluloses are
sidered as propellant fuels (Ref 1). Nitrogen , formed. Its use in explosives was recommended
tetroxide and hydrocarbons (kerosine) are by Luck, Durnford and Ungania (Ref 2, p, 557).
claimed as a blasting explosive (Ref 2) Trauzl (Ref 2, p 199) proposed using detona-
Refs: 1) J. D. Clark, Ordnance 36, 661 (1952) tors charged with a gel prepd by impregnating
2) D. H. Ross & T. J. McGonigle, USP 1 part of Nitrohydrocellulose with 1 to 3 parts
2,759,418 (1956) & CA 51, 719 (1956) of NG. Such detonators could be used underwater
Refs: 1) P. Vieille, MP 2, 21 (1884) (Prepa-
Hydrocellulose. C12H22011, rnw 342.30. The ration and properties) 2) Daniel (1902) 199,
term has been employed since about 1880 to pp 381 & 556-7 3) Marshall, 1, (1917), 153
designate a cellulose which has been weakened 4) Marsh & Wood, Cellulose (1945), p 222
or tendered as the result of treatment with 5) Stettbacher (1933), 124 6) C. Dor6e,
acids. It retains water strongly.’ Hydrocellulose “The Methods of Cellulose Chemistry”, Chap-
is not a single substance but a mixture of man & Hall, London (1947), pp’ 144-77
hydrolyzed products less complex than cellulose 7) P. Tavernier, MP 38, 305 & 308 (1956) &
itself and more or less related to it and to CA 51, 15952 (1957)
glucose (Refs 4 & 6)
Hydrocellulose differs from hydrated Hydrochloric Acid or Muriatic Acid. See
cellulose in its properties (Ref 3). According Hydrogen Chloride, Anydrous and Hydrochloric
to Stettbacher (Ref 5) hydrocellulose lies Acid
between the hydrated cellulose and oxycellulose.
Its use as a flash reducer in a propellant has Hydrocinnamic Acid and Derivatives
been claimed by C.R. Franklin in USP 1564549 Hydrocinnamic Acid or 3-Phenylpropionic Acid,
(1925) &CA 20,505 (1926). Accdg to CIOS Cb H~CH2CH2COOH; mw 150.17, crystals, mp
Rept 31-68 (1945), pp 6–7, hydrocellulose was 46°; S1sol in w; sol in alc or eth. Prepd by the
used during WWII by Germans in some rocket reduction of cinnamic acid with Na-amalgam
propellants, presumably to improve their burning
characteristics. For instance the so-called Ammon- cX-Azidohydrocinnamic Acid or rX-Azido-b
pulver contained 5% hydrocellulose and the EP phenylpropionic (called ~-Amido-Hydro-
Acid
(Einheitspulver) contained about 3%. Hydro- zimtsaure in Ger), C6H5 .CH2 .CH(N s).COOH;
ceilulose was also used in some rocket pro- mw 191.19, N 21 .98%;,plates, mp 24–7°. Its
pellants to increase the rate of burning at Silver salt, AgC9H8N~02, tryst (from w), ex-
low temperature plodes mildly on heating; the Ammonium salt,
Note: Their Einheitspulver Standard (or white tryst, burns quietly on contact with a
Unit) Propellant was “G” Pulver (qv), which flame
contd 3~0 hydrocellulose & 1.5% K-nitrate. Its Refs: 1) Beil 8, (205-6) 2) A. Darapsky &
props are given in PATR 2510 (1958), p Ger H. Berger, JPraktChem 96, 320-1 (1917); JCS
190-R 114 I, 507-8 (1918) & CA 13, 1304-5 (1919)
Hydrocellulose can be nitrated, forming, an 3) No further refs found in CA thru 1971
explosive (Refs 2 & 5). Hydrocellulose is claimed
to be Cw~ 020 mw 648.56 by Tavernier
 H 214

Hydrocinnamic Acid Azide (called Hydrozimt- vation energy for HCN/Oz flames is claimed to
sdure-Azid in Ger). C6H5CH2CH2CON3; mw be 42-44 kcal/mole (Ref 11). HCN has also been
175.19, N 23.99%, powdery trysts (from eth); considered as a rocket fuel. Its combustion en-
insol in w; sol in alc or eth. Puffs off .on heating. thalpy and specific impulse are high & even its
Prepd by reacting hydrocinnamic acid hydrazide toxicity is relatively low when compared with
in HC1 with Na-nitrite diborane & hydrazine (Ref 10)
Refs: 1) Beil 9, 513 2) No further refs found Some of its salts are also explosive, for
in CA thru 1971 example, Hg(CN)z and Hg(CN)z oHgO. Its methyl
salt is explosive when in the CH3 NC form,
Hydrocyanic Acid or Hydrogen Cyanide (For- while the CH3 CN form is not an explosive
monitrile or Prussic. Acid), HCN, mw 27.03, N HCN is used in the manufacture of polymers
51.82%, OB to C02 -14.9%; highly poisonous, & fumigants (Ref 14)
colorless liquid or gas; d 0.697 at 18°, fr p NOTE: Accdg to Blatt, OSRD 2014 (1944),
-13.3°, bp +25.6°, fl p O“F, auto ignition temp HCN is an expl of low sensitivity to initiation
10O”F. Very sol in w, alc & eth. Exists in two because it cannot be detonated by No 8 cap.
isomers, H.C:N and H.N: C. This fact was first In order to detn its power by Trauzl Test, a
stated by Enklaar and then confirmed by 3g sample in lead block 10xl Ocm, cooled to
W6hler and Roth, who also examined the ex- 0° was detonated with 0.4g LA+ I .25g PETN
plosive properties of HCN (Ref 3). May be initiator. It gave an expansion of 95–100CC
prepd by treating a cyanide, such as calcium and this usually split the block
cyanide, with dilute sulfuric acid; also cata- Refs: 1) Beil, 2, 29 (22) & [37] 2) Ullmann,
lytically from hydrocarbons and ammonia (Ref 3, (1926), 470-510 3) L. W6hler & J. Roth,
6). HCN is present in the products of detonation ChemZtg, 50, 761-3, 781-2 & CA 21, 496
of various explosives. The dissociation energy (1927) 4) Marshall, 3, (1932), 137 5) W.M.
for H-CN is 129 t 3 kcal/mole, (Ref 9). It is an Latimer & J.H. Hildebrandj “Reference Book
explosive which requires a stronger initiation of Inorganic Chemistry,” MacMillan, NY, (1940)
than that supplied by a No 8 cap for its deto- p 284 6) K.J. McCallum & H.M. Trainor, Canad
nation. For instance, 3g of HCN, cooled to 0°, JRes 27B, ,412 (1949) 7) GerPatApplNo B20028
may be detonated with a cap containing 0.4g ((12k, 9) (April 17, 1952) 8) E.H. Cause & P..
of Lead Azide and 1.25g of PETN. If the D. Montgomery, JChemEngData 5, 351 (1960)
detonation takes place in a lead block 10 x 10 & CA 55, 18112 (1961) 9) H.T. Knight &
cm, the block is generally split in two. The J.P. Rink, JChemPhys 35, 199 (1961) & CA 56,
explosion of HCN is favored by its preliminary 2008 (1962) 10) A. Beckers, Waerme,70(3), 96
polymerization by alkalies (Ref 3). It may even (1964) & CA 61, 14454 (1964) 11) M. Ailliet
polymerize explosively (Ref 12). Presence of & A. Van Tiggelen, BullSocChemBelg, 77, 433
NaOH, but not water, and increasing temp were (1968) & CA 70, 3194 (1969) 12) Sax, 3rd
found to favor violent HCN polymerization. The Edit (1968), p 822 13) L.J. Drummond, Corn
heat of polym is 377 cal/g (Ref 8). In the bustSciTechnol 1 (6) 415 (1970) & CA 73,
presence of NO & argon, HCN explodes when 68154 (1970) 14) CondChemDict, 8th Edit
heated in a reflected shock wave to give CN, (1971), p 453
NCN, NH & OH radicals during the pre-explo-
sion induction period. The reaction NO+HCN= Hydrodynamics. Flow systems are governed by
CN+HNO is claimed to be rate-controlling (Ref the laws of hydrodynamics. How these laws re-
13) late to detonation was discussed in Vol 4, pp
The combustion of HCN has been studied D602-22. Recent books and reviews on this
extensively. Ignition limits in air are ca 42.5 & subject are listed below:
8 VO1’70.In the presence of C02 these limits 1) H.R. Valentine, “Applied Hydrodynamics”,
coalesce for the mixture C02 36 vol% & HCN Butterworth Scientific Publications, London
12 VOI% (Ref 6). Burning velocity, flame temp (1959)
& thickness of reaction zone for HCN/Oz /N2 2) D.H. Wilson, “Hydrodynamics”, E, Arnold,
mixtures have been measured. The overall acti- London (1959)
 H 215

3) S. Chandrasekhar, “Hydrodynamic & Hydro- review of the 1967 fluid dynamics literature.
magnetic Stability”, Clarendon Press, London IndEngChem 61, 41 (1969) & CA 70, 69515
(1961) (1969)
4) G.H.A. Cole, “Fluid Dynamics”, John Wiley, 21) W. N. Gill et al “Fluid Dynamics.” Review of
NY (1962) literature for 1968 with 791 refs. IndEngChem
5) V.G. Levich, “Physiochemical Hydrodyna- 62, 49 (1970) & CA 72134564 (1970)
mics”, Prentice-Hall, Englewood Cliffs, NJ 22) W. N. Gill et al “Fluid Dynamics:” Review
(1962) for 1969. IndEngChem 62, 108 (1970) & CA
6) C. Truesdell, “Fluid Dynamics II”, Vol VIII 74, 55600 (1971)
of Encycl of Physics, ed S. Fluegge, B.H.
Blackwell, Oxford (1963) Hydrodynamic Detonation Velocity. Same as
7) R.H. Sabersky & A.J. Acosta, “Fluid Flow”, Ideal Detonation Velocity, briefly described in
Macmillan, NY (1964) Vol 4 of Encycl, p D630-R
8) M. Weintraub “Chemical Engineering Aspects
of Fluid Dynamics.” Review with 252 references. Hydrodynamic Theories of Detonation. See
IndEngChem 56 (4), 43 (1964) & CA 60, 15453 Vol 4 of Encycl, p D61O-L
(1964)
9) B. Alder et al, Eds, “Fundamental Methods in Hydrofluoric Acid or Fluorhydric Acid. See
Hydrodynamics” (Methods in ,Compytational Hydrogen Fluoride, Anhydrous and Hydro-
Physics, Vol 3), AcademicPress, NY (1964) fluoric Acid in this Vol
10) J. Happel & H. Brenner, “Low Reynolds
Number Hydrodynamics”, Prentice-Hall, Engle- Hydrofluosilicic Acid. See Fluorosilicic Acid
wood Cliffs, NJ (1 965) in Vol 6 of Encycl, p F141-R
11) R.J. Seeger & G. Temple, Eds, “Research
Frontiers in Fluid Dynamics”, Interscience, NY Hydrogen, H, at wt 1.008. The lightest element;
(1965) usually exists as a molecule (H ~) of mw 2.016
12) M.A.T. Cocquerel “Unit Operations, Heat in the form of colorless, highly flammable gas;
Transfer, Fluid Flow:” Review with 73 refs. sp gr of gas 0.06948 (Air 1.0); and of liq
ReptProgrApplChem 50, 117 (1965) & CA 66, 0.0709 at –252.7°; fr p –259.18°; bp –252.77°;
39243 (1967) autoignition temp 1085°F; low expln limit 4.1%
13) J. C. Pearson “Hydrodynamic Elastic Plastic by vol, upper expln limit 74.2%; very S1sol in
Theory and Plane Shock Waves in Metals. I. w, alc or eth. It can be prepd by the follow-
Theory.” Title of the paper in 4thONRSympDeton ing methods: a) By the action of steam on
(1965), p 289 (Abstract) and of PATR 3464 (1966) natural gas at high temperatures, and subsequent
14) L. G. Loitsyanskii “Mechanics of Liquids & purification b) By treatment of water gas
Gases”, PergamonPress, London (1966) with steam and absorption of the carbon dioxide
15) Ya. B. Zel’dovich & Yu. P. Raizer “Physics c) Dissociation of ammonia d) Thermal de-
of Shock Waves & High-Temperature Hydrody- composition of hydrocarbons e) Catalytic re-
namic Phenomena” 2nd Ed Moscow, Nauka (1966) forming of petroleum f) By reaction of iron
16) S. I. Pai et al, Eds, “Dynamics of Fluids and steam g) Catalytic reaction of methanol
& Plasmas”, AcademicPress, NY (1966) & steam and h) By electrolysis of water
17) R.H.F. Pao, “Fluid Dynamics”, Merrill; (Ref 2, p 587-R)
Columbus (1967) Accdg to Ref 2, p 588-L, the molecular hy-
18) R. A. Strehlow “Detonation & the Hydro- drogen exists in two varieties: ortho and para,
dynamics of Reactive Shock Waves.” Review of named accdg to their nuclear spin types. Ortho
recent work. ACS, DivFuelChemPreprints, 11, 1 molecules have a parallel spin, para an antiparal-
(1967) & CA 70, 98391 (1969) lel spin. By cooling to liquid air temp and using
19) W. N. Gill et al “Fluid Dynamics.” Review a catalyst, the normal equilibrium of three
with 1065 refs. IndEngChem 59, 69 (1967) & ortho to one para molecules is displaced and
CA 6851292 (1968) para-H2 may be isolated. Para type of Hz is
20) W. N. Gill et al “Fluid Dynamics.” Critical preferred for liquid fuels
 H216

Liquid hydrogen is used in rocket fuels, Refs: 1) L. Pauling, “The Nature of the Chem-
while hydrogen gas can be used for the following ical Bond” Cornell Press (1960) 2) G. C.
purposes: production of synthetic ammonia and Pimentel & A. L. McClell~ “The Hydrogen
methanol; hydrogenation of org materirds such Bond” Reinhold (1960) 3) CondChemDict
as oils, phenol or naphthalene; reducing agent (8th Edit 1971), p 455
for organic synthesis; reduction of metallic
ores; reducing atmospheres to prevent oxidation; Hydrogen Bonding Concept in Gelatinization
as oxyhydrogen flame for high temps; for atomic of NC. Tests of a number of hydrogen bonding
hydrogen welding; making hydrochloric and hy- agents dissolved in ether, alcohol or benzene
drobromic acids; for ffling small balloons, etc. showed that the concept of hydrogen bonding
It was formerly used in Europe for i@lation of was certainly involved in the mechanism of
passenger-carrying balloons and for observation gelatinization, but that the results were modified
and barrage balloons (during WWII). Its use in by the character of the volatile solvent used
dirigibles was discontinued after disastrous fire Tests of the best hydrogen bonding agents
of Ger dirigible, “Hindenburg”. Hydrogen has in ether-alcohol showed the following compds:
not been used for inflation of US dirigibles or trimethyl-, trimethallyl-, & tributyl phosphates,
balloons because the non-combustible, lighter isophorone, dimethyl acetamide, and dibut yl
than air helium is readily available tartrate were superior to dibutyl phthalate or
Note: The explosion and combustion properties triacetin in the amts reqd for gelatinization and
of hydrogen mixtures are described as a separate in the viscosities of the resulting solns
item When a major portion of Guncotton was
Refs: 1) Gmelins Hndb (1936), not found dispersed with acetone-alcohol and the residual
2) CondChemDict (1961), pp 587-R & 588-L portion with one of the above compds, equal
3) Kirk& Othrner, Vol 11 (1966), pp 338-79 weights of the ,compds were superior .to dibutyl
by R.M. Reed, 4) Sax (1968), p 823 phthalate and to triacetin first, with respect to
5) CondChemDict (1971), p 454-L time reqd for complete dispersion and secondly,
in producing solns of low viscosity
Hydrogen Bomb. See under Atomic Bomb in Rejl A.J. Philips, “The Relation of the Hydrogen
Vol 1, A499-L Bonding Concept to the Gelatinization of Nitro-
cellulose,” PATR 1249 (March 1943)
Hydrogen bond. An attractive force, or bridge
occurring in polar compounds such as water,, Hydrogen Chloride, Anhydrous and Hydro-
in which a hydrogen atom of one molecule is chloric Acid.
attracted to two unshared electrons of another. Anhydrous Hydrogen Chloride is a color-
The hydrogen atom is. the positive end of one less gas, which on liquefaction gives colorless
polar molecule and forms a linkage with the (or S1yellowish) fuming, strongly corrosive
electronegative end of another such molecule. liquid; mw 36.47, sp gr of gas at 0°1.268
In the formula below, the hydrogen atom in (Air); frp–114.3”; bp -111° (Lange); bp
the center is the “bridge”: –84.8°; sol in w, ale, eth & benz. It can be
H:@ H: O:H:O: prepd by furnace combstn of hydrogen, methane
HHH or water-gas, in chlorine or by solvent extrac-
Hydrogen bonds are only one-tenth to one- tion from hydrochloric acid (aqueous HC1).
thirtieth as strong as covalent bonds, but they It is used in reactions where aq HCI is not
have pronounced effects on the properties of suitable, such as production of vinyl chloride
substances in which they occur, especially as from acetylene or of a.lkyl chlorides from
regards melting and boiling points and crystal olefins (Ref 2, p 256 & Ref 3, p 588-R)
structure. They are found in compounds con- Hydrochlon”c Acid (known in commerce as
taining such strongly electronegative atoms as Muriatic Acid), is a coned aq soln of anhydrous
nitrogen, oxygen and fluorine. The y play an HC1. It is colorless or “s1yel, fuming, pungent,
important part in the bonding of cellulosic liquid, poisonous unless it is very diluted. The
compounds, eg, in the paper industry commercial product contains 38’%0HC1 and has
 H 217

sp gr of 1.19. A more coned product of 45.2% solving HF liquid in w

HC1 listed in Lange (Ref 2), has sp gr 1.48 and Lange (Ref 2, p 256) gives aor 35.35% acid,
freezes at –15.35°. The acid is sol in w & rdc. sp gr 1.15, fr p –35° & bp 120°
It can be prepd by several methods such as: Hydrofluoric acid is used for polishing, etch-
a) By-product of chlorination of benz or other ing & frosting of glass; pickling Cu & other
hydrocarbons b) By the action of sulfuric metals; electropolishing of metals; purification
acid on common salt; or c) By Hargreaves of falter paper and cleaning castings (Ref 3,
process which is described in Ref 3, p 585-R p 587-L)
The acid has many uses in them & metal- Refs: 1) Gmelins Hndb, Syst No 5 (1926),
lurgicrd industries, as indicated on p 586-R p 31 & 5 (1959), p 142 2) Lange (1961),
of Ref 3 256 3) CondChemDict (1961), 587-L &
Note: Salts of HC1 are called chlorides, many of 588-R 4) Kirk & Othmer 9 (1966), pp
which are described in Vol 3 of Encycl, pp 610–25 by J.F. Gall 5) Sax (1968), 823
C236ff 6) CondChemDict (1971), pp 454 & 455
Re~s: 1) GmelinsHdb, Syst No 6 (1927), 7) US ‘Spec O-H-795(2) (July 1957) (Hydro-
p 86& Teil B (1968), p 2 2) Lange (1961), fluoric Acid, Technical Grade) 8) US Mili-
256 3) CondChemDict (1961), pp 585-R & tary Spec Ml L-H-I 0925A (Dee 1958) (Anhy-
588-R 4) Khk & Othmer, Vol 11 (1966), drous Acid)
pp 307–37 by W.R. Kleckner & R.C. Sutter
5) US Spec O-H-765B (May 1969) (Inhibited Hydrogen Gun. A gun that shoots bullets at a
Hydrochloric Acid for Rust Removal) speed of 4 miles” per sec (or even faster) was
6) CondChemDict (1971), pp 453 & 455 constructed by E. B. Mayfield of the Naval
Ordnance Test Station, Inyokern, California. The
propellant is liquid hydrogen touched off by an
Hydrogen Fluoride, Anhydrous and Hydro- injection of oxygen and the projectiles are
fluoric Acid. smaller than rifle bullets. The prime purpose of
Anhydrous Hydrogen Fluoride, HF, mw this gun is the study of what happens when a
20.01; colorless, corrosive gas which forms at projectile moves through air at very high speeds
temp below 19.4°, colorless, fuming, corrosive, Ref: Anon, Ordn 36, (No 191), 780 (1952)
poisonous liquid, producing painful burns on
the skin. It freezes at –83° and its sp gr is Hydrogen-ion Concentration (pH) or Potential
0.988 at 3.6° (Lange). Both gas and liquid of Hydrogen. The concentration of H+ per liter
consist of associated molecules; the vapor den- [H+] of an aqueous solution. h denotes the
sity corresponds. to HF only at high temps. true acidity or alkalinity .of such solutions, and
Both gas and liquid are very sol in water. Can is expressed by the pH value (potential of
be prepd by distillation from the product of hydrogen). This value is the concentration of
reaction of Ca fluoride (fluorspar) and sulfuric H+ in terms of the reciprocal logarithm of the
acid. “Used as fluoridating agent in organic and number of gram ions of hydrogen per liter:
inorganic reactions; production of fluorine and pH = log lo 1/CH = -log10CH where CH is
Al fluoride; prepn of hydrofluoric acid; pro- effective concentration of hydrogen (molal or
duction of fluoroborates, fluorosilicates, etc; normal). Pure water has pH value = 7.0, because
as an additive in liquid rocket propellants; and one liter dissociates ‘to contain only 10-7 g of
for refting of uranium (Ref 3, p 588-R) H+. As there is also an equal number of
Hydrojluonc Acid is an aqueous soln of hy- [OH-] present, its pOH is also 7, which makes
drogen fluoride of strength up to 70%. These a total pH + pOH = 14. Accordingly pH values
solns are colorless, fuming, corrosive, mobile from O to 7 indicate an acid solution, pH = 7
liquids, producing terrible sores when allowed to indicates neutrality and pH 7 to 14 an alkaline
touch the skin. Only a moderately strong acid, solution
but unlike other acids will attack glass and any Hack~s Dictionary, p 422 (Ref 13) gives a
silica-contg substance. Prepd by absorbing in table of relation between pH, pOH, Hydrogen-
w, HF gas, which is distilled from a mixture of ion concentration (normality and hydroxyl ion
fluorspar (CaF z) and sulfuric acid; also by dis- concentration (normality)
 H218

pH values may easily be calculated if the Bates & E.R. Smith, Hydrogen-Ion Concentration
value CH (rdso denoted as AH+) is known. For 16) J.E. Ricci, “Hydrogen Ion Concentration,”
.. .
instance, pH of a solution which is 0.0002 Princeton Univ Press, Princeton, NJ (1952)
molrd in, hydrogen ion (CH = 2 x 10-4) 17) Catalogs and Bulletins of Beckman, Cole-
pH = log10 l/CH = loglo 1/2 X 10-4= loglo 5 X 103= man, Photovolt Corp, Taylor & Co, LaMotte,
3.699 etc
Determination of pH vahres may be ‘done
Hydrogen-ion Concentration Stability Test. See
either by electromotive force measurements, by
colormetric methods (indicator papers, or in- Hansen’s Stability Test in this Vol
dicator solutions), or by the glass electrode
method Hydrogenite. A mixt of Si 25, NaOH 60
Since the pH value is of great importance in. & slaked lime 15% which ignites and, on
many manufacturing processes (including ex- burning, gives 270–370 liters of hydrogen gas
plosives), pH meters are installed to exercise per kg
control over the pH (See Refs 5 & 6) Rejl Hackh’s Diet (1944), 422-R; (1969),
There are also other methods for measuring 333-R
hydrogen ion concentration, for instance,
S6rensen’s (psH) unit or the activity coefficient Hydrogen Peroxide, Hydrogen Dioxide or T-stuff.
unit (paH), based on emf measurements HOO,H; mw 34.02; colorless or faint blue syrupy
Refsj 1) L. Michaelis, “Die Wasserstoffionen- liq, fr p –2°, bp 158° (Ref 24), vap press 1mm
Konzent ration,” trarislated from the 2nd German at 15° & 47rnm at 80°, d 1.46; sol in w, alc &
edition (1922) by W.A. Perlzweig and published eth; insol in pet eth. Thennodyn data: AH;
by Williams & Wilkins, Baltimore (1926) 2) 44.84 & AF~ -28.2 kcal/mole for liq; AH; 45.65
E. Mislowitzer, “Die Bestimmung der Wasser- kcal/mole for aq Hz 02 & -31.83 kcal/mole for
stoffionkon’zentration von Fliissigkeiten,” J. gaseous Hz 02 (Ref 6). Bond strengths: H-OOH
Springer, Berlin (1927) 3) J. Grant, “Measure- 89.6 kcal/mole (Ref 18); HO-OH 47.1 kcal/mole
ments of Hydrogen Ion Concentration,” Long’ (Ref 22)
mans, Green, London (1930) 4) H.H. Willard & Prepns: a) ‘Ba02 + “’H2S04 (aq) =, BaS04 +
N.H. Furman, “Elementary Quantitative Analysis,” Hz 02: the aq Hz 02 is then concentrated by
Van Nostrand, NY (1935) 5) A. Kufferath, SS evaporating w under reduced press (Ref 2)
31, 327-30 (1936) & CA 31, 258 (1937) 6) b), Electrolytic oxidation of coned Hz S04
M. D&-ib&< ‘RevG6nMatPlastiques 12, 356–58, with subsequent hydrolysis of the peroxydisul~
(1936) & CA 31, 2007 (1937) 7) J. Rouvillois, furic acid .(Ref 2)
MefnArtilFr 17, 773-797 (1938) (Le pH et la c) Hydrogen reduction of 2-ethylanthraqui-
stabilite des poudres); Ibid 18, 1077159 (1939) none followed by air oxidation to regenerate
8) D.A. McInnes, “The Principles of Electro- the quinone (Ref 25)
chemistry~’ Reinhold, NY (1939) 9) I.M. Pure Hz 02 is a very unstable material which
Kolthoff & H. A. Laitinon, “pH and Electro- decomposes violently above 80”. The decompn
titrations,” J. Wiley, NY (1941) 10) M.’ Dole, Hz 02 = Hz O + 1/20z is catalyzed by many substs
“The Glass Electrode,” J. Wiley, NY (1941) such as Ag, Mn02, HBr & saliva. Because of this
(Contains complete bibliography) 11) H.T.S. instability, commercial Hz 02 is usually ‘a water
Britton, “Hydrogen Ions,” Chapman & Hall, soln–commonly 27.5, 35, 50 & 70%, although
London (1942) 12) J. Reilly & W.N. Rae, solns ranging from 3 to 90% are also available.
“Physico-chemical Methods,” Van Nostrand Hz 02 solns are stabilized with small amts of
(1943), v 2, pp 449-500 13) Hackh’s acetophenetidin inhibitor (Ref 25)
Diet (1944), p 422; (1969, 333-R 14) A.L. Toxicolofl: Pure Hz Oz, its solutions, vapors and
Chaplin, “Applications of Industrial pH mists are irritating to body tissue. This irritation
Controls”, Instruments Pub Co, Pittsburgh, can vary from mild to severe depending upon the
Pa (1950) 15) R.E. Kirk & D.F. Othmer, Ed, concn of H *02. For instance solutions of H202
“Encyclopedia of Chemical Technology,” Inter- of 35 wt~o and over can easily cause blistering of
science, NY, v 7, (1951), pp 71 1-726; R.G. the skin. Irritation carised by Hz 02 which does
 H 219

not subside upon flushing of the affected part In an earlier study the min concns of H202
with water should be treated by a physician. in a vapor mixt below which powerful external
The eyes are particularly sensitive to irritation ignition cannot initiate a self-propagating re-
by this material (Ref 24) action were determined over the pressure ranges
Uses: Bleaching and deodorizing of textiles, of 1 to 6.5 atm. These min concns were found
wood pulp, hair, fur, etc; source of organic and to be 25.6 mole% at 1 atm (or a little lower
inorganic peroxides: pulp and paper industry; than above) and 20.7 mole% in the 2-6 atm
plasticizers; rocket fuel; foam rubber; manufacture region (Ref 13)
of glycerol; antichlor; dyeing; electroplating; The explosive limits of H202 vapor were also
antiseptic; laboratory reagent; epoxidation; determined by using hot wire heated surfaces &
hydroxylation; oxidation and reduction; viscosity catalytic surfaces for ignition. At 1 atm, vapors
control for starch and cellulose derivatives; contg 26.0 mole’% or more H202 could be ex-
refining and cleaning metals; bleaching and ploded but only when catalytic surfaces were
oxidizing agent in foods; neutralizing “agent in used. Non-catalytic surfaces had to be pre-heated
wine distillation; seed disinfectant; cosmetics to 150° to obtain explosions. The lower limits
(Ref 25 ) at 200 and at 40mm Hg were 33 and 55 mole%
resp. Hydrogen Peroxide explosion is believed
Chemistry: In. some respects chemistry of Hz 02
to be thermal, involving straight chains only,
is quite similar to that of H2NNH2 or NH2 OH
with the initiating reaction being thermal
its ammonia system analogs. It is a powerful,
rupture of the O–O bond (Ref 5)
but usually slow, oxidizing agent in acid or alkaline
At lower pressures (200mm), presumably at
solns. It can also act as a reducing agent, eg with
elevated temps or on catalytic surfaces, the
MnO~or Ag2 O (Ref 2). On the other hand, H202
ign limit is 32.5 mol% H2 02. It is not affected
does not tend to form salts or substitute comps
by diluting the air with oxygen, nitrogen or He
(replacement of H) like its ammonia analogs
in amounts of O to 39 mol%. Decreasing the
(SeeRef 17)
system volume by packing it with Raschig rings
Analytical: Delicate qual tests forH202 are its shifts the ign limit to higher Hydrogen Peroxide
reactions with titanic chromate or sulfate in concns (Ref 10)
acid to produce the bright blue peroxychromic Quenching distances & minimum ignition
or bright yellow peroxy titanic acid both of energies of H202 & H2 O vapor mixtures were
which are sol in ether. Quantitatively H202 studied in a flow system in which liq H202
may be detd by its oxidation of 1- and titration of & H2 O was fed to a boiler where it completely
the 12 (or Ii) thus formed (Ref 2) vaporized and passed through the explosion
Explosive and Combustion fiops: Pure Hz 02 vessel contg the ignition source & then was
is readily detonable and its heat of expln is given condensed (Ref 14). The quenching distances &
as 24.6 kcal/mole. It is claimed that aq solns of min spark ignition energies of mixts contg be-
less than 94% H202 will decomp explosively if tween 35 & 50 mol% H202 were detd at pres-
catalyzed, but will not detonate (Ref 4). More sures between 25 & 200 mg of Hg at a temp 9°.
recent studies, however, show that 86% H2 02, above the condensation temp. The quenching
at 50° or higher and contained in 1.61 inch distances varied between 0.51 & 1.63cm & the
ID Al tubes, will detonate at 5600 m/see when ignition energies between 0.53 & 25.5 millijoules,
strongly boostered, but not at smaller diameters. decreasing with increasing H202 content &
A 90.7% soln detonates at ‘5500 to 6000 mlsec pressure. The observed min energy for ign (in
even at 0.5 inch ID and 25°. The gap over millijoules) is related to the quench distance
which the 90.7’% soln will propagate detonation (in cm) by:
increases with increasing temp (Ref 23) ~ti = 3.84d ‘“w
Mixtures of (H202 )gas/air ~1 not detonate Hydrogen peroxide, pu!e or aq, is readily
at subatmospheric press. However, a 35 mol$% detonable when mixed with organic materials.
mixt will detonate at 6700 ft/sec at 1 atm. The Detonation rates for H202 mixes with MeOH,
ignition’ limit under these conditions is about EtOH & glycerol were’ measured by Haeuseler
30 mol% H202 vapor (Ref 21) (Ref 7). These rates could be as high as 6700
 H 220

m/see for Hz 02 /H2 O/EtOH. The amount of c~stalline compound of high brisance and
energy to sustain explosive reaction in sensitiveness, melting at about 50°
Hz 02 /H2 O/organic mixes depends not only on b) A mixture was prepd by treating cellulose
the peroxide/organic ratio but also on the water with 83.4% Hz 02 to form a gelatinous mass.
in the mix, the water acting as an energy sink. This mixt is more powerful than TNT or
To a lesser extent explosibility is also affected Tetranitroaniline, but is insensitive to shock or
by sample VOI, initial temp, and to a consider- friction and burns without detonation when
able degree by the type of initiation used. Chem dropped in a red hot crucible or ignited by
changes that occur in a mix can make a power- flame. Its ignition temp is 194-208°. It cannot
ful explosive out of an apparently non-explosive be stored for longer than 24-48 hours, as
mixt. Consequently, careful experimentation bubbles, resulting from decomposition of the
should precede the mixing or use of mixtures Hz 02, are evolved and the masshardens. More-
containing Hydrogen Peroxide and organic over its explosive power decreased after 48
substances (Ref 15) hours of standing (Ref 1)
In view of these many factors found to in- A Spanish patent claims an explosive compn
fluence the explosibility of Hz 02 /H2 O/erg prepd by mixhrg hexamethylenetetramine (See
subst mixes, the simplified approach of Shardey p H79 in this Vol) with Hydrogen Perioxide,
and Perrin (Ref 12), which is based primarily and then adding HC1 (Ref 9)
on the enthalpy contents of these mixes, An explosive insensitive to mech and rifle
should only be used as a first attempt at bullet impact, but detonable by a blasting cap,
determining the explosion hazard of these mixes. is claimed in a US patent. It consists of
Their suggested isoenthalpy line of 0.8kcal/g of Hydrogen Peroxide, water & glycerol (Ref 3)
mixt defines the experimentally observed expl Another patented high explosive composition
limits fairly well for initiation by blasting cap. contains powdered metal and Hydrogen Peroxide,
However, their value of 1.2kcal/g for impact eg 29.7% powd B & 70.3% H202 (Ref 19)
initiation suggests that some mixes are safe Hydrogen Peroxide in l%opulsion. German use
which in fact were found to be in the ex- of high-concn Hydrogen Peroxide in propulsion,
plosive range (Ref 15) assisted take-off, torpedoes, special submarine
The work of Kuchta (Ref 16) confirms turbines, etc during WI is described in Ref 8
that the relative concns of Hydrogen Peroxidt Use of high-concn Hydrogen Peroxide for
/erg subs are more important in defining the rocket propulsion, details of its manufacture and
explosibility of a mixt than the type of safety are described by Cleaver (Ref 11)
org subst used. He points out that detonation A review of the fire and explosion hazards
can be initiated in certain Hz 02 purge liquors of flight vehicle fuels includes discussion of
that may form in commercial production of Hydrogen Peroxide. It gives vap press data
Hydrogen Peroxide (Ref 19)
Accdg to Ref 14a, Hydrogen Peroxide has
Hydrogen Peroxide Explosives. Attempts were been used as torpedo proplnt anti rocket fuel
made in Austria during WWI to use Hz 02 for. oxidizer’
the preparation of explosives, but they were Refs: 1) M. Bamberger & J.Nussbaum SS 22, 125
not successful. Later, Bamberger and Nussbaum (1927) & CA 21, 4070 (1927) 2) W:L.Latimer
(Ref 1) succeeded in preparing several Hydrogen & J.H. Hildebrand, “Reference Book of Inorganic
Peroxide explosives, which were successfully Chemistry,” Macmillan, NY(1941) 3) E.S. Shardey &
tried in blasting operations. The following ex- H. O.Kauffmann,,USP 2452074 (1948) & CA 43,
plosives were prepared by mixing organic com- 1190 (1949) 4) L. M6dard MP 31, 273 (1949)
pounds with strong aqueous solutions (about & CA 46, 11687 (1952) 5) C. N. Satterfield et al,
60% or higher) of peroxide JACS 72, 4308 (1950) & CA 45, 2294 (1951);
a) Mixture of H202 (60Y0solution) with IEC 43, 2507 (1951) & CA 46, 1767 (1952)
paraformaldehyde forms a brisant explosive, which 6) F. Rossini et al, NBS Circular 500 (1952)
may be detonated either by heat or by a blasting 7) E.Haeuseler, Explosivst 5/664 (1953) &
cap. This mixt,ure reacts with lead forming a CA 48373 (1954) ‘8) H.Walther, Jet Prop 24,
 H 221

166 (1954) & CA 48, 11061 (1954) 9) J.R. was not possible to prevent on prolonged sto-
Mediavilla, SpanishP .203467 (1952) & CA 48, rage, a slow decompn into water and oxygen
14210 (1954) 10) C.N. Satterfield et al, IEC For rapid estimation of its strength, either
47, 1040 (1955) & CA 49, 9927 (1955) 11) a hydrometer or titration with K or Na per-
A.C.Cleaver, JBritInterplanetSoc 14, 159 (1955) manganate was used
&CA 49,9929 (1955) 1 la) PATR 2510 Methods of manuf of H 202 in Germany are
(1958), pp Ger 95-R & Ger 21 O-L (T-Stof~ described in Refs 2, 3, 5 & 6
12) E.S. Shardey & J.R. Perrin, JetProp 28, One of the most interesting applications of
382 (1958) & CA 52, 21110 (1958) T-Stoff was as a source of power turbines
13) C.N. Satterfield et al, JChemEngData 4, driving submarines as proposed by Dr Helmuth ~
131 (1959) & CA 54, 898 (1960) 14) J.S. Walter (See U-Boot, Walter in Ref 13, p Ger
Marshall, TransFaradSoc 55, 288 (1959) & 21 l-R). Seven of such submarines (300 to
CA 54, 1044 (1960) 14a) CondChemDict 500 tons each) were accepted by the German
(1961), p 589-L 15) J.M. Monger, JChem- Navy up to the end of WWII
EngData 6, 23 (1961) & CA 56, 3713 Besides submarine, the following applica-
(1962) 16) J.M.Kuchta et al, US Bur of Mines tions of T-Stoff are listed in Ref 13, p Ger 210
RI 5877 (1961) & CA 565010 (1962) 17) a) A 500kg ATO (Assisted Take-Off) T-Stoff
J.G.Williams “Hydrogen Peroxide in Organic monofuel unit
Chemistry Pamphlet, Electrochem Dept, b) A 300-kg thrust, rocket propulsion unit for
Peroxygen Prod Div, EI Dupont de Numours guided missiles
(1962) 18) S.N. Foner & R. L. Mudson, JChem c) A bipropellmt 1000 to 1500-kg ATO
Phys 36, 2681 (1962) & CA 57, 15960 (1962) d) A catapult with T-Stoff propulsion unit
19) R.W.VanDolah et al, US Bur of Mines Circ (decompn only) for launching V-1, 2 hich is
8137 (1963) & CA 58, 7779 (1963) “20) S. described in Ref 13, p Ger 213-L
Brunauer, USP 3111439 (1963) & CA 60, 2720 e) Controllable propulsion of a 750-kg thrust
(1964) 21) J.M. Monger et al, JChemEngData unit for Messerschmitt 263
9 (11) 124) (1964) & CA 60, 7860 (1964) f) Rocket training airplane and a controllable
22) A.F. Richter, Casopis Lekaru Ceskych (Czech) power plant giving to 2000 kg thrust for the
104 (39) 1076 (1965) & CA 64, 4276 (1966) Messerschmitt 263B
23) Anon, USBur of Mines Info Circ 8387 (1968) Accdg to Ref 4, p 8, T-Stoff was used as an
& CA 69, 78878 (1968) 24) Sax (1968), p 824 oxygen carrier in some guided missile proplnts,
25) CondChemDict (8th Edit, 1971) p 456 such as in Hecht (Pike), listed in Ref 13, p
Ger 132-L as Pike Missile and described in
Hydrogen Peroxide (Additional Information on
Ref 11, pp 116–17. In order to accomplish
German Manufacture and Uses During WWII). this, T-Stoff was mixed with Z-Stoff which
Accdg to Dr Hans Walter, communicated during was an aq soln of K or Na permanganate, de-
his work at Picatinny Arsenal, the name Wasser- scribed in Ref 13, p Ger 264-R. This mixt
stoffperoxyd or Wasserstoffsuperox~ applies produces superheated steam, attaining temp of
to any strength compd, while the name T-Stoff 180°. This steam was also suitable for driving
(T-stuff in Engl) is applied to 80–85% H *02 rockets and ATO, but was not suitable for
and 20– 1570H 20. It was a clear viscous li- driving turbines, because it contd small particles
quid fairly stable at ordinary temp and pressure of Mn02 which might foul the blades of tur-
when stored with a small amt of phosphoric bine. However, the superheated steam formed as
acid, serving as a stabilizer. Such a mixt was result of mixing T-Stoff with MP- 14 catalyst,
known as T-Stoff(S) (Ref 4, p 8 & Ref 13, p described in Ref 13, p Ger 114-L can be used
Ger 21O-R) for driving steam turbines
When H202, contg ca 20% HzO, was stabi- When T-Stoff was mixed with B-Stoff (Hy-
lized with oxyquinoline (400mg per liter), the drazine Hydrate), in the presence of K cupro-
mixt was known as T-Stoff@S) (Ref 4, P ? & cyanide, the resulting liquid spontaneously ig-
Ref 13, pp Ger 21OR & 211-L) nited
However, even with the greatest care, it Accdg to Ref 4, p 8, T-Stoff was also known
 H 222

as I ngolin. Accdg to Ref 7, p 23, the code name oxidizing materials and forms expl mixts with
T-Stoff was used only for 82% H ~02, while the air (Refs 1, 3 & 4)
code names Aurol, Neuralin and Subsidol were Refs: 1) Gmelin Syst No 10 (1949), p 2
used for any 80 to 86% Hydrogen Peroxides 2) Partington (1950), 498–99 3) Sax (1968),
Refs: 1) Dr, Nitschmann, “Physical and Che- 825-R 4) CondChemDict (1971), 456’L
mical Investigations of T-Stoff Solutions”,
IGFarbenind Rept 597, Oppau, Germany Hydrogen Sulfide. H2 S, mw 34.08, colorless gas,
(1944) 2) B.E.A. Vigers et al, “Hydiogen mp -83.8°, bp -60.2°, auto ign temp 500”F,
Peroxide Production by Electrolysis of 35% d 1.54g/l at 0°. It is highly toxic by inhalation
Per Cent Solutions”, BIOS FinalRept 683 and is a strong irritant to eyes and mucous
(1945) 3) V.W. Slater et al, “The Anthra- membranes. It is highly flammable and has
quinone Autoxidation Process for the Production wide explosive limits in air: lower limit 4.3
of Hydrogen Peroxide”, CIOS Rept 31-15 (1945) vol’%; upper limit 46 VOI%
4) R.C. Stiff, CIOS Rept 30-115 (1945), pp Refi CondChemDict (1971), p 456
8–9 & 12–13 5) J. McAulay, “Hydrogen
Peroxide Manufactured by All-Liquid Process Hydrogen Telluride. Hz Te, mw 129.63, color-
from Ammonium Persulfate”, CIOS Rept less gas or yellow needles, mp -49.0°, bp -2°,
33-43 (1945) 6) J. McAulay, “Direct Syn- d 5.81 g/1. It is highly toxic and is an irritant
thesis of Hydrogen Peroxide by Electric Dis- but it does not present the fire & explosion
charge”, CIOS Rept 33-44 (1945) 7) H.A. hazard of Hz S or Hj Se
Curtis, CIOS Rept 28-62 (1946) 8) Logan Refi CondChemDict (1971), p 456
McKee, MechEngrg 68, 1045–48 (1946) (Hy-
drogen Peroxide for propulsive power; produc- Hydrogen Tetraoxide. Hz 04 , mw 66.02. , This
tion and use by the Germans during WWH) substance exists only at low temps and is
9) E.S. Shanley & F.P. Greenspan, IEC 39, probably H2 OQ rather than H203 (Ref 3). It
1536–43 (1947) (Props of highly coned Hy- is probably non-planar with a AH?= -27.9 kcal/
drogen Peroxide) 10) R. Simard, The En- mole (Ref 1). It has been prepd by reacting
gineering Journal of Canada 31, 219–25 (1948) H+03 or H+O and its reactions with NH3, Cl
11) F. Ross, Jr, “Guided Missiles”, Lothrop, & Cz ~ have been examined (Ref 2). A review
NY (1951), 45-6 11a) K.W. Gatland, “De- of the general subject of higher peroxides,
velopment of the Guided Missiles”, Iliffe, including Hz 04 is given in Ref 3
London (1952), 116– 17 (Pike or Hecht Missile Refs: 1) D. A. Csjeka et al, JPhysChem 68, 3878
developed in 1941 by the Rheinmetall Borsig (1964) & CA 62, 5947 (1965) 2) D. A.Csjeka,
AG) 12) Hans Walter, JetPropulsion 24, US Govt Res Develop Rept 40 (7), 53 (1965)
166–7 1 (1954) (Experience with the applica- AD617964 & CA 64, 267 (1966) 3) L.I.
tion of Hydrogen Peroxide for production of Nekrasov et al, ZhFizKhim 45 (4) 1017 (1971)
power) 13) B.T. Fedoroff et al, PATR & CA 75, 29790 (1971)
2510 (1958), p Ger 95 (Hydrogen Peroxide)
& Ger 210 (T-Stoff). Other pages are indicated Hydrolysis. The chemical reaction of a sub-
in the text stance with water to form one or more new
substantes. Examples of hydrolysis are: the
Hydrogen Selenide, H2 Se, mw 80.98; colorless catalytic conversion of starch into ghrcose;
gas, fr p –64°, bp –41 .4°, d 3.614g/liter (gas), the catalytic or enzymatic conversion of
2.12 at –42° (liq); vap press 10 atm at 23.4°; sucrose into glucose and fructose; the conver-
can be formed in small amts on heating Se in sion of natural fats into fatty acids and
hydrogen & by action of nascent H on selenious glycerin
acid. Pure H 2Se is obtd by action of water on In general hydrolysis is a reaction of the
Al selenide (Refs 1 & 2) “ type: AB+H2 O = AOH+HB, which in its ionic
The compd is highly toxic by inhalation, form: H2 O = H ‘+ OH- is the reverse of neu-
strongly irritating to the skin, and causes damage tralization. As examples:
to the lungs & liver. It reacts violently with In inorganic chemistry:
 H 223

CUS04+2H *O = Cu(OH) ~+H ~S04 Table

In organic chemistry: Hydrolysis of Plasticizers for NC
RCOOR’ +H2 O = RCOOH+R’OH
In biochemistry (by enzymes): Hydrolysis; % acidity
R.CONH.R’+H20 = R.COOH+NH2R’ Substance At 22 At 60°
C~~H~~oI~+H@ = 2CrjHlzoG Butanediol- 1,3-dinitrate — 1.1
Refs: 1) Hackh’s Diet (1944), 423-R (BDN-1 ,3)
2) Grog@ss (1952), 651–70 Butanediol- 1,4-dinitrate — 1.7
(BDN-1 ,4)
Diacetin mononitrate — 28.5
Hydrolysis of Plasticizers for NC by Water at (DAM)
22° and 60”C. Following tests were conducted Dibutylphthalate 0.002 0.011
in 1945 at Picatinny Arsenal by P. F. Macy (DBP)
and A. A. Saffitz: Diethyleneglycoldinitrate 0.003 0.003
a) Place a sample of about 5g of material to (DEGDN)
test in a small flask contg 12.5 ml of C02 –free Dinitroethylbenzene 0.007 0.028
neutral distilled water. Stopper and shake for (DNEB)
10 days at 22° in a “rotary, end over end, shaker Dipropyleneglycol- — 0.123
apparatus placed in a constant temperature room dinitrate (DPGDN)
b) Determine the acid liberated during the Dimethylmethylol- — 0.185
exposure period by titrating the sample water nitromethenemono-
mixture -with either N/10, or N/50 sodium hy- nitrate
droxide solutions in presence of phenolphthalein Ethyltrimethylol- 0.003 0.002
indicator. Thrations should be conducted sepa. methanetrinitrate
rately on the oil and water layers of the mixture. (EMMET)
If the organic acid liberated during the hydro- Glycerol mono- 0.021 0.014
lysis is more soluble in the oil layer than in the Iactatetrinitrate
water layer, 5ml of cp acetone should be added (GLTN)
to the oil to reduce possible errors arising due Glycolmono&hylether- ‘ — 0.637
to low volubility of the standard alkali in the mononitrate (GEEN)
oil. Blank determination shall be made J, in all Glycolmonomethyle ther- — 0.181
cases with water and acetone, and the necessary mononitrate (GMEN)
corrections applied Metroil trinitrate 0.018 0.115
c) Express the acidity as grams of acid” pro- (MTN)
duced (mineral acid in case of ester nitrates, Monoacetinedinitrate — 21.3
and organic acid in case of phthalates, acetates, (MAD)
lactate-nitrates, acetate nitrates) per 100g of Nitroglycerin (NC) <0.002 0.005
starting material at the specified temperature Triethyleneglycol- 0.032 0.003
for the entire test period dinitrate (TEGDN)
d) Hydrolysis at 60° * 1‘C was conducted Trinitrophenyl- <0.001 0.01
by shaking for 5 days in a rocker device con- ethanolnitrate
tained in Cenco Electric Oven, Model No 95, (TNPEN)
105A Refi P.F. Macy & A.A. Saffitz, PATR’s 1616
Following are some results: (1946); 1638 (1947)

Hydrolysis Test for Nitrocelluloses. The fol-

lowing hydrolysis test was developed and is
used at Picatinny Arsenal
a) Weigh accurately a 5g sample of dry NC,
place in a tared 250ml Pyrex flask provided
with a ground connection to fit a Pyrex condenser
 H 224
b) Add 100m1 of distilled neutral (conducti- HN:N.NHZ; Tetrazene (tetrazone, or 2-
vity) water and boil the water under reflux tetrazene) Hz N.N:N. NH2; Isotetrazene (1 -tetra-
condenser during 240 hours zene, diazohydrazene, buzylene) HN: N. NH.NH2;
c) Cool the flask and falter off the water Ammonium Azide, NH4 .N3; Hydrazine Azide,
into a 500rnl volumetric flask. Rinse the NC ‘2 HS.N3
with several portions of conductivity water, Type formula NnHn.2
using sufficient amount to fill the flask to 500MI Hydrogen Azide(hydrazoic acid, azoimide, hydro-
mark nitric acid, triazoic’ acid) HN:N:N; Diimino-
d) Stopper the flask, shake and take an Hydrazine ‘HN:N.NH.N:NH; Bisdiazoamine
aliquot. Determine its pH, using a standard HN:N.NH.N:NH; Hexazodiazene HN:N.NH.NH.
procedure N: NH; Heptazodiazene Hz N.N: N. NH.N:N.NH*
e) Take another aliquot and titrate it with a Type formula NnHn4
standard NaOH soln in presence of methyl Octazotriene (octazone) HN:N.NH.N:N.NH.N:NH
red indicator Many of the derivatives of the above com-
Note: In one of the tests conducted at Pic, pounds are explosive and they are described
Arsenal the Pyro (N=l 2.6%N) gave 1.22%, separately under corresponding names. Some of
calcd as HN03 and Guncotton, (N=l 3.45%) the compounds included in these tables (as
gave 1.03% for instance ammonium azide and hydrazine
Refs: 1) D.D. Sager, PATR 174 (1932) azide), do not possess the structural formula of
2) W.R. Tomlinson & O.E. Sheffield, AMCP real hydronitrogens but they are included for
706-177 (Jan 1971), p 9 the sake of comparison, because their empirical
formulas correspond to the type NnHn.z
Hydrolytic Reaction. Pertaining to Hydrolysis. Refs: 1) L.F. Audrieth & B.A. Q#, “The Che-
Comp with Hydroxylation mistry of Hydrazine”, J. Wiley, NY (195 1),
Rej2 Hackh’s Diet (1944), 423-R p 3-6 2) C.C. Clark, “Hydrazine”, Mathieson
Chem Corp, Baltimore, Md (1953)
Hydrometer. A device for measuring specific
gravity of liquids. Its description with Fig is Hydronitrous Acid or Nitroxylic Acid, H NO ,
given in Vol 3 of Encycl, p D67, under mw 48.02. The hypothetical acid from which
DENSITY AND SPECIFIC GRAVITY nitroxyls are derived. The nitroxyl radical is
–N02, when attached to a strongly electro-
Hydronitric Acid. Same as Hydrazoic Acid or
negative group such as F or Cl or to metal
Azoimide. See in Vol 1, p A537-R forming compds such as N02 F, N02C1 or
CU2(N02)
Hydronitrides. Same as Azides Refi Hackh’s Diet (1944), 424-R & 580-R

HYDRONITROGENS. Compounds containing

Hydronium Ion. The solvented hydrogen ion,
only hydrogens and nitrogens. Some thirteen H+(H2 O) or H3 0+, which is considered to
different hydronitrogens are known, mostly not be present in all acids:
in the free state, but as derivatives. There are HC1+H20 + H@++Cl-
saturated and unsaturated derivatives
Saturated (Type formula
Hydronitrogens Hydroperoxides, Organic. Are monosubstituted
NnHn+z ). NH3; Hydrazine (dia-
Ammonia derivatives of hydrogen peroxide ROOH, where
mide) H2 N. NHZ; Triazane (prozane) Hz N. NH. NH2 R is alkyl or aralkyl radical. They generally may
Tetrazane(buzane, hydrotetrazane) H2 N. NH. NH. be prepd by the following methods: a) alkylation
NH2. Ammonia and Hydrazine are known in the of H2 Oz with alkyl halides, sulfates, or
free state; the Triazanes are rather poorly defined alcohols in the presence of strong acids; b)
as a class, whereas’Tetrazanes exhibit a tendency controlled oxidation of the hydrocarbon RH
towards instability by undergoing dissociation with Oz; c) addition of 02 to Grigmrrd reagents.
in solution to yield hydrazyl radicals A brief discussion of prepn and properties of
hydroperoxides (including explosive: methyl-,
ethyl—, isopropyl-, t-butYl-, @trajin_,
Unsaturated Hydronitrogens (Type formula
decalin–, and phenylhydrazone– hydroperoxi.
NnH1l). Diamide HN:NH; Triazene (diazoamine)
ales) is given in Ref 2
 A table of the explosive nature of peroxides, taken from Ref 3, is given below:

EXPLOSIVE NATURE OF PEROXIDES

Remarks Concerning
Peroxide Explosiveness Ref
ALKYL HYDROPEROXIDES
Methyl Hydroperoxide Explodes violently ; sensitive to A. Rieche & F. Hitz, Ber 62, 2458
jarring especially at warm temps; (1929)
greatest caution in making, Ba
salt in dry state extremely explo-
sive
Ethyl Hydroperoxide Explodes on Superheating quite A. Baeyer & V. Villiger, Ber 34, 738
violently, Ba salt, heat and per- (1901)
cussion sensitive

Isopropyl Hydroperoxide Explodes just above bp S. Medvedev & E.N. Alexejeva,

Ber 65, 133 (1932)
t-Butyl Hydroperoxide By distn under normal pressures N.A. Milas & D. Surgener, JACS
explosions can result; otherwise 68, 205 (1946)
relatively harmle~s
Tetralin Hydroperoxide Detonated by superheating H. Hock & W. Susemiehl, Ber 66,
22 (1944)
Decalin Hydroperoxide VeW stable; can be sublimed in R. Criegee, Ber 77, 22 (1944)
small quantities at atm pressure
Triphenylmethyl Not explosive H. Wieland & J. Maier, Ber 64,
Hydroperoxide 1205 (1931)
Phenylhydrazone Detonates in dry state after a W. Busch & W. Dietz, Ber 47,
Hydroperoxide short time with no evident cause 3277 (1914)

DIALKYL PEROXIDES
Dimethyl Peroxide Extremely explosive on heating A. Rieche & W. Brumshagen,
and jarring; vapors also sensitive Ber 61,951 (1928)
to shock
Methylethyl Peroxide Liquid and vapor forms shock- A. Rieche, Ber 62, 218 (1929)
sensitive; explodes violently on
superheating

DIACYL PEROXIDES
Diacetyl Peroxide Highly explosive; to be handled L.P. Kuhn, C&EN 26, 3197 (1948)
only with extraordinary caution v

Dicapronyl. Peroxide Detonates at 85°C F. Fichter & R. Zumbrunn,

HelvChimAtta 10, 869 (1927)
Bishexahydrobenzoyl Large quantities can explode F. Fichter & W. Siegrist,
Peroxide without apparent reason HelvChimActa 15, 1304 (1932)
Difuroyl Peroxide Explodes violently by rubbing N.A. Miles & A. McAlevy,
and heating JACS 56, 1219 (1934)
Dibenzoyl Peroxide Exploded by heat; carry out re- K. Nozaki & P.D. Bartlett,
crystns of large quantities without JACS 66, 1686 (1946)
heating
l-Naphthoyl Peroxide Explodes by rubbing S. Mededeco & O. Bloch,
ChemZbl 1935 L 2670
 ‘x H 226

EXPLOSIVE NATURE OF PEROXIDES (Cont’n)

,.
/
Remarks Concerning
Peroxide Explosiveness Ref
PEROXY DERIVATIVES OF ALDEHYDES AND KETONES
Hydroxyrnethyl Explodes on heating; not sensitive A. Rieche & R. Meister,, Ber 68,
Hydroperoxide to friction; higher homologs not 1465 (1935)
explosive A. Rieche, Ber 64, 2328 (1931)
Hydroxymethyl Violently explosive, on heating A. Rieche & F. Hitz, Ber 62,
Methyl Peroxide becomes percussion-sensitive 2458 (1929)
.l-Hydroxyethyl Detonates on heating A. Rieche, Ber 63, 2642 (1930)
Ethyl Peroxide
Bishydroxymethyl Highly explosive; strongly friction- H. Wieland & H. Sutter, Ber 63,
Peroxide sensitive 66 (1930)
Bis(l-hydroxycyclohexyl) Harmless by itselfi but explodes on M. Stoll & W. Scherrer,
Peroxide’ attempted vacuum distn HelvChimActa 13, 142 (1930)
Bishydroperoxydicyclo- Detonates very actively in a flame R. Criegee, W. Schnorrenberg
hexyl Peroxide & J. Becke, Ann 565,7 (1949)
1-Hydroperoxy- 1-acetoxy- Detonates on removal from a ‘R. Criegee & G. Wenner,
cyclodecan-6-one freezing mixture Ann 564, 9 (1949)
Dimeric Ethylidene Explodes with extreme violence A. Rieche & R. Meister, Ber 72,
Peroxide just by touching; greatest cauti”on! 1933 (1939)
Polymeric Ethylidene Extremely explosive, even below Eg, A. Rieche & R. Meister,
Peroxide (Ether Peroxide) 1Oo”c AngewChem 49, 101 (1936)
Trimeric Propylidene Extremely explosive; very friction- A. Rieche & R. Meister,
Perioxide sensitive Ber 72, 1938 (1939)
Dimeric Acetone Explodes violently by percussion A. Baeyer & V. Villiger,
Peroxide and rubbing Ber 32, 3632 (1899)
Trimeric Acetone Very explosive; can penetrate a A. Baeyer & V. Villiger, ‘
Peroxide plate of “iron when heated on it Ber 32, 3632 (1899)
 H 227

Properties of hydroxalkyl hydroperoxides and

hydroxyalkyl peroxides are shown in the follow-
ing table (from Ref 3):

PEROXY DERIVATIVES OF ALDEHYDES AND KETONES

A. l-Hydroxyalkyl Hydroperoxides
Name ‘ Formula n? mp, C bp, C/mm Hg
Hydroxymethyl HOCH’ OOH 1.4205 (16 ) — .
Hydroperoxide
l-Hydroxyethyl CH CH(OH)OOH 1.4250 (24 ) — —
Hydroperoxide
l-Hydroxyheptyl C H CH(OH)OOH — 40 —

Hydroperoxide
l-Hydroxydodecyl C H CH(OH)OOH — 65 to 67 –
Hydroperoxide

l-Hydroxycyclohexyl HO OOH — 76 to 78 –

o
B. Bis(l-hydroxyalkyl) Peroxides
Bishydroxymethyl CH (OH)OOCH (OH) — 62 tO 64 –
Peroxide
Bis(l-hydroxyethyl) CH CH(OH)OOCH(OH)CH 1.4265 16 ) – —
Peroxide
Bis(cwhydroxybeWyl) C H CH(OH)OOCH(OH)C H — —
Peroxide
Bis(@hydroxy-&P,@ CC1 CH(OH)OOCH(OH)CC1 . 122 —

trichioroethyl)
Peroxide
Bis(l -hydroxycyclo- — 68 to 70 –
hexyl) Peroxide

The reduction of hydroperoxides with LiAlfi 3) Tobolsky & Mesrobian (1954), 2-17, 158 &
yields the corresponding alcohols probably via an 177 4) A. hROUX, MP 39, 49 (1955) & CA
LiAl(OR)4 intermediate. However this reaction 51, 718 (1956)
with BZ202 resulted in an explosion (Ref 1)
Cumene hydroperoxide (91-95% pure) will not Hydroquinone and Derivatives,
detonate even when strongly boostered. However, Hydroquinone, Hydroquinol, 1,4-Benzenediol
it is easily ignitable & can burn with sufficient or p-Dihydroxybenzene (Hydrochinon in Ger).
violence to rupture steel distillatiori equipment See 1,4-Dihydroxybenzene in Vol 5 of Encycl,
(Ref 4) p D1270-R
Refs:, 1) D.A. .Sutton, Chem & Indust” (195 1),
272 & CA 45, 8885 (1951) 2) R. Criegee, Hydrous. A compd contg water, as opposed to
“Herstelling und Umwanglung von Peroxyden” arrhydrous. In case of salts it is water of
in Houben-Weyl, Methoden der organischen crystallization
Chemic, 4th edit, Stuttgart, Vol Vll 1, 6 (1952) Ref: Hackh’s Diet (1944), 425-R; (1969),
335-L
 ?

H 228

Azidohydroquinone, N3.L-6H3~UH)2; mw 151.12, 2-6 Dinitrohydr?quinone, (OH)2 Cc Hz (NOZ )2,

N“27.81 %, OB to C02 - 132.3; leaflets, rep-explodes mw 200.11, N 14.00%, golden platelets (from w)
violently on heating; sol in alc or eth, insol in mp 135-136° (some color change), sol hot
petr eth. It can be prepd from quinone and an water, ale, eth. Prepd by nitrating hydroquinone-
excess of hydrazoic acid in benz diacetate (Ref 1); nitration of monobenzene-
Refs: 1) Beil 6, (419) 2) E. Oliveri-Manda12 & stdfonate [Ref 2). Its Ba salt, BaC6H2N20G3Hz0,
E. Calderaro, Gazz 45 I, 312 (1915); 45 II, 120’ dk-blue trysts, when anhyd is very expl (Ref la)
(1915) & CA 10, 596-7 & 1514-5 (1916) Refs; 1) Beil 6, 858, (418), [850] & {4444}
2) E.M. Kampouris, JChemSoc (1967), 1235 &
CA 67, 63964 (1967)
Diazidodinitro hydroquinone. (OH)Z Cb Hz (N3 )2
(NO,), (probably), mw 284.15, N 39.41%, OB-
Trinitrohydroquinonediethylether,
11.2, fme yellow needles (from mixed acid)
(O, N), C ~(OC,H5),; mw 301.21, N 13.95%;
It is claimed that the K salt is prepd by
yellow needles that turn yellow-orange on exposure
reacting nitroaminoresorcinol with cone mixed
to light, mp 130°, insol in w, somewhat sol in ale,
acid containing an excess of K-nitrate
eth or benz. Prepd by nitrating hydroquinone-
The 3,5-dihydroxyquinonediazide (sic) is
diethylether with mixed acid
claimed to be prepd similarly from the mono
Refs: 1) Beil 6, 859 2) Nietzki, Ann 215,
or diaminophloroglucinols. These compds are
153 (1882)
claimed to be unstable in detonators in con-
junction with PETN or other HE as the base
Hydrosilicofluoric Acid. See Fluorosilicic Acid
charge
in Vol 6 of Encycl, p F141-R
Ref E. von Herz, BritPat 207563 (1922) &
CA 18, 1574 (1924)
Hydrosol. A colloidal suspension in water (Ref
1). Also Brand name of L.B. Holliday & Co,
Ltd, Huddersfield, England for a proprietary
Nitrohydroquinone OH C ~H3(N0 ~)OH, mw product of the hydrosulfite class for wool
155.11, N 9.03%, red rhombohedral grains or bleaching (Ref 2)
pyramids (from w) mp 133-134°, S1sol in w; Refs: 1) Hackh’s Diet (1944), p 425-R
v sol in alc & eth. Prepd from o-nitrophenol & 2) CondChemDict (1961), p 591-L; (1971),
aq NaOH + ammonium persulphate and then p 457-R
dil sulfuric acid (Ref 1); by nitrating monoben-
zenesulfonate (Ref 4) Hydrostatic Fuze. See Vol 4, p D881-R
The effect of pH on the uv spectrum of
nitrohydroquinone has been studied (Ref 2), Hydrostatics. The science of physics which deals
also its dissociation constants, redox po- with liquids in equilibrium (Comp with Hydro-
tentials & dipole moments (Ref 5), as well dynamics)
as its electronic spectra (Ref 6). Its thin Refs: 1) Hackh’s Diet (1944), 425-L; (1 969),
layer chromatographic props were also 335-L
investigated (Ref 3)
Refs: 1) Beil 6, 856 (418) & [848] 2) H. Hydrox. Isa blasting device for underground
Staude & M. ,Tempel, Z Electrochem 61, 181 mining primarily used in coal mines. Like Cardox
(1957) & CA 52, 2533 (1958) 3) D. B. Parihar (see Vol 2, p C67-R) it employs a gas generating
et al, JChromatog 24 (1) 230 (1966) & CA chemical reaction to rupture a disk in a
66, 8141 (1967) 4) E.M. Kampouris, JChemSoc heavy-walled steel tube with the resulting flow
(1967) 1235 & CA 67, 63964 (1967) 5) of high pressure gas then doing mechanical
J. Sunkel & H. Staude,, BerBunsengesPhysChem work on the surroundings. The usual gas
72 (4) 567 (1968) & CA 69, 86177 (1968) producing system is (Ref 1):
6) Ibid 73 (2) 203 (1969) & CA 70, 91936 NaN02 + N~Cl = NaCl + Nz + 2H20
(1969
This reaction is self-sustaining (once started) but
 H 229

does not generate flames. Usually the rupture Aluminum hydroxide. Al(OH)3, mw 77.99, white
disk is selected to break at about 10 tons per sq tryst powder, d 2.42, insol in w, sol in aci!.ls &
inch (Ref 1) NaOH. Derived ‘from bauxite
A simple calcn shows that for this reaction the Rejl CondChemDict (1971), p 33
heat of explosion is 52.4 kcal/mole or 428 kcal/
Ammonium Hydroxide or Ammonia, Aqu~ous.
kg; the explosion temp (the temp that can be
Seeunder AMMONIA in Vol 1 of Encycl, pp
reached by explosion within a closed vessel) is
A296 to A305 and in CondChemDict (1971~,
about 1430°, and the vol of the gas evolved at
p 52-R
normal temp & pressure is 5401/kg. The
ignition temps of mixts of various NaN02 / Barium Hydroxide. Exists as Anhydrous,
NI-LC1 ratios, r; was found to be the lowest for Ba(OH)2, available commercially; lllonohydra~
r= 1:2. The m&ts, when stored over CaC12,undergo Ba(OH)2.H20, wh powd, highly toxic, has many
spontaneous explosion after 30-50 days, but industrial uses; Pentahydrate, Ba(OH)2 .5H 20~
stabilizers such as 2’ZOof: MgO, CaO, CaCz, translucent free-flowing wh flakes, d 651bs/c~ ft,
BaC12,MgC03,Naz C03 were effective in highly toxic; and Octahydrate, wh trysts, m~
preventing explosions for more than a year. 78°, loses w of crystallization at 408°, d 2.18
The max pressure developed by the explosion was g/cc; sol in water, alc & eth, highly toxic; pr~pd
790 kg/sq cm at a loading dens of 0.3; 1200 by dissolving Ba oxide in w with subsequent
kg/sq cm at a loading dens of 0.4; and 1700 crystallization and by other methods, used in
kg/sq cm at a loading dens of 0.5 (Ref 2) org prepns, Ba salts & in analytical them
Other reactions have been patented for use Refs: 1) CondChemDict (1971), p 92-R to
in Hydrox. Some additional irigredients 93-L 2) US Spec MIL-B-36212 (May 1964I
claimed in these patents are AN, NH4 HC03, (Ba Hydroxide, Lime, USP, Granular)
chromates and dichromates. These compositions Culcium hydroxide. Ca(OH)2, mw 74.10,
and the use of Hydrox are discussed in detail rhombic colorless crystals, mp (loses water ~t)
in Refs 3&4 580°, d 2.343, v S1sol in w, insol in ale, sol
Refs: 1) J. Taylor, Ind Chemist 24,289 (1948) in acids; absorbs carbon dioxide from air.
&CA 42,6116 (1948) 2) S. Yamamoto et al
Prepd by action of water on CaO
JlndExplosSoc, Japan 15,77 (1954)&CA 49,
Refs: 1) CondChemDict (1971), p 156
11281 (1955) 3) J. Taylor &P. F. Gay “British
2) Spec for Tech grade: O-C-1 10A (March 1962)
Coal Mining Explosives” pp 127-133, Gee.
Newnes, London (1958)&CA 53,719 (1958) Lithium Hydroxide. LiOH, mw 23.95, white
4) R. McAdam & R. Westwater “Mining Explosives” powder, mp 450°, d 1.43; sol in water & acids,
pp 90-91, Oliver& Boyd, Edinburgh (1958)& S1sol in ale. Prepd by action of water on Li or
CA 53,9673 (1958) Li20
Refs: 1) CondChemDict (1971), p 524
Hydrox Fuel Cell. See under Fuel Cells in Vol
2) SpecMIL-L-20213D (July 1964)
6 of Encycl, p F21O-R
Ref CondChemDict (1961), 517-L (Fuel Magnesium Hydroxide. Mg(OH)2, mw 58.3 4,
Cells); (197 1), 403-R colorless trigonrd crystals, loses w at 380°, d
2.38, d sol in hot water, sol in ale, sol in acids
&in solns of ammonium salts. Obtainable fro m
seawater by precipitation with CaO
Hydroxides. The generic name for compounds of
Ret CondChemDict (1 971,), p 535
the type Ma(OH~ where M is a metal and a & b
are integers. Most hydroxides are insol or Potassium Hydroxide. KOH; mw 56.11, whhe,
sparingly sol in water but are sol in aq acid with rhombic, deliquescent crystals; mp 360°, bp I
the formation of salts. Most hydroxides have 1320°, d 2.044; sol in w, alc or acids; insol
been used in neutralizing nitrated explosives in eth. Prepd by electrolysis of coned KC1
made by mxied acid or nitric acid nitration al- solns
though bicarbonates are more commonly em Refs: 1) CondChemDict (1971), p 722
ployed. The more common hydroxides are 2) US Spec for KOH Soln: MIL-P-1 175 lB
listed below: (Dee 1958) 3) US Spec for Tech KOH:
D-P-566 (NOV 1960)
 H 230

Sodium Hydroxide. NaOH; mw 40.01; white Hydroxy-trinitro-acetophenone (called Trinitro-

deliqtiescent crystals, mp 318°, bp 1390°, d 4-oxy-acetophenon in
Ger); HOC GH(NO2)3COCHs;
2.13; sol in w, ale, glycerin & acids; insol in mw 271.14, N 15.50T0, trysts; S1sol in hot w.
eth or acetone. Prepd by electrolysis of NaCl Prepd by heating 4-hydroxyacetophenone with
solns 1.3 g/cc nitric acid, No explosive props
Refs: 1) CondChemDict (1971), p 802 mentioned
2) US Spec for Tech NaOH O-S-598A, IntAmed Refs: 1) Beil 8,89’ 2) Nencki & Stoeber, Ber
(1) (July 1968) 30, 1770 (1897)

Hydroxy (Hydroxyl). A prefix indicating the Hydroxyalkyl Alkylene Dinitramines and Their
presence of “the monovalent OH group in an org Nitrate Esters. Nitrate esters such as N, N’-bis-
compd arialogous to acids of the lactic series. (2-nitroxyethyl) ethylenedinitramine.
It is preferable to oxy- used by the Germans Oz NO-C2 H4 -N(N02 )-C2 H4 -N(N02 )-C2 H4 -ON02
Refi Hackh’s Diet (1944), 425-R; (1969), (qv); were proposed as non-volatile plasticizers
335-R for NC in prepn of propellants. The method of
prepn consists of the hydroxyalkylation of a
nitramine (such as ethylenedinitramine) by means
Hydroxyacetanilide and Derivatives of an alkylene oxide (such as ethylene oxide),
Hydroxyacetarzilide. Same as Acetamidophenol, followed by nitration:
Vol 1, p A20-R CHZ-NH.N02 CH2 CH2 -N(NQ )-Cfi . Cfi . OH
+2] x+/
2-Hydroxy-3,4,6-trinitroacetanilide. See 3,5,6-
Trinitro-2-acetamidophenol in Vol 1, p A21-R CH2 -NH.NOZ CHZ CH2 -N(N02 -CH2 .CH2 . OH
~ CH,-N(N0,)-CH2 .CH,-ONO,
Hydroxyacetazide. Glycolic Acid Azide, or
See
Glycolyl Azide in Vol 6, p G1 15-R CH2-N(N02)-CH2 .CH2 -ON02
N,N’-bis(2-hydroxyethyl) ethylenedhitramine
Refi J. R. Johnson et al, USP 2683165 (1954)
Hydroxyacetophenone and Derivatives
& CA 49, 7590 (1955)
[email protected]. 0HC6 ~ COCH3, mw
136.14. Three isomers are known: ortho –
greenish-yel oil, fr p 4–6°, bp 213° at 7 17mm, Hydroxyaminoanthraquinones and Derivatives.
sp gr 1.1307 at 21°, refr ind 1.5580 at 20°; al See Aminohydroxyanthraquinone and Derivatives
sol in w; sol in alc & eth (Refs 1, 4 & 5); meta – in Vol 1 of Encycl, p A2 17-L. Its Tetranitro-
trysts, mp 95–6°, bp 296° at 756mm; sol in derivative (Aminochrysammic Acid), described
alc & eth and hot w (Ref 2);para – trysts, mp on p A21 7-L, forms expl salts of Ammonium,
109°, bp 147–48° at 3mm, S1sol in, w, sol in Barium and Potassium
alc & eth (Ref 3)
Refs: 1) Beil 8, 85, (534)& [81] 2) Beil
8, 86, (535) & [84] 3) Beil 8, 87, (536) Hydroxyaminobenzene. See Aminophenol in
& [84] 4) CondChemDict (1961), 592-L Vol , pp A241-L to A244-R. Its expl derivs:
5) Ibid (1971), p 457-R (ortho) l-Hydroxy-2-amino-4,6-dinitrobenzene or
Picramic Acid and l-Hydroxy-4-amino-2,6-
Hydroxyacetophenone Azide (called Azido-4- dinitrobenzene or Isopicramic Acid are on pp
oxy-acetophenone in Ger) HOC6H4COCH2N3, A241-R & A243-R
mw 177.16, N 23.72%; yel leaflets, (from w)
mp 136°, sol in the usual solvents except ben-
zene; decomposes in boiling w Prepd by heating Hydroxyaminobenzoic Acid. See Aminosalicylic
4-hydroxy-chloroacetophenone with Na Azide Acid in Vol 1, p A257
in ale. No explosive props are mentioned
Refi Beil 8 [87]
 H 231

1-Hydroxy-6-aminobenztriazole or 6-Aminobenz- Hydroxy - and Amino-methylnitramines. A review

azimidole(called oxy-6-amino-benztriazol in Cer) with 93 refs of the chemistry of nit ramines is
reported by Lamberton (Ref)
/N~
Hz NC6H3\ N, mw 150.14, N 37.32%, rose- Refi A. H. Lamberton, Quart Revs 5, 92-95
N~H) (1951) & CA 46, 6081 (1”952)
colored powder, mp 220° (with, carbonization),
puffs off at 235-36° without melting; sol in hot
water & hot ale, insol in eth or ligroin. Prepd Hydroxyanilinobenzene-diazonium. See Arrilino-
by treating 1-hydroxy-6-nitro-benztriazole with benzenediazonium Hydroxide in Vol 1, p A421
Sn & coned HC1
Refs: 1) Beil 26, 326 2) T. Curtius & (?)
Mayer, JPraktChem [2] 76, 395 (1907) Hydroxyanilinopropane. See Anilinopropanol
in Vol 1, p A436-L

Hydroxyaminobutane. See Aminobutanol in

Vol 1, p A192-R Hydroxyanthroquinone and Derivatives
l-Hydroxyanthraquinone, C J-14(C@2 .C6H3 .OH;
mw 224.20. Two isomers of this formula are
Hydroxy and Amino Compounds, Explosives known:
from. A number of commercially available amino I-lfydroxy-, red-orn ndls (ale), mp 194–950,
alcohols have been condensed with 2,4-dichloro- bp – subl; sol in alc & v sol in eth.’ Can be
benzene to give products which, when nitrated, prepd by heating phthaiic acid anhydride with
are explosive. Products from the nitration of phenol in the presence of ZnC12 & HC1 at
several glycerol derivs, guanidine derivs & 120–25 0 (Refs 1 & 3)
phenylbenzotriazole derivs were also studied. 2-Hydroxy-, yel ndls (ale), mp 306–08°, bp –
Prepn of the following compds & their props subl; v S1sol in w; sol in alc & eth. Can be
are reported: prepd by diazotizing 2-aminoanthraquinone in
Trinitrophenylnitroguanidine HC1 soln and boiling the diazonium sulfate soln
N-(J3-Hydroxyethyl) -N’-nitroguanidine Nitrate (Refs 2 & 4)
Tris-Hydroxymethylmethylguanidine Refs: 1) Beil 8, 338, (650) & [388] ‘
N,N’-Dirritropiperazine 2) Beil 8, 343, (658) & [393] 3)IM.
Tetryl Copisaron, JChemSoc 117, 214 (1920)
Of other expls produced, Heptryl, Ditetryl 4) A.G. Perkin & T.W. Whattam, JChemSoc
& Trinitrophenylisobutylolnitramine Nitrate 121,289 (1922)
appeared especially worthy of further study
Refi R. C. Elderfield et al, “Explosives from
Hydroxy and Amino Compounds,” OSRD Repts 1-Hydroxy-4, 5, 8-trinitroanthraquinone
158 (1941) & 907 (1942) (NO, ), C,(OH) COCOC, H., mw 359.20,N’11 .10%,
tryst, mp 245°. Prepd by treating the correspond-
ing dihalogen or dinitro anthraquinone with a
Hydroxyaminomethylbenzene or Hydroxyamino- metal nitrite in an organic solvent
toluene. See Aminocresol in. Vol 1, p A 193-R Refs: 1) P. Belshaw et al, USP 2,587,093
(1952) & CA 46, 8679 (1952) 2) P. Belshaw
et al, “BritPat 670,720 (1952) & CA 46, 10205
Hydroxyaminomethylpropane. See Aminomethyl- (1952)
propanol in Vol 1, p A233-L
Hydroxyazapropane Nitroxy-Nitro Derivative.
See NENA or N-((? Nitroxyethyl)-nitramine in
Hydroxyaminopropane. See Aminopropanol, Vol 1 of Encycl, p A201 -L
Vol 1, p A253-L & R
J

H 232

l-Hydroxy-lII-azidoiminomethyl-triazene or N’- the copper salt, CN7 HOCU, with other com-
Hydroxy-N-azidoiminomethyl-triazene, pounds, which Hofmann called “Amidotetrazot-
HON:NNHC(:NH)N3; mw 129.09, N 75.97%. kupfer,” but did not give a formula for it.
Inasmuch as this compound was never isolated The fdtrate remaining was evaporated to
in the free state but was prepd only in solution, dryness in vacuum over phosphorous pentoxide
its structure has not been definitely established. which gave thin plates, appearing sky-blue by
Hofmann et al (Refs 1 & 2) claimed that when reflected light and pale-green by transmitted
they treated guanyldiazoguanyltetrazene (called light. The analysis gave Cu 32.84% and 33.85%
by them simply “diazohydrate,” but now known and N 5 1,78Y0, which closely coincides with the
as “Tetracene”) with KOH or NaOH in the composition; Cu 33.37%, N 51.41 ~0 of the
prescence of water, the insoluble Tetracene went formula CN7 HOCU
into solution accompanied by the evolution of The dry copper salt is very sensitive to
ammonia. When this solution was acidified, the friction or impact, but it is insensitive when
original “Tetracene”~ was not recovered. When wet. It explodes violently on heating
the alkaline solution of Tetracene was allowed When a solution of the copper salt in very
to evaporate in a vacuum over coned Hz S04, dilute nitric or hydrochloric acid was evaporated
an explosion took place while the mass was still to dryness on a water bath, a greenish powder
wet remained. This residue is so sensitive that it
When an alkaline solution of Tetracene was exploded on being touched with a glass rod
acidified with dilute HN03 and then treated even when wet. It is presumed that this is
with an excess of AgN03, a pale-yellow ppt was me copper salt of Tetrazyl-azoimide, since it
obtained. This ppt was washed with a 370 solu- was converted to the corresponding silver salt,
tion of HN03 and the residue dissolved in a N3 .CNQAg
2.5% solution of ammonia. The resulting solu- Refs: 1) Beil, 3 (60) 2) K. A. Hofmann et al,
tion with a pale yellow color gave, after evapor- Ber 43, 1093 (1910)
ating the ammonia in vacuum over Hz SOOor on
acidification by HN03, a white ppt which the
authors called “Tetrazylazoimidesilber,” Hydroxyazobenzene and Derivatives
N3 Cm. Ag. This compound exploded violently Hydroxyazobenzene, H0.C6H4.N:N.C6~ ; mw
when heated in water on a water bath. It also 198.22. Three isomers are known: ortho –
exploded when the incompletely dried material orn ndls, mp 82.5–83° (Ref 1); meta – yel
was touched with a feather trysts, mp 114–150 (Ref 2); and para – orn
The same authors claimed that they prepd trysts, mp 155–56° (Ref 3); all three S1sol in
a copper salt of the following composition: w; sol in alc & eth
// ‘“c””o Refs: 1) Beil 16, 90, (233)& [32] 2) Beil
CN7H0.CU, or N3.. C I ,N51.41%,light- 16, 94& {85} 3) Beil 16, 96, (233), [38]
\ NH.N:N & {86}
green plates
For preparation of this salt,, they dissolved Mononitrohydroxyazobenzene, C ~ ~H9N3 03; mw
Tetracene,in very dihrte pure NaOH solution and 243.22, N 17.28%. Several isomers are found in
then added immediately, without acidification, an Beil:
excess of copper acetate solution. The resulting 5-Afitro-2-hydroxy-azobenzene,
brownish ppt was separated and washed with H0.C6H3(N02)N :N.C ~H5, orn-red pltlts (from
2-3~0 solution of acetic acid followed with water. dil acetic acid), mp 150–51° (Ref 1)
On treating the ppt with 3% solution of 3-Nitro=#-hydroxy -azobenzene, lt-yel pltlts (from
ammonia, a blue solution was obtained, benz), mp 128° (Ref 2)
leaving a brown residue of copper cyanimide. 2’-Nitro4hydroxy-azobenzene,
When the blue filtrate was evaporated partly H0.C6H4 .N:N.C ~H4.N02; dk-red ndls (from
in vacuum over coned Hz S04 until the dil MeOH), mp 162–63° (Ref 3)
separation of a small amount of greenish plates 3’-Nitro-4-hydroxy-azobenzene, om-yel trysts
was obtained, they proved to be a mixture of (from acet at), mp 147-64° (Ref 3)
 H 233

4’-Nitro4-hydroxyirzobenzene, trysts’(from alc yel pltlts, exploding violently on heating; and

or xylol), mp 219–219.5° (Ref 5) as Ba salt, BaC2N1 OO+4H2C), yel trysts, just as
Other props & methods of prepn are given expl as Ba srdt. Salts can be prepd by passing
in Refs C02 thru a boiling soln of either Na or Ba salt
Refs: 1) Beil 16, 93 2) Beil 16, 123, (239) of 5-diazotetrazole
& [57] 3) Beil 16, 99, (234), [39] & { 88} Refs: 1) Beil 26, 596 2) Thiele & Marais, ,
4) Beil 16, 100, (235), [39] & { 88} Am 273, 150 (1893)
.
Dinitrohydroxyazobenzene, C H N O : mw
288.22, N 19.44%. Four isomers are known: Hydroxybenzaldehyde and Derivatives
2,3’-Dinitro4-hydroxy-azobenzene, Hydroxybenzaldehyde, H0.C6H4.CHO; mw 122.12.
HO.C# ~(N02 )N:N.C6H4.N02; red c~sts Three isomers are known: ortho – or Salicyl-
(from acet acid), mp 202° (Ref 4) aldehyde, colorless liq or dark-red oil with bitter
3,2’-Dinitro4-hydroxy-azobenzene, brn-red trysts almond odor; combustible; fr p -7°, bp 196.5°,
(from l-ethoxy-2-ethanol), mp 190° (Ref 3) sp gr 1.153 at 25°/4; refr ind 1.5736 at 20°; v
5,4’-Dinitro4hydroxyqzobenzene, orn-colored S1sol in w, v sol in alc & eth; can be prepd by
trysts (from aq ale), mp 205–07° (Ref 1) the interaction of phenol & chlf in presence of
2’,4’-Dinitro4-hydroxy-azobenzene, aquebus alkalies. It is used in anal them &
HO.C da .N:N.C ~3(N02)2; trysts (from MeOH), perfumery (Refs 1, 4 & 5); meta – orn-pink
mp 185–86° (Ref 2) trysts; mp 106–08° (Ref 1), bp ca 240°; sol
Other props & methods of prepn are found in ale, benz, hot w & aromatic hydrocarbons.
in Beil It is used as intermediate for dyes, plastics &
Refs: 1) Bed 16, { 84} 2) Beil 16, { 88} pharmaceuticals and in anal them (Refs 2, 3
3) Beil 16, { 100} 4) Beil 16, { 101} & 4); para – colorless trysts, mp 116–1 7°;
bp – subl; sol in ale, eth, acet, benz & w. It
Trinitrohydroxyazobenzene, Cl 2H7N5 07; mw is used in pharmaceuticals (Refs 3, 4 & 5)
333.22, N 21.02%. Two isomers are known: Refs: 1) Beil 8, 31, (515), [35] & {135}
4, 6,4’-Trinitro-3-hydroxy+zobenzene, 2) Bed 8, 58, (524), [52] & {197} 3) Beil
HO.C ~H2(N02)2N:N.C ~H4.N02; red ndls (from 8, 64, (527), [63] & {215} 4) CondChemDict
acet ac + w), mp 179°; was prepd by heating (1961), 592-L & 999-L 5) Ibid (1971), 771-R
benzoquinone-(1 ,4)-oxime-4,6-dinitro-3 -hydroxy- (ortho) & 458-L (meta & para)
phenylhydrazone with nitric acid (d 1.39) &
acetic acid (Refs 1 & 3). No expl props are ortho-Salicylaldehyde Azide or Salicylic Acid
reported Azide, H0.C6H4.CON ; mw 163.13, N 25.76%;
2’,4’, 6’-Trinitro-4-hydroxy-azobenzene, plates (from eth), mp 27°, extremely volatile;
H0.C6H4 .N :N.C ~H2(N02)3; dk-red, blue was obtd by action of ice cold fuming HN03 &
colored nd.ls (from dil acetic acid), mp 194– NaN~ on salicylic acid hydrazide. No expl
95°; was prepd from 2,4,6 -trinitrophenylhy dra- props recorded (Refs 1 &2)
zinc & benzoquinone-(1 ,4) in alc HC1 (Refs 2 Refs: 1) Beil 10, 100 2) Struve & Raden-
& 3). No expl props reported hausen, JPraktChem [2] 52, 240 (1895)
Refs: 1) Beil 16, [37] 2) Beil 16, [40]
3) W. Borsche, Ber 54, 678 & 1287 (1921) 4, 6-Dinitro-3-hydroxybenzaldehyde gives dark
NOTE: No higher nitrated derivs of Hydroxy- crimson needles of 2,4,6-Trinitro-hy droxy -
azobenzene were found in the literature benzaldehyde- [4-nitro-phenyl hydrazone] ,
Oz NCC I& NN:CC6 H(N02 )3 OH; which explode
at 228-30°. Its p-Bromophenylhy drazone, deep
5-Hydroxy-1,5‘-azotetrazole. olive green crystals with a metallic luster, also
N=N–N —N:N—C=N explodes violently at 218-20°. The p-nitro-
II derived from 2,6dinitrohydroxy-
II phenylhydrazone
benzaldehyde, deep terra cotta crystals, explodes
N= C.OH HN–N=N; mw 182.12,
N 76.92%; exists as Na salt, Na2C2Nl ~O+5H20, at 240-42°, but the corresponding p-bromophenyl-
 H 234

hydrazone is not explosive. Many other phenyl- 16, (454) ‘ 3) Beil 16, 874, (455), [466] &
hydrazone derivatives are known but although { 1070}
they are unstable to heat they do not appear
‘to be explosive (Ref 2)
Refs: 1) Beil 15 [199] 2) H.H. Hodgson& H. Hydroxybenzenearsonic Acid and Derivatives
G. Beard, JChemSoc 1927, 2375 &CA 22, Hydroxybenzenearsonic Acid (called Oxy-
64 (1928) phenylarson$iure in Ger), H0.C6H4ASO(OH)2;
Many nitro derivs of hydroxybenzaldehyde mw 218.03. Three isomers are known:
are known (See Beil 8, 56-7, 62-3, 83 & [63]) 2-Hydroxybenzenear~onic Acid, ndls (from w),
but none of these isexplosive, even the mp, 190–91! readily sol in water, MeOH & ale;
trinitro derivative, (N02 )~t~ H(OH)CHO, al- insol in eth (Ref 1)
though it melts (1610, with decomposition. 3-Hydroxybenzenearsonic Acid, trysts (from w),
However reacting the latter with hydrazine mp 159–73°; sol in w, MeOH, alc & glac acet
sulfate produces the explosive: acid; insol in chlf & benz (Ref 2)
4-Hydroxybenzenearsonic Acid, trysts or ndls
Azin of 2,4,6-trinitro-3-hydroxy-benzaldehyde, (from hot acet), mp 177–78°; sol in w, alc &
also called 2,4,6,2’,4’,6’-Hexanitro-3,3’-dihy- dil mineral acids; S1sol in eth & eth acet (Ref 3)
droxybenzadazin (also called Azin des 2,4,6- Other props & methods of prepn are found
Trinitrobenzaldehyds in Ger). [HOC 6H(N02)3CH: in Beil
N-] *; mw 510.28, N 21.96%, OB -53.0%; in the form Refs: 1) Beil 16, (454) & [464] 2) Bed
of bright yellow needles that are sol in alc or 16, (454) 3) Beil 16, 874, (455), [466]
50% .HAc, but insol in benz. Prepd by treating & {1070}
2,4,6-Trinitro-3 -hydroxybenzaldehyde in hot aq
NaOH with hydrazine sulfate
Refs: 1) Beil 8, [63] 2) H.H. Hodgson & Mononitrohydroxybenzenearsonic Acid,
H.G. Geard, JChemSoc 1927,2379 C6H6N06AS; mw 263.03, N 6.2W0. .Many mono
nitro derivs are found in Beil
Ref Beil 16, (454, 455, 456), [465, 466, 468,
Hydroxybenzazide or Hydroxybenzoylazide. 469] & {1070, 1073}
See under Hydroxybenzoic Acid and Deriva-
tives in this Vol
Dinitrohydroxybenzenearsonic Acid,,
(02 N)2C6H2’.ASO(OH)2; mw 308.03, N 9.16%.
Hydroxybenzene. See Phenol or Carbolic Acid Two derivs are found in the literature:
3,5-Dinitro-2-hydroxybenzenearsonic Acid, yel
ndls (from w), mp 244–460; prepd by diazo-
Hydroxybenzenearsonic Acid and Derivatives tizing picramic acid with Na arsonite in alc soln;
Hydroxybenzenearsonic Acid (called Oxy- forms trysts & amorph salts (Ref 1)
phenylarsoniaure in Ger), H0.C6H4ASO(OH)2; 3,5-Dinitro-4-hydroxybenzenearsonic Acid, yel
mw 218.03. Three isomers are known: trysts (from w), mp >275° w/o melting, d
2-Hydroxybenzerzearsonic Acid, ndls (from w), 2.0565 at 20°; dec on heating in a flame; an
mp 190–9 1°; readily sol in water, MeOH & expl which liberates a poisonous gas (AsH ~).
ale; insol in eth (Ref 1) It can be prepd by nitrating 4,hydroxybenzene-
3-Hydroxybenzenearsonic Acid, trysts (from w), arsonic acid Na salt with 4 moles of nitric
mp 159–73°; sol in w, MeOH, alc & glac acet acid (d 1.52) in coned sulfuric acid at 15–20°
acid; insol in chlf & benz (Ref 2) (Ref 2)
4-Hydroxybenzenearsonic Acid; trysts or ndls A lab expln took place when a thick wet
(from hot acet), mp 177-78°; sol in w, alc & cake of the compd was heated in a flask (Ref
dil mineral acids; S1sol in eth & eth acet (Ref 3) 3): Some work done in Phillip’s Lab indicates
Other props & methods of prepn are found in Beil that the acid as well as its salts might prove to
Refs: 1) Beil 16, (454) & [464] 2) Beil be as expl as PA to which it is closely related
 H 235

Refs: 1) Beil 16, (454) & [465] 2) Beil OH ‘

16, (457), [470] & { 1075} 3) M.A. 02N N:N.C ~~H6 .OH; purple-red cr@s,
Phillips, Chern & Ind 1947, 61 & CA ,43, 2437 o
mp 228 ; sol in ale, glac acet ac,& eth acet; d
(1949) 4) No further refs found in CA ‘thru S01in benz & Chlfi fOITnSa K Sak, KC1 fjHloN@Q,
1971 green + bronze luster trysts (from ale), which
NOTE: No higher nitrated derivs of Hydroxy- explodes ‘on heating (Refs 1 & 5)
benzenearsonic Acid were found 4Nitro-1-hydroxybenzene- (3 azo 1)-2-naphthol,
.,, .
HO

Hydroxybenzeneazonaphthol and Derivatives

N: N.CIOH ~OH; red trysts,. mp
N02 t’.
Hydroxybenzeneazonaphthol (called Phenol-
azo-naphthol in Ger), Cl6H12N202; mw 264.27, >260°; SO1in H2S04; v d SO1in org SOIVS(Ref 2)
N 10.60’%. Four isomers are known: 2-Nitro-l-hydioxybenzene-(4 azo 1)-2-naphthol,
l-(2-hydroxyb’enzeneazo)-2-naph thol, red nclls (from Nitrobenz), mp 2210; sol, in benz
& coned H2S04; v S1sol in hot ale, eth & cold
acet (Ref 3)
OH “ l-f5-Nitro-2-hydroxybenzeneazf?)-2-naphthol,
OH
–N:N
~ 8 ‘ N:N.C 10H6.0H; no description
HO; dk-violet trysts (from alc o
N02 ..
or eth acet), mp 193° (Ref 1); forms numerous
reported (Ref 4) ,.
metal salts
l-(3-hydroxybenzeneazo)-2-naph thol, Other props & methods of prepn are found
in Bed
Refs: 1) Beil 16, (263) 2) Beil 16, (264)
OH 3) Beil 16, (265) & [74] 4) Beil 16, {143}

N:N 5) G.T. Morgan & J.W. Porter, JCS 107,

08 651–56 (1915) & CA,9, 2061–62 (1915)
HO; red-brn powd, mp
231–33°; forms a Cu, sqlt (Ref 2) . Dinitrohydroxybenzeneazonaphthol, C 1fj HI 0N406;
l-(4-hydroxybenzene)-(4 azo 1$2-naphthol, mw 354.27, N 15.81%. Three isomers are found
HO N:N.C ~~H6 .OH; red trysts, ndls in Beil:
(from 4,6-Dinitro-l-hydroxybenzene-(3 azo 1)-2-naphthol,
w MeOH , pltlts (from ale) or dk-violet
ndls (from alc + benz), mp 194°; forms Cu & HO
Ni tryst salts (Ref 3)
l-(4-hydroxybenzene)-{4 azo 4>1-naphthol, ‘ 02NGN:N:c@600H’brn-rednds
,. N02
HO (-~ N: N-C ~~H6 .OH; pltlts, mp – (from benz), mp s260°; insol in ale; sol in coned
not reported; readily sol in alkalies giving a dk H2S04 giving a violet color (Ref 1)
red color (Ref 4) 2,6-Dinitro-l-hydroxybenzene-(4 azo 1)-2-rraphthol,
Other props & methods of prepn are found
in Beil
HaNNcloH60H;redn~s(from
Refs: 1) Beil 16, 169, (262) & {141} N02
2) Beil 16, {144} 3) Beil 16, 170, (264) & Nitrobenz), mp 269–70°; sol in alk; S1sol in
[74] 4) Beil 16, 158 ale; v d sol in glac acet acid (Ref 2)
5-Nitro:l-hydroxybenzene-(2 azo l)4-nitro-2-
naphthol,
Mononitrohydroxybenzeneazonaphthol,

8
Cl ~Hl ~N304; mw 309.27, N 13.59%. Several
isomers are known:
o2NdN’: ‘H ’02;
5-Nitro-l-hvdroxybenzene-’&? azo 1)-2-naphthol,
 H 236

dk-brn, red trysts (from anisole), mp 132–66° Refs: 1) Beil 10,43, (20), [25] & {87}
(unsharp); sol in coned H2S04 giving a red- 2) Beil 10, 134, (63), [79] & {242}
violet color (Ref 3) 3) Beil 10, 149, (68), [88] & {277}
Other props & methods of prepn are given 4) CondChemDict (1961), 592-R & 997-L
in Refs 5) Ibid (1971), 771-R (ortho) & 458-R
Refs: 1) Beil 16, (264) 2) Beil 16, 171 (meta & para)
3) Beil 16, (268)
Hydroxybenzoic Acid Azide, Hydroxybenz-
2,4,6-Trinitro-1-hydroxybenzene-(3 azo 1)-2- azide or Hydroxybenzoyl Azide, H0.C6 ~ C0.N3;
naphthol, mw 163.13, N 25.76%. Three isomers are known:
2-Hydroxybenzoyl Aztie or Salicylic Acid Azide,
pltlts (from eth), mp 27°, extremely volatile;
o’”5”’”’lo”60H’rn”3”2’ was prepd from salicylic acid hydrazide by
“02
action of an ice-cold soln of aq HNOs & NaN02
N 17.54%; brownish trysts (from Nitrobenz),
(Refs 1 &4)
mp – not reported; sol in coned H2 S04 with
3-Hydroxybenzoyl Azide, trysts (from alc + w),
blue color; sol, in dil NaOH with dk-red color;
mp 95°; sol in ale, eth & chlfi S1sol in petr eth;
the alkaline soln decomp on warming gently. prepd by nitrating 3-hydroxybenzhydrazide with
It was prepd by coupling the diazotized salt of H2S04 & NaN02 (Refs 2 &4)
2,4,6-Trinitro-3 -aminophenol with ~-naphthol 4-Hydroxybenzoyl Azide, ndls (from alc + w),
in glac acet ac + coned sulfuric acid (Refs 1 & mp 132°; was prepd by action of NaOH, NaNQ
2). No expl props are reported & acetic acid on 4-hydroxybenzhydrazide (Refs
Refs: 1) Beil 16, [73] 2) E. Misslin, Helv 3,
3&4)
637 (1920)
No expl props were reported for the above
NOTE: No higher nitrated derivs of Hydroxy- azides
benzeneazonaphthol were found in the literature Refs: 1) Beil 10, 100 2) Bed 10, 142
3) Beil 10, 175 4) Struve & Radenhausen,
JPraktChem [2] 52, 240, 235, 237 (1895)
Hydroxybenzoic Acid and Derivatives
Hydroxybenzoic Acid, H0.C6H4.COOH; mw 5-Nitro-3-hydroxybenzoyl Azide (called 5-Nitro-
138.12. Three isomers ortho or
are known: 3-oxy-benzazid in Ger), H0.C6H3 (NO 2)C0.N3;
Salicylic Acid, colorless, combustible, monocl mw 208.15, N 26.92%, OB to C02 –92.2%;
trysts (from w) or pdr of sweetish taste; sp gr red-yel flocculent ppt, mp — deflgr on heating;
1.443 at 20°; mp 158.3° (subl at 760), bp ca insol in w; sol in alc or eth. Prepd from 5-
211° at 20mm; v S1sol in w; sol in ale, eth, nitro-3-aminobenzhydrazide in acet acid + aq
acetone, oil or turpentine. Prepd by treating NaN02 (Refs 1 & 2)
hot soln of Na phenolate with C02 and acidifying Refs: 1) Beil 10, 147 2) T. Curtius & A.
the Na salt thus formed. Used as org intermediate Riedel, JPraktChem [2] 76, 260 (1907)
and for manuf of aspirin (See Vol 1, p A87) &
other medicinrds. Its dust forms an expl mixt Hydroxybenzoic Acid, 3-Chloro-5-diazo or
with air (Refs 1, 4 & 5); meta, colorless trysts, 5-Diazo-3-Chloro-Hydroxybenzoic Acid (called
sp gr 1.473, mp 200–01°; sol in w, eth & hot 3-chlor-5-diazo-salicylsaiire in Gerl
ale. Can be prepd by passing light thru a hot
suspension of 3-hydroxybenzrddehyde in NaOH.
Used as intermediate for plasticizers, in resins HOOC cl
and as petroleum additives (Refs 2 & 4); para,
colorless trysts, sp gr 1.468 at 4°; mp ca 215°
(Lange); 210° (Ref 4); sol in w, alc & eth.
Prepd by interaction of p-aminobenzoic acid
N=N
with nitrous acid. Used as intermediate and for mw 198.57, N 14.1 l$ZO;
yel scale-like crystrds
prepn of synthetic drugs (Refs 3 & 4) (from glac HAc); v S1sol in water or ale.
 H 237

Prepd from 3-chloro-5-amino-salicylic acid and It is prepd by nitrating 2,4,6-Tribromo-3-hydroxy-

Na-nitrite in dil, HC1. Explodes at 193° benzoic acid with nitric acid and neutralizing
Refs: 1) Beil 16, (369) 2) R. Meldola et with Ca-hydroxide (Ref 1)
al, JChemSoc 111, 543 (1917) 3,5-Dinitro-4-Hydroxybenzoic Acid, Copper
Salt. Cu [OOCC6 H2 (OH)(N02 )2 ] ~ . 3H2 O;
Hydroxybenzoic Acid, 4- Diazo or 4-Diazo-3- green crystals, starts to decompose at 110° when
chloro-hydroxybenzoic Acid, [called Anhydro- heated slowly (Ref 6), loses water at 180° &
(3-oxy-benzoes%rre-(4) in Ger], explodes violently at 320° (Ref 2). It also
COOH COOH explodes on rapid heating (Ref 6). Prepd by
action of CUAC on Dinitrohydroxybenzoic acid
3,5-Dinitro-4-Hydroxybenzoic Acid, Lead Salt.
Pb [OOCC6H2(OH)(N02 )2] ~ .3H20; mw 715.50,
N=~ N2. ; N 7.83%; yellow ndls (from water or dil HAc),
mw 164.12, N 17.07%; yel powd, mp – very SI sol in water. Prepd by reaction of Pb-nitrate
unstable; prepd by diazotizing 4-arnino-3-hydroxy- and Dinitrohydroxybenzoic Acid (Refs 2 & 5).
benzoic acid (Refs 1 & 2) It explodes violently on rapid heating (ref 6)
Refs: 1) Beil 16, (369) 2) R. Mellet, Chem- and is claimed to’ be as shock- sensitive as
Ztg 34, 1073 (1910) Mercuric Fulminate (Ref 3). Its use as a pri-
mary explosive has been claimed in Ref 4
Hydroxybenzoic Acid, 3-Diazo-5-nitro or Refs: Beil 10, 148 2) Beil 10, [69] 3) J.
3-Diazo-5-Nitro-Hydroxybenzoic Acid (called Bums, USP 1,928,780 (1932) & CA 27, 5981
5-Nitro-3-diazo-salicyliaure in Ger). (1933) 4) W. Bruen, USP 2,021,497 (1936)
OOH & CA 30, 618 (1936) 5) M. Schaefer, MP 27,
0 153 (1937) & CA 31, 7864 (1937) 6) J.
“N; Nevole, Ber 77B, 61 (1944) & CA 39, 288
02 N o N# (1945)
2,4,6-Trinitro-3-hdroxybenzoic Acid, (called
mw 209.13, N 20.10%, OB to C02 –80.3%; yel
ndls (from ale); turns brown at 100°, decomp at Trinitro-oxy-bepzoesaiire in Ger).
HOC6H(N02)3COOH; , mw 273.13, N 15.39%,
145-150°, explodes on rapid heating. Prepd by
OB -38.2%; shiny crystals (from cone nitric acid),
reacting 3-amino-salicylic acid with Na-nitrite in
platelets and prisms, containing I mole H2 O
HC1. [nfra-red spectra confirm diazonium
(from w), mp ca 105° (loses water) of
structure shown above (Ref 2). Its lead salts :
hydrated compd, 186° of anhydrous,darkens at
also have this structure. They are light yellow,
200° & puffs off on rapid heating; sol in
sparingly sol in org solvents, and are sensitive
water, alc or eth, d sol in benz. Prepd by
to impact, friction & flame
heating diazoaminobenzoic acid with coned nitric
Refs: 1) Beil 16, (368) 2) B. Glowiak, Bull
acid, or reacting 3-amino-benzoic acid with fum-
acad polon sci, ser, sci, chim, geol et geograph
ing nitric acid (Ref 1). It is quantitatively pre-
8, 1 (1960) & CA 54, 12019 (1960)
The mono & dinitro derivatives of hydroxy- cipitated by a phenylacridine soln (Ref 3)
benzoic acid are stable, non-explosive compounds The Barium, Copper and Lead salts of Tki-
(Refs 1, 3 &4) nitrohydroxybenzoic acid are explosive:
Barium Salt. Ba [OOCC6 H(N02 )3 (OH)] ~ .2H2 O;
Refs: 1) Beil 10, 183, (52, 80) & [85, 108] 2)
R. Schmitt, SS 38 11 (1943) & CA 38, 2822 yellow needles; very explosive (Ref 1)
(1944) 3) H. Goldstein & R. Staum, HelvChim Copper Salt. Cu [OOC~ H(NQ )3 (OH)] ~. 5H2 O;
Acts 35, 1470 (1952) & CA 47, 4859 (1953) green needles; explodes at 299” or on rapid
heating (Ref 1)
Some of the srdts of the dinitro derivative Lead Salt. Pb [OOCC6 H(N02)3 OH] ~. Schmitt
are explosive: determined the ignitability of pellets of this
2-Bromo-4,6-Dinitro-Hydroxybenzoic Acid, salt (Ref 2). On exposure to flame, pellets
Calcium Salt. Ca [OOCC6 H(OH)(Br)(N02 )2 ] ~ pressed at 500 kg/cm2 detonated, while pellets
 H 238

pressed at 1000, 2000 or 3000 kg/cm2 merely (decomp); insol in water; sol in. ale, benz or
burned Iigroin. Prepd by mixed acid nitration of 2-
See Dead-Pressed Explosives in Vol 3, p D20-L. hydroxybenzylaniline
Ficheroulle & Kovache claim that this salt is Ret Beil, 13, 580 “
not useful as an explosive primer (Ref 4)
‘ Refs: 1) Beil 10, 148-49 & (67-8) 2) R. Hydroxybenzyltoluidine, Tetranitro Derivative
Schmitt, SS 38, 133 (1943) & CA 38, 2823 {called Tetranitro [(2-oxy-benzyl)-p-toluidin] in
(1944) 3)’ Ibid, p 149 4) H. Ficheroulle & Ger}. XXXX(N02)4(OH)C6 HZCH2NHC6H2(CH3);*
A. Kovache MP 31, 7 (1949) & CA 46, mw 393.30, N 17.81%; yellow ndls (from benz),
1“1686 (1952) mp 168°; sol in alc or benz; insol in water.
Prepd by mixed acid nitration of 2-hydroxy-
benzyl-p-toluidine. Explodes on rapid heating
Hydroxybenzotriazole. in
See Benzotriazolol *Note: Posih”on of NOZ groups has not been
Vol 2, p B87-R. Additional explosive deriv-’ determined. Consequently, the number of H
atives of Benzotriazolol are described below: groups on each benzene ring is also uncertain
l-Bromobenzo-3,4-( 3’-azimidole), C ~HQBrN30; Refi 1) Beil, 13, 581 2) Not found in CA,
mp 201.5-202.5°, sol in alkalies. Explodes on heat- 1957-71 “
ing (Ref 1)
Vis (Ref 2) lists some other explosive ct-Hydroxybibenzyl or u,~Diphenyl-fi -hydroxy -
derivatives of l-hydroxy-l ,2,3 -benzotriazole, ethane. Its pentanitro deriv is’i ‘ ,
for example: 2,4,2’,4‘,5’-Pentanitro-,ct-hydroxybibenzyl” or a-
4,6-Dichlor-l-hydroxy-1,2,3-benzotriazole, mp 2,4,5-Trinitrophenyl-b-2’,4’-dinitrophenyl-~ -
193°; powerful ‘explosive hydroxyethane.
fHz— ~H.OH
Hydrazine salt of the above compound, mp
186-93°; explodes violently on heating
4,6-Dibrom-l-hydroxy -l,2,3-benzotriazole, -N02 -N02
mp ,222°; powerful explosive
Hydrazine salt of the “above compound, mp 02
00
about 222°; very explosive
N02 N02
Hydrazine salt of 4-nitro-6-chlor-1-hydroxy-
1,2,3-benzotriazole, orange-yellow amorphous mw 423.25, N 16.5570; pale cream needles (from
solid; powerful explosive
very toluene), mp 187.3°; v 51 sol in alc or eth; ap-
Goldstein & Voegeli (Ref 3) describe: preciably sol in benz, toluene, acetone, ethylene
3-Hydroxybenzotriazole-5-carboxylic acid, dichloride & acetylene tetrachloride. It was prepd
decomp 225°; deflagrates at 245-7° by adding tetranitro-diphenylamine to fuming ‘
Refs: 1) A. Mangini, Gazz Chim Ital, 66, 675- sulfuric acid at 85° for 4 days,, after cooling
84 (1936) & CA 31, 4961 (1937) ‘2) B. Vis, fuming nitric acid (95%) was added and the temp
Rec Trav Chim, 58, 847-55 (1939) & CA 33, was raised slowly and maintained at 85° for
8612 (1939) 3) H. Goldstein & R. Voegeli, two days. The separated solid was collected,
Helv Chim Acts, 46, 475-81 (1943) & CA 37, washed with alc & recrystallized from toluene
5709 (1943), The compd exploded in 5 sees when heated
to 360°, and exploded at 18 inches when im-
Hydroxy-6-nitro-1,2,3-benzotriazole-5-acetic Acid. pacted with a 2 kg wt. It could not be deto-
See under Benzotriazolol in Vol 2, p B88-R nated with 0.4g of MF, but when initiated with
0.25g of Tetryl & 0.25g MF in the sand test,
it crushed 2 lg of sand (Ref)
Hydroxybenzylaniline, Tetranitro Derivative Refi W.H. Rinkenbach & H.A. Aaronson, JACS
(called Tetranitro in Ger).
[2-oxy-benzyl-anilin] 52, 5042-44 (1930) & CA 25, 508 (1931)
XXXX(N02 )4 (OH)C6 H2 CH2 NHC6 H3; mw 379.27,
N 18.47%; yellow ndls (from benz), mp 66°
 H 239

Hydroxybutyl See Butanol and

and Derivatives. are DINA, EtNENA, MeNENA and Me2 NENA.
Derivatives in Vol 2, p B372-R : ‘ They are described separately
Refl A.T. Blomquist & F.T. Fiedorek, USP
2678946 (1954) & CA 49, 4704 (1955)
Hydroxychlorophenyl and Derivatives. ”See
Chlorophenyl and Derivatives in Vol 3, p C362-L 7-Hydroxy-2,5-diazaheptane. See N-Ethanol-N’-
methyl-ethylenediamine in Vol 6, p E 183-L

3-Hydroxycumarone-2-azide. 2-Azide,3- See Hydroxydichlorobenzene and Derivatives. See

coumaranone in Vol 3, p C548-L Dichlorophenol and Derivatives in Vol 5, p
D1213-R
1-Hydroxycyclohexyl-1-hydroperoxide and 1-
Hydroxy-1’-hydroperoxidecyclohexylperoxide. Hydroxydiethylperoxide. See Ethylethanol-
See under Cyclohexanone Peroxide in Vol 3, peroxide in Vol 6, p E294-L
p C598-L
Hydroxydimethylperoxide. (Called methyl-
2-Hydroxy-1,1,3,3-Cyclopentanetetramethanol- oxymethyl-peroxid in Ger). CH 300 CH20H, mw
pentanitrate. 78.07, OB –82%; colorless oil of penetrating odor,
will not freeze in ice-salt mixture, bp’ 45°
02‘OcH% /cH20N02 at 17 mm; d 1.11 at 15°, refract index 1.398
/c\ at 15°; sol in water, ale, eth, benz & pet eth.
H2 C HCON02
Prepd by reacting methylhydroperoxide with
I ,CH20N02 formaldehyde in ether. Explodes on heating
H2C— above 50° & decomposes on long storage.
c\
CH20N02 Claimed to become impact sensitive on heating
(Ref 3)
mw 431.23, N 26.24%, OB to C02 –35.2; mp ~efs: 1) Beil 1, [641] 2) A: Rieche & F. Hitz;’
90.5 . Prepd by mixed acid nitration of 2-hydroxy- Ber 62B, 2458 (1929) & CA 24, 1079 (1930)
1,1,3 ,3-cyclopentanetetramethanol. It is a 3) See table under Hydroperoxides in this Vol
,., .,
powerful explosive only slightly weaker than
RDX: ballistic mortar 151%TNTVS161 %TNT 2-Hydroxy-3,5dinitrophenyl Azide or 2-Azido-
for RDX. It is slightly less impact & friction 4,6-dinitrophenol. N3
sensitive than RDX and has unsatisfactory
vacuum stability (12-1 5rrd at 10d in 12 hrs) A
-OH
(Ref 1)., Its lowest explosion temp is 200°
(Ref 2) 02 N- .-N02 ,
V
Refs: 1) D. C. Downing, CanJChem 30, 124
(1952) & CA 47, 8663 (1953) 2) H. Henkin . mw 225.12, N 31.1 l%; prepd from diazodi-’
& R. McGill, IEC 44, 1391 (1952) & CA 46, nitrophenol & Na Azide. Its alkali or alkaline
8858 (1952) earth metal salts are used with various admix-
tures, such as basic Pb “1’rinitroresorcinate, bari-
Hydroxydialkylamines, Nitrated Derivatives. um nitrate, Sb sulfide, Pb sulfocyanate &
Compounds of the general formula ground glass, for use as priming .compns to
initiate expls (Refs)
/R’ ; where RI is a nitroxyalkyl group Refs: 1) J.D. McNutt, USP 1906394 (1933) &
02N.N
\R CA 27, 3612 (1933); USP 1930653 (1934) &
2
and R2 is either a nitroxyalkyl or an alkyl group CA 28, 328 (1934); & USP 2005197 (1935) &
(alicyclic, cyclic or substituted) were proposed as CA 29, 5274 (1935) 2) A. H. Blatt ‘& F. C.
explosive, essentially non-volatile, plasticizers for Whitmore, OSRD 1085 (1942), p 54 3) Blatt,
NC used in prepn of double-base propellants OSRD 2014 (1944) (Under Azides) ,.
Typical examples of this type of nitramine ,,
 H 240

Hydroxydiphenylamine. See Anilinophenol Rej A.T. Blomquist & F.T. Fiedorek, USP
in Vol 1, p A433-R and additional entries below: 2485855,(1949), pp 6 & 14 & CA 44, 3516-17
(1950)
Hydroxy-tetranitro-diphenylamine (called 3,5,2’,4’-
Tetranitro-oxy-diphenylamin in Ger). Hydroxyethylcelluloses. Title of a doctorate
(O2 N)z Cc H3 NHC6 Hz (N02)2(OH), mw 365.22-Z thesis submitted to the University of Paris,
N 19.18%, yellow powder, mp 236°, almost insol in France, 9 June 1960, 89pp & 144 refs
all usual solvents. Prepd by condensation reaction Refi J. Quinchon, “Contribution 2 I’<tude des
of 4-chloro- 1,3-dinitro-4 aminophenol in alc hydroxyethylcelluloses,” MP 42, (1960)
containing NaAc. No explosive props mentioned
Refi 1) Beil 13,528 2) Not found in CA thru 1971 N-(2-Hydroxyethyl)-cyclohexylamine. Its nitrated
deriv N-(2-Nitroxyethy l)-cyclohexylnitramine
4-Hydroxy-3,5,2’,4’,6-Pentanitrodiphenylamine (Cyclohexyl-NENA),
(Also called 2,6-Dinitro-4-Picrylaminephenol in ,CH2–CH~
Cer). (Q N)3 C6 H2 NHC6 Hz (N02 )2 OH; mw 02 N0.CH2 .CH2 . N(N02 )-C< CH2 _cH2 CH2 ;
/
410.22, N 20.49%, OB to C02 -62.4%; ochre-yel
crystals (from HAc), rnp 248°; insol in water, S1 mw 233.22,. N 18.0270; is described in Vol 3,
sol in ale; sol in alkalis with formation of a deep- p C600-L
brown color. Prepd by heating picryl chloride,
isopicraminic acid & NaAc in aq ale. No explo- N-(2-Hydroxyethyl)-ethylamine. Its nitrated deriv
sive props are mentioned for it nor for the N-(2-Nitroxyethy l)-ethylnitramine (EtNENA),
tetranitro derivatives (Ref 2). The Na salt, of 02 NO. CH2. CH2.N(N02).C2H~; mw 179.14, N
the pentanitro derivative NaC12H50] I N6, red 23.46%; pale yel oil, frp 4-5.5°, d 1.32 at 25°,
platelets, explodes above 300°. The 3’-Hydroxy- RI 1.479 at 25°; prepd by addg ethylethanol-
4-methyl-pentanitro diphenylamine is not amine dropwise to a stjrred 9870 nitric acid soln
explosive (Ref 3) at 10° and adding the resulting rnixt to a soln
Refs: 1) Beil 13, (191) 2) Beil 13, 396, 528 of acetic anhydride & acctyl chloride at 35° (Ref)
&531 3) Beil 13, 412 Refi A.T. Blomquist & F.T. Fiedorek, USP
2485855 (1949), pp 5 & 11-12; USP 2678946
N-Hydroxyethenylamidooxime. See under (1954), pp 13 & 44
Ethenylamidooxime in Vol 6, p E185-L
N-(2-Hydroxyethyl)-gluconamide Hexanitrate.
Hydroxyethyl. See Ethanol and Derivatives in CG H5 (ON02)5 CONHCH2 CH2 ON02; mw 520.26,
...
VO1 6, p E154-L N 18.85%, OB to C02 -12.3%; prepd by nitric acid
nitration N-2-hydroxyethylgluconamide,
Hydroxyethylamine and Derivatives. See under C~Hc (OH)5 CONHCH2 CH2 OH. Claimed to be
Amino-ethanol and Derivatives in Vol 1, pp useful in blasting cap charges
‘4200-202 Ref W.F. Filbert, USP .2443903 (1948) &
CA 43, 1796 (1949)
B-Hydroxyethylaminobenzene or B-Hydroxy-
ethylaniline. See under 2-Anilinoethanol and N-(2-Hydroxyethyl)-glycolamide Dinitrate.
Derivatives in Vol 1, pp A424-31. This includes 02NOCH2CONHCH2CH20N02; mw 209.12, N
Pentryl ,(Trinit roanilinoethanol Nitrate) & various 20. 10%, OB -34.4%; prepd by nitric acid nitra-
halogen derivs of anilinoethanol tion of N-2-hydroxyethylgly colamide,
HOCH2 CONHCZ H5 OH. Claimed to be useful
N-(2-Hydroxyethy l)-butylamine. Its nitrated as a blasting cap charge
derjv N-(2-Nitroxyethy l)-butylnitramine (BuNENA), Rej W.F. Filbert, USP 2443903 (1948) & CA
02 N0.CH2 .CH2 .N(N02).Cq H9; mw 207.19, N 43, 1796 (1949)
20.28%; pale yel oil, frp -9.9°, RI 1.4750 at
20°, was prepd & described by Blomquist & Hydroxyethylglycolurethane, N-Nitro-Dinitrate.
Fiedorek (Ref) o
0N02CH2CH20CN(N02 )CH2CH20N02; mw
 H 241

284.14, N 19.72%, OB -22.4%; white trysts. Prepd nitrate added to effect nitrosation
by nitrating N-hydroxy-ethylglycolurethane with Refsj 1) Beil, not found 2) A.F. McKay & J.E.
98% nitric acid. No properties given Milks, JACS 72, 1619 (1950) & CA 44, 10661
Ref G. Desseigne, FrP 1094959 (1955) & CA (1950)
53, 11159 (1959) N-(B-Nitroxyethyl)-N-nitroso-N’-nitroguanidine or
l-(2-Nitroxyethyl)-l-nitroso-3-nitroguanidine.
02 N0.CH2 .CH2 .N(NO). C(:NH). NH.NOZ; mw
Hydroxyethylguanidine and Derivatives
222.13, N 37.84%, yel trysts (from 95% ale),
Hydroxyethylguanidine [called /3-Guanidino- mp 112.5° (dec); was prepd by nitrosation of
;thylalkohol or (2-Hydroxy-ithy l)-guanidin in
N-/J-Nitroxylethyl-N-nitroguanidine
Ger] ~. CH2.CHz.0H Refs: 1) Beil, not found 2) A.F. McKay & J.E.
C:NH Milks, JACS 72, 1619 (1950) & CA 44, 10661 ~
I$H2 (1950)
mw 103.13, N 40.75%; exists in the form of its
salts. May be considered ‘a; the parent compd N-(B-Nitroxyethyl)-N-nitro-N’-nitroguanidine or
of its nitrated derivs, although not used to 1-(2-Nitroxyethyl)-1,3-dinitroguanidine.
prep them 02 N0.CH~ .CH2 .N(N02).C(:NH). NH.N02 ;
Ref Beil, 4, [730] & {710} mw 238.13, N 35.30%; wh trysts (from MeOH),
mp 84.5 to 85 .3°; was prepd by addg /3-hydroxy-
N-(B-Hydroxyethyl)-N’-nitroguanidine or 1-(2- ethylnitroguanidine to a nitration mixt of 99 .8’%0
Hydroxyethyl)-3-nitroguanidine. nitric acid & acetic anhydride at 0° and after 30
H0.CH2CH2 .NH.C(:NH)NH. N02; mw 148.13, , reins pouring the mixt onto ice. This compd is
N 37.83%; wh trysts (from ale), mp 118° (decj; useful in proplnts (Ref 3)
was obtd when methylnitrosoguanidine was Refs: 1) Beil, not found 2) A.F. McKay & J~E.
added portionwise to a soln of ethanolamine in Milks, JACS 72, 1619 (1950) & CA 44, 10661
water cooled to 5-10° (1950) 3) A.F. McKay, USP 2538907 (1951)
Refs: 1) Beil, not found 2) A.F. McKay,& J.E. & CA 45, 4264 (1951); BritP 673709 (1952)
hfikS, JACS 72, 1617-18 (1950) & CA 44, , & CA 46; 9123 (1952)
..
10661 (1950)
1-Hydroxyethyl Hydroperoxide.
N-(B-Nitroxyethyl)-N’-nitroguanidine. or 1-(2-
CH3 CH(OH)OOH, or its higher homologs are
Nitroxyethyl)-3-nitro-guanidine.
not explosive. See Table under Hydroperoxides
OZNO. CHZ .CHZNH.C(:NH)NH. NOZ; mw 193.13, in this Vol
N 36.26%; trysts (from 95% ale), mp 161° ‘(dec),
explodes by impact. The compd was prepd by N-(B-Hydroxyethyl)-hydroxyaceternide. ‘
suspending ~-Hydroxyethylnitroguanidine in acetic HOCH2CONHCH2CH2 OH; mw 119.12, “
anhydride and adding dropwise 99% nitric acid crystals, mp 72.5-73.5°. May be prepd by “
at -5° for 10 reins. The compd explodes by treating methyl glycolate with monoethanolamine
impact (Ref 2)
,4$colorless oil was obtained when 2g of the
Refs: 1) Beil, not found 2) R.C. Elderfied, :
compound were dissolved in 10ml of white nitric
OSRD 907 (1942) 3) A.F. McKay & J.E. acid and then heated at 50-60° for one-half
Milks, JACS 72, 1618 (1950) & CA 44, 10661 hour and poured on ice. This oil was not further
(1950) investigated, but it might have been a liquid
N-(B-Hydroxyethyl)-N-nitroso-N’-nitroguanidine explosive, suitable as a plasticizer for NC etc
or 1-(2-Hydroxy-ethyl)-1-nitroso-3-nitroguanidine. Refs: 1) Beil, ‘not found 2) R. Adams & C.S.
H0.CH2CH2 .N(NO).C(:NH). NH. N02;mw 177. Marvel, OSRD No 86 (1941), pp 12 & 36-37
13, N 39.54%; yel crjsts (from MeOH), mp 3) CA not found thru 1971
111.5° (dec), unstable compd which decomposed
on ‘standing in the dark for 7 days; was obtd N-(B-Hydroxyethyl)-methylamine. Us nitrated
when /3-Hydroxyethylnitroguanidine was dissolved deriv N-(~-Nitroxyethy l)-methylnitramine (MeNE-
in 70% nitric acid, diluted with water & Na NA). 02 N0.CH2 .CH2 .N(N02).CH3 ; mw 165.11,
 H 242

N 25.45%, OB to C02 -43.6%; trysts, mp 38- Desseigne,also prepd in a similar manner

40°, d 1.53 at 25°; sol in acetic acid; S1sol in Hydroxypropyl-3-oxy-1,2-propanediol Trinitrate.
water; was prepd by nitrating the parent compd CH3CH(ONOZ)CH2 OCHZCH(ONO*)CHZ ONOi ,
with nitric acid. The product is practically non- and also claimed its use as an explosive and
hygroscopic, its expln temp is 360°, impact gelatinizing agent
value 90cm + (RDX = 48-50cm), power 1367Q Refs: 1) G. hsseign~ FrPat 1,127,647(1956)
TNT, and Vac Stab at 100° = 6.81 cc/5g/48 Hrs &CA 53, 16970 (1959) 2) G. Desseign< MP 39,
(Refs 1 & 2) , 181 (1957) &CA52, 21107 (1958)
Refs: 1) A.T. Blomquist, OSRD 4134 (1944), “
pp’30-44, 72 & 110-11 2) A.T. Blomquist & Hydroxyethylpicramide, or 2,4,6-Trinitrophenyl-
F.T. Fiedorek, USP 2485855 (1949) aminoethanol. ,See under Anilino-ethanol
and its Derivatives in Vol 1, p A425-L

N-(b-Hydroxyethyl)-N’- methyl-ethylenediamine. N-(B-Hydroxyethyl)-N’-phenyl-1,2-diaminoethane

Its nitrated, deriv N-(~-Nitroxyethyl) -N’-methyl- and Derivatives. See Anilinoethylaminoethanol

ethylenedinitramine. and Derivatives in Vol 1, p A431 -L
Oz N0.CH2CH2 .N(N02). CH2 .CH2 .N(NOZ ).CHa;
mw “253.,18, N, 22.64%; glistening trysts (from Hydroxyheptylperoxide. [CH ~(CH2) ~CH(OH)] ~0 ~;
50%, acetone), mp 88.5-90°; was prepd by mw 262.38
cleavage with 9870 nitric acid of the compd The commercial prod~ct of the Lucidol Division
iso-N 1,N4-dimethyl-triethylenetetranitramine, contains a minimum of 95% ’of peroxide; active
H3C. N(NOZ). CH2.CH2.N(N02).CH2 .CH2 .O.~: oxygen 5 .8’%0 (tin). It is a white fine powder;
N. CH2. CH2 .N(N02 )CH3, at 10° mp 60-65°
Ret A.T. Blomquist, OSRD 4134 0 It is insol in w and moderately sol in organic
(1944), pp 9 & 81 solvents or monomers. Unstable at ord;nary
room temp and should not be stored at above
a-Hydroxyethylmethylperoxide or Methylhydroxy- 70”F (in order to avoid loss of active oxygen)
ethylperoxide in
i (a-Oxyathyl-methyl-peroxyd and away from all sources of heat. lt should
Ger). CH3 CH(OH)OOCH3; mw 92.09, easily not be subjected to frictional heat or grinding.
flowing oil, fairly stable;. bp 29-31° at 22mm; It has been used as a room or low temp cata-
d 1.029 at 15°, RI 1.3930 at 15°. May be lyst for polymerization of polyester resins
prepd from methy~ydroperoxide, CH300H, and Ret Lucidol Division, Novadel-AgenS Corp,
acetaldehyde, CH3 CHO; cliff sol in water, Buffalo, NY, Organic Peroxides, Data Sheets No
miscible with alc and eth; easily sol in benz 18 (1948) and No 32 (1950)
Puffs off weakly on heating
Refs: 1) Beil, not found 2) A. Rieche & F. Hitz, 1-Hydroxy-1'-hydroperoxy-dicyclohexyl peroxide.
Ber 63, 2642 (1930) & CA 25, 911 (1931) See under Cyclohexanone Peroxide in Vol ~3,
p C598-R “‘,
N,N’-bis(2-Hydroxyethyl)-oxamide. Diethylol- See
oxamide and Derivatives in Vol 5, p D1 243-R 1-Hydroxy-5-hydroxymethyltetrazole and Deriv-
atives.
Hydroxyethyl-3-oxy-1,2-propanediol trinitrate or 1-Hydroxy-5-hydroxymethyltetrazole (called 1-
3(b-Hydroxyethoxy)-1,2-propanediol trinitrate. 0xy-5-hydroxymethyltetrazol in Ger).
0N02CH2CH20CH2 CH(ON02)CH20N02, mw N—N.OH
271.18, N 15.50%, OB -26.5%. Prepd by mixed acid ~_NC.CH,OH; mw 116.08, N 48.27%, OB
or straight nitric acid nitration of 3(@Hydroxy-
ethoxy)-1 ,2-propanediol (Ref 1) or nitrating -55.1 %. Prepd by treating l:hydroxytetrazol with
the reaction product of bpichlorohydrin & formaldehyde. It is a volatile material which is
glycol (Ref 2). It is a liquid which is less an explosive less powerful & brisant than PA
volatile than NC. Desseigne has claimed its use (Ref 2)
as an explosive and as a, gelatinizing agent Refs: 1) Bed 26 (109) 2) Blatt OSRD 2014
(1944)
 H 243

1-Hydroxy-5-nitroxymethyltetrazole. kcal/mole (Ref 7). Dissocn const for dil soln

N—N.OH 1.1 x 10+; AH subl 15.3 kcal/mole (Ref 9)
II J.c.cH,oNO,; mw 161.08, N 43.48%; It is an acute local irritant, and systemically
N—N it can cause methernoglobimenia (Ref 10)
OB -14.9%. Prepd by nitrating above compd. It Preparation
is less brisant and powerful than PA Since free NH2 OH is unstable it is usual to
Ref Blatt OSRD 2014(1944) prepare it in the form of the hydroxylammonium
salts, which resemble ammonium salts. A num-
6-Hydroxyindazole (called 6-Oxyindazol in Ger). ber of methods were proposed but only 5 offer
practicrd methods
1) Reduction of HN02 or its Salts. When a
-<N soln of NaN02 is reduced by NaHS03, sodium
H J3 -N’ hydroxylamine-N,N-disulfate —.— is formecd:
H NaN03 +NaHS03 +H2S04- N(S03 Na)2 OH+HZ O.
mw 134.13, N 20.89%; leaflets, mp 215–16°; Heating of the resulting soln produces hydroxyl-.
sol in dil acid or alkali, S1sol in water or eth. ammonium hydrogen sulfate:
Prepd by diazotizing 6-aminoindazole. When ni- N(S03 Na)2 OH+2H2 Q + (NH ~OH)HS04+Na 2S04
trated it forms: The crude hydroxylammonium salt may be
5,7-Dinitro-6-hydroxyindazole,
obtained from the soln by fractional crystal-
lization. Several modifications of the method
.:\ exist (Ref ,3)
02N
2) Reduction of Nitric Acid. Electrolytic
HQ /N reduction of HN03 in the presence of HC1
NOZH produces hydroxylammonia chloride:
HN03 +6 H+ HCl+6e + (NH3 OH)C1+2H2O
mw 224.13, N 25.00%; OB to C02 -78.5%, pale-yel Yield ab 80% (Ref 2)
leaflets (from glacial HAc); mp 232-33°; sol in 3) Hydrolysis of primary nitroparaffins. ,A
water. Puffs off above mp primary nitroparaffin gives on hydrolysis with a
Refs: 1) Beil 23, 377 2) Not found in CA i.hru 1971 strong acid, the corresponding fatty acid and the
hydroxylammonium salt of the acid. For in-
Hydroxymethylbenzene, Hydroxytoluene or stance: CH3 CHZN02 +H2 OtHCl + (NH3 C)H)C1+
Methylphenol. See Cresol and Derivatives in CH3 COOH. This reaction is used for producing
Vol 3, p C556-L hydroxylammonium salts industrially
Free NH2 OH may be liberated from any of
2-Hydroxymethyl-1,3-propanediol-2-aniline. See the above salts, by a base stronger than hydro-
Anilinotrimethylolmethane and Derivatives in xylamine itself, eg K, Na, hydroxides or
Vol 1, p A441. Its highly expl deriv, designated carbonates in aq or alc solns would liberate
as Heptryl is on pp A441 -R to A442-R the base (Ref 4)
4) In the prepn of crystalline NH2 OH it is ‘
1-Hydroxy-2-propanone. See Acetol and Deriva- impractical to use a water solvent since it is
tives, in Vol 1, p A33-R difficult to remove it. It is bette~ to use the
anhydrous alcoholate of the corresponding solvent
eg:
HYDROXYLAMINE AND DERIVATIVES NH2 OH” HCl+BuONa ‘n BuOH }NH20H+NaCl
Hydroxylamine, Oxammonium (HA), NH2 OH, +BuC)H. MeOH or EtOH and their alcoholates
mw 33.03, N 42.370, colorless, deliq low melt may also be used (Ref 5)
needles, mp 33°, bp 56.5° at 22mm, 110° a; 5) Similarly:
760mm (Ref 8), flp explodes at 265”F, d 1.23, NH20HoHC1+NH3 (Iiq) ~ NH2 OH+NI& Cl
for liq RI 1.440 at 23.5°, sol in cold w, alc The excess NH3 is evaporated and the HA is
& acet; v S1sol in eth, CM & benz; decomp in extracted with abs alc (Ref 6)
hot w. AH; - 25.5, for tryst, -21.7, for soln, Removal of HA from the solvent alc is
 1 :’

H 244

achieved by cooling (the HA crystallizes) substances such as KI,. KCN, KBr, NaNOs,
and/or addn of ether. Volatile ales may be re- Ba(N03 )Z, NaCl, KC1, NaOH, Ba(OH)2, NH3 (Ref 6)
moved by vac distillation Explosive & Combustion fiops. NH2 OH, like
Chemical Props NZH4, is a strong reducing agent. The base ignites
There is similarity in them props between , in a stream of chlorine and even reacts violently
NH2 OH and hydrazine. HA may be regarded as if air is blown through it
hydroxylation product of ammonia, thus If it is heated in air, it explodes between 60
representing the first member of such series, and 100°. It will explode upon contact with
which includes dihydroxyammonia and ortho an open flame. On oxidation HA liberates a con-
nitrous acid. It may be regarded as ammonolyzed siderable amount of energy and may therefore
HOOH (Hydrogen Peroxide). Hydroxylamine, be considered as a specialty fuel
like NH and NH NH , forms a large group of
l
A rough calculation of the overall heat of the
salts, but only strong acids form stable salts, of reaction according to: ~
which chlorides and sulfates are the best known. 2NH3 OH(gas) + 1?402 $“ 3HZ O(gas) + Nz
However, all of these salts decompose at about indicates that the heat of combustion of HA should
150° liberate about 59.2 kcal/mol
Like Hz 02 and Nz ~, solns of the free base, The combustion vel of a decomposition flame
NH2 OH, are susceptible to thermal and catalytic of a 7470 HA in nitric acid soln is 0.1 cm/sec.
decomposition. It is not improbable that auto- The flame is orange and ammonia is one of the
oxidation and catalytic decomp reactions are flame products (Ref 8)
catalyzed by traces of metallic ions, as has been Stability. Some authors claim that NHZ OH de-
noted in case of H2 Oz and of Nz ~. The stability composes merely on standing, but L. L. deBruyn
of HA is intermediate between hydrazine & hydro- (Ber 27, 967 (1894)) claimed that one sample
gen peroxide. It is less stable than Nz ~ and some- decomposed only very slightly after a period of
what more stable than H2 02. Hydroxylamine ii a highl~ several years. In the opinion of Audrieth et al
hydrogen bonded subst in both the solid and (Ref 6~ some of the ~rnpurities cause catalytic
liquid forms, but the vapor is a single molecule decomposition and removal of these “impurities
at low press (Ref 11). The latter studies give improves the stability of product. On standing
the bond strength of NH2 –OH as 61.3 kcal/mole NH2 OH presumably decomposes, either as
NH2 OH very seldom exhibits acidic properties. 3NHZOH + NH3 + N2 + 3H20, or 4NH20H +
It is claimed, however, that it forms unstable 2NH3+N20+3H2 O depending on conditions
hydroxylamites, NaONH2, Ca(ONH2 )2 (Ref 6). (Ref 6)
As a base NHZ OH resembles ammonia and other Analytical. A number of analytical procedures
amines. Although its basic ionization constant for detecting and determining of NH2 OH are
is considerably lower than that of NH3 and available (Ref 6). The best method is to add
Nz ~ it forms a series of ammonia-like inorg and an excess of some oxidizing agent such as
org salts. In general, these salts are more stable ferric ammonium sulfate to a soln of free
than the parent base. Therefore, hydroxylamine base or one of its salts, and then determine the
is usually prepd and shipped in the free form amt of oxidizing agent which has been reduced
of its salts by standard permanganate or eerie sulfate solns
NH2 OH also forms few double salts and An alternate method consists of titrating
coordination compds analogous to those formed by aq NH2 OH with a std acid using a methyl orange
ammonia. Some of these compds are very stable indicator
to heat Qualitatively, amounts” as low as 1 part/
Sohr of HA, especially acidic solns are strong 100,000, may be detected by treating aq NH20H
reducing agents. They will reduce FeC13, ammoni- with ammonium CUSOQ to get a red ppt of CU20
cal AgN03, CuSOq etc. In some instances, how-
ever, particularly in alkaline solns, HA is capable Uses: Besides its uses as a reducing agent and
of oxidizing such subs as chromous chloride & in org synth, HA is claimed as an ingredient in
CUOH several propellant formulations, in combination
Liquid anhydrous NH2 OH will dissolve many with AN & AP
 H 245

Refs: 1) Gmelin, Syst 23, 569-602 & Mellor 8, Refs: 1) Mellor 8 (1928)p 303 2) H. Fox, USP
279-304 2) Schock & Pritchett, JACS 38, 2970898 (1961) & CA 55, 1285 (1961) 3)
2042 (1916) 3) Clark, OrgSynt, 3, 61-4 (1923) Sax (1968) p 830
4) S.B. Lippincott & H.B. Hass, IEC, 31, 118-20
(1939) & CA 33, 2104 (1939) 5) C.D. Hurd, Hydroxylamine Perchlorate (HAP).
Inorg Synth I, 87 (1939) 6) L.F. Audrieth et NH20H. HC104, mw 133.50, N 10.50%; hygr
rd, “Compounds of High Nitrogen Content,” 1st trysts, mp 87.5-90°, decomp 120°, sol eth.
Quart Rept, Univ of Illinois, Jan 1951 7) F.D. AH~66.2 kcal/mole (Ref 3). Prepd by reacting
Rossini, NBSCirc 500, Washington, DC (1952) NH2 OH. HC1 or (NH2 OH)2. H2 S04 with BaCIOq.
8) N.W. Luft, Monatsh 94, 330 (1963) & CA Used to increase burning rate in propellants. Im-
58, 13414 (1963) 9) R.A. Black & J. Betts, pact sens 15cm with 2 kg falling wt
CanadJChem 43 (8) 2157 (1965) & CA 63, A solid propell formulation based on HAP has
9082 (1965) 10) Sax (1968) p 829 been patented (Ref 2). It contains about 80%
HAP (or LiCIOa .2NH2 OH or MgC104 .4NH2 OH)
Hydroxylamine Salts & Complexes and 20% epoxy binder
Most strong acids form acid salts with HA. The self deflagration of HAP & hydrazine
The following are fairly stable but some of nitroform was studied (Ref 4). It was found that
them are explosive: HAP exhibits a low pressure deflagration limit
Hydroxylamine acid sulfate. NH20H .H2SOQ; of 146 atm analogous to the 20 atm limit of AP.
mw 131.12, N 10.68%, white to brown trysts; v Combust temps were determined
hygrosc, mp indefinite, bp decomp; sol w, MeOH; Refs: 1) J. H. Robinson, ‘USP 2,768,874 (1956)
S1sol EtOH. Toxic and may explode on heating. & CA 51, 3146 (1957) 2) J. P. Flynn & E. J.
It is used as a reducing agent, photog developer Strayer, USP 3,305,413 (1967) & CA 66, 97092
& in synth of dyes, pharmaceuticals & rubber (1968) 3) M. F. Zimmer et al, JChemEngData
chems 13 (2) 212 (1968) & CA 69, 22651 (1968) 4j
Refi CondChemDict, 8th Edit (1971), p 460 E. T. McHale & G. Von Elbe, Combust Sci
Techn 2 (4) 227 (1971) & CA 74, 66209 (1971)
Hydroxylamine hydrochloride. NHz OH. HC1;
mw 69.50, N 20.16%; colorl, hygr trysts (mono- Hydroxylamine sulfate. (NH20H)#12 S04, mw
clinic), mp 152°, bp decomp, d 1.67; sol w, ale, 164.14, N 17.07%; colorl monoclinic trysts, mp
glyc; insol eth. It is an irritant. It is toxic 177°, bp decomp. Sol w, eth, S1sol alc (Ref 2).
(causes prolonged methemoglobinema [Ref 3] ) Prepd by hydrolysis of MeN02 with H2 SOQ.
and ,it may react violently when heated. It is This reaction yields HA in an anhydrous medium:
used in org synths, in photography & in CH3 N02 +H2 S04 =HOSO, CCH:NOH(I)
medicine (Ref 3) (I)+2H2 O=H,ZSOq+HCOOH+NH2 OH or H2 SOq+
Prepd by hydrolyzing MeNOz with HC1 ., C()+NH2 OH (Ref 1), FIydroxylamine sulfate is highly
(Ref 1); from aceto-oxime, water & Me*CO toxic. Its uses are similar to those for the acid
with product crystallized at 20° (Ref 2) sulfate
Refs: 1) G. Bourjol, MP 34, 63 (1952) & CA Refs: 1) G. Bourjoul, MP 34, 63 (1952) & CA
46, 9236 (1955) 2) F. Mikula et al, Chem 46, 9236 (1953) 2) CondChemDict (1971),
Prum (Czech) 17 (8) 415 (1967) & CA 67, 1971) p 460-L
92406 (1967) 3) K.A. Arnol’dova & N.N. Hydroxylamine complexes of some inorganic
Speanski, Gigiena Truda 7 (12) 38 (1963) & salts. The prepn & characterization of some
CA 60, 16358 (1964) 4) CondChemDict, 8th NH2 OH complexes of various inorg salts are
Edit (1971), p 460 described. (NH3 OH)CIOQ forms complexes with
Hydroxylamine nitrate. NH2 OH. HN03; mw both 1 and 2 moles of NH2 OH (see HAP) while
96.05, N 29.17%; white trysts, mp 48°, bp de- the nitrate forms only a single complex. These
comp at about 100°. Sol cold w, ale; decomp complexes are, in general, less hydroscopic than
in 70° water. Prepd by reacting NH2 OH. HC1 the salt itself
with AgNOs or (NH20H)2H2S04 with Ba(NOs )2 Rej R. H. Quacchia et al, IndEngChem, Prod
(Ref 1). It is claimed as a propell ingred in Res Develop, 8 (2), 197 (1969) & CA 71,
combination with AN, AP & a curable liq 35585 (1969)
binder (Ref 2)
 H 246

Hydroxylamine Derivatives. Many NHZ OH deriv- thru an alc soln of ethylicsoda-acetoacetate and.
atives may be obtained by substituting for the then reacting the acid to form the lead salt
NH2 or OH hydrogens. Replacement of the NH2 Its silver, calcium & ammonium salts are
hydrogens gives hydroxylamates, and N-hydroxyl- explosive
amines (also called (3-hydroxylamines) of various Refs: 1) Beil 4, 575 2) W. Traube, Ber 28,
degrees of substitution. Replacement of the OH 1791-3 (1895) & JCS 68i, 503 (1895)
hydrogens gives o-hydroxylamines (also called 2-( Hydroxylamino):l -butanoic Acid or a-H@wi-
a-hydroxylarnines) and hydroxykzmine-acids. In- aminobutyric (2-Hydioxylamino- butaniiure -
Acid.
organic and organic derivatives produced by both (1) in Ger). HO. NH. CH(C, H5).COOH is de-
types of hydrogen replacement are listed below: scribed in Beil 4, 543. It may be considered as
the parent compd of its nitroso-deriv described
NH2 Hydrogen Substitution below
Calcium Hydroxylamate. Ca(NHOH)2,
mw 104.13, 2-(Nitrosohydroxylamino)-1-butanoic Acid or a-
N 26.90%. HA reacts with Ca at 5° to form a Isonitraminobutyric (a- [Nitrosohydroxyl-
“Acid.
very explosive salt amino] -buttersaure or a-Isonitrarninobtitteri~ tire
Ref E. Ebler & E- Schott ,JPraktChem 78, 289 in Ger). HO. N(NO). CH(C2H5). COOH, mw 148.12,
(1908) &CA 3,754 (1909) N 18.91%. It is stable only in solns. May be ‘prepd
Sodium Hydroxylamate. NaNHOH, mw 54.0, N by passing NO gas through an alc soln of ethylic
26.0%. When an ether soln of NH2 OH is treated ethyl-acetoacetate to which some potassium
with metallic Na an extremely unstable explosive ethylate was added, followed by saponification.
compd is formed Evaporation of this soln yielded a gummy sub-
Ref L. F. Audrieth et al “Compounds of High stance which could not be crystallized (Refs 1
Nitrogen Content,” 1st Quart Rept, U of Illinois, & 2)
Jan 1951 Its lead salt, Cq H6 Nz 04Pb, is explosive (Ref 2)
Zinc Hydroxylamate. HA reacts with Zn at 5° to Refs: 1) Beil 4, 576 2) W. Traube, Ber 28,
give an explosive salt of indeterminate composition 1793 (1895) & JCS 68i, 502 (1895)
Refi E. Ebler & E. Schott, JPraktChem 78, 289 2-(Hydroxylamino)-3-butanone-1-ic Acid,
(no year) & CA 3, 754 (1908) Ethylester or a-(Hydroxylamino)-ethylacerate.
““Many N-hydroxylamine derivatives are known. CH3 CO. CH(NH. OH). COOC2H5 is not found in
They appear to be non-explosive, stable com- Beil 4, but its nitroso deriv (see below) is
pounds eg CH3 HNOH (Ref 1) or HOOCCHZ - described
NHOH (Ref 2) 2-(Nitrosohydroxylamino)-3-butanone-1-ic Acid,
Refs: 1) Bei.14, 534, [1952] & {1715} 2) ,Beil 4, Ethylester; a-(Nitrosohydroxylamino)-ethyl-
542 acetoacetate or a-lsonitraminoacetoacetic Acid,
However some of N-hydroxylamino-alkanoic Ethylester. {Ger names: Athylester der 2- [Nitro-
acids form nitroso compounds and some of the sohydroxylamino] -butanon-(3)-s51rre, &Oxo-a-
metal salts of such compounds are explosive [nitrosohydroxylamino] -propan-a-carbons~ure-
as shown below: ~thylester, a- [Nitrosohydroxylamino] -acetessigsYure-
Hydroxylaminoacetic Acid or 2-( Hydroxylamino)- ~thylester or a-lsonitramino-acetessigs~ure-
ethanoic Acid. (Hydroxylaminoessigsiiure or h’thylester } CH3. CO. CHIN(NO). OH] . COOC2 H5
Hydroxylaminoathansaure in Ger), Its disodiuni salt, Cb H8 Nz 05 Na2+H2 O is explo-
HO. NH. CH2. COOH is described in Beil 4, sive and was obtained when dry nitric oxide was
542. It is the parent compd of its nitroso passed into a 10 per cent alc soln of ethylic
deriv described below sodacetoacetate as described in Ref 2
Refs: 1) Beil 4, 577 2) W. Traube, Ber 27,
Nitrosohydroxylaminoacetic Acid, lsonitramino-
1507 (1894) & JCS 66i, 400 (1894)
acetic Acid or 2-( Nitrosohydroxylamino)-
ethanoic Acid. (Isonitraminoessig~dure in Ger),
2-(Hydroxylamino)-1-propanoic Acid or a-
HO. N(NO). CH2 .COOH, mw 120.07, N 23.33%.
Hydroxylaminopropionic HO .NH. CH(CH3 ).
Acid.
Needles (from ether + Iigroin), mp–decomp
COOH, is not found in Beil 4, but its nitroso
103-4°; stable only in solns. Prepd by passing NO
deriv (see below) is described
 H 247

2-(Nitrosohydroxylamino)-1-Propanoic Acid or oxidizes readily in air. Formed (in addn to

a-lsonitraminopropionic Acid {a-[Nitroso- other products, see above) by heating, in air,
hydroxylamino] -propions;ure or cx-lsonitra- 2,4,6,2’,4’,6’-Hexanitro 3,3’-dioxy-azobenzene
mino-propionsdure } H0.N(NO).CH(CH3 ). COOH; in a coned KC03 soln; is converted to the
mw 134.09, N 20.89%. It is stable only in solns tn”nitrophloroglucin in boiling w
May be prepd by warming with soda the crude Refi Beil 15 [27]
soln obtained by the action of nitric oxide on
ethylic methylacetoacetate, until the alcohol is 2,4,6- Trinitro-3-hydroxylamino toluene, N-[2,4,6-
driven oft the acid is then precipitated as the Tkinitro-3-methyl-ph enyl] hydroxylamine.
Lead Salt, PbC3~ Nz 04, which is explosive H3CC6 H(N02)3(NHOH); mw 258.15, N 21 .71%,
Refs: 1) Beil 4, 576 2) W. Traube, Ber 28, OB -62%; dark yellow crystals (from aq ale),
1793 (1895) & JCS 68, 503 (1895) mp 99° (decomp); sol in alkalis or aq ammonia.
Prepd by heating 2,4,6 -Trinitro-3-methoxy-
Aryl derivatives of N-hydroxylamine form azo toluene with an alc soln of hydroxylamine.
and nitro compounds which are unstable With coned nitric acid it forms 2,3,4,6-
towards heat but not explosive tetranitrotoluene
The 4,6-dinitro derivative has also been
Azo-Derivatives of N-phenylhydroxylamine prepared
tryst comps of the type Rgf Beil 15 [15]

Y{–~::N<–jNHOH OH Hydrogen Substitution

Hydroxylamine-o-Sulfonic acid, NH20S03 H; mw
113.10, N 12.40%; white, hygr, microcrystalline
are known where X is Cl or OH, & Y is N02 solid, decomp 210°. Stable if stored in moisture-
or NO. They decomp in the range of 210-230” free atmos. Prepd by: the room temp reaction of
The dinitro Cl deriv is prepd by reacting benzo- (NH, OH): H, SO. + 2H, so. .s0, = 2NH, oso, H +
quione- 1,4-monoxime with 5-chloro-2,4-dinitro- 3H2 SOq; by reacting a hydroxylamine salt with
phenylhydrazine, and 4,6-Dinitro-3-hy drazino- an excess of chlorosulfonic acid; by bubbling HN3
phenol to get the OH compd. Similarly, the thru fuming Hz SOQ at 60-80°
cyano deriv is prepd from the above oxime and NHz 0S03 H reacts with ammonia and amines
2-nitro-4-cyanophenylhydrazine to give, respectively, hydrazine and substd
Refi Beil 16, [260] hydrazines
Nitro-Denvatives of Aryl-N-hydroxylamine Refi H.J. Matsuguma & L. F. Audrieth,
InorgSynth 5, 122 (1957)
6-Nitro-2,4-Dihydroxylamino-ph loroglucinol
(called -phloroglucin in Ger). (HO), CS(NOZ)
o-Methylhydroxylamine, a-Methylhydroxylamine,
(NHOH),; mw 233.14, N 18.03%, OB -58.5%;
Methoxylamine. CH3 ONHZ; mw 47~06, N 29.77%,
yellowish needles, mp 166° (decomp) has
OB -153%; fluid liq, bp 49-50°; sol in w, alc &
similar props and same meth of prep as the di-
eth. Prepd by reaction of C6 H5 C(OC2 H5 ):
nitro derivative described below
NOCH3. &~ HC1; by heating the di-K salt of
o-methylhydroxy lamine-N,N-disulfonic acid in
2,4,6-Trihydroxylaminophloroglucinol.
dilute acid soln. Explodes at 300°. Atomic
(OH)3 C6(NHOH)3; alum colorl needles (from
constants and IR spectra have been measured
eth); sol in eth & dil alk solns. Very unstable.
(Ref 1)
Other props and method of prep same as above
It can be stabilized against explosion by
4,6-Dinitro-2-hydroxylamino:phloroglucinol shock (adiabatic compression by a piston) by
(called 4,6-Dinitro-2-hydroxylatino-pMorogluch adding 75 parts by weight of either EtOH,
in Ger). (HO)3C6(N02)2(NHOH); mw 247.12, MeOH, Nz F& or MeNHz (Ref 2)
N 17.01%, OB -42.3%; yel needles (from eth), Refs:ll) Beil 1, 288 (143) [275] & {1212} 2)
mp 146-148° (decomp); readily sol in hot w, S.A. Greene, USP 3117415 (1964) & CA 60,
org solns & dil nimeral acids. Alc or eth soln 9093 (1964)
Written by J. ROTH
 H 248

Hydroxymethyl alkanes. Compounds such as Its IR absorption spectrum has been studied
CH3 .C. (CHZ.0H)3 or C* H ~C(CHzOH)3, called (Ref 5)
also “polymethylolalkanes.” See under “Poly- Refs: 1) Beil not found 2) A. Rieche & R.
hydroxy Compounds” Meister, Ber 68, 1468-1473 (1935) & CA 29,
6877 (1935) 3) F. Walker, “Formaldehyde,”
Hydroxymethylbenzoic Acid. Reinhold, NY (1944), p 127 4) See Table in
5-Hydroxy, 2,4,6-Trinitro-3-methylbenzoic acid article on Hydroperoxides in this Vol 5) A.V.
(also called 5-Oxy-2,4,6-trinitro-m-toluic acid). Karyakin & V.A. Nikitin, IzvestAkadNauk,
HOCC(N02)S(CHS)COOH; mw 287.16, N 16.64%, SSSR, Ser Fiz 17, 636 (1953) & CA 48, 5652
OB to C02 -52.9%; trysts containing 1 mole H20, (1954)
starts to melt (with decomp) between 170 &
180°, puffs off above 180°. Prepd by heating Hydroxymethylnitramines. See under Hydroxy -
5-hydroxy-3-methyl benzoic acid with 1.38 and Amino-methyl- nitramines
g/cc nitric acid
Refi Beil 10, 227 & (98)
3-Hydroxy-6-nitro-2-phenylindazole. H
– C: N”C6H5
2,2-Bishydroxymethylbutanol (1) trinitrate. 02
C2H5C(CHZON02)3 ; mw 269.17, N 15.61%, OB OH
to C02 trysts (from acetone), mp 51.2°.
-50.5%; 0
Prepd by mixed acid rritration of 2,2-Bis- mw 242.23, N 11 .57%; crysts,l mp >260°. Prepd
hydroxymethylbutanol (1). It was used in by refluxing 2,4-Dinitrobenzy lidene aniline,
explosive compositions by the Dupont Co (02 N)zC, H3CH:NPh, with Na-carbonate in EtOH
Ref Beil 1, {2350} 2) Not found in CA and then treating with HAc. The Na salt of this
1957-1971 product explodes on heating
Ref S. Secareanu & I. Lupas, Bull soc chim (5) 1,
N-Hydroxymethylethylenedinitramine or N- 373 (1934) & CA 28, 5445 (1934)
[(Hydroxymethyl)-N,N’-dinitro] ethylenediamine.
02 N. HN.CH2 .CH2 .N(N02)CH2 OH; mw 1-Hydroxy-2-propanone. See Acetol in Vol 1 of
196.13, N 31.1%, OB -40.7%; prisms, mp 127- Encycl, p A33-R
130° (decomp on prolonged heating in water
bath) Hydroxypropylamine and N-(2-Nitroxypropyl)-
May be prepd by adding 40% formaldehyde nitrarnine, as lso-Me-N EN A, are
designated
to ethylenedinitramine in boiling water described under ,%-ninopropanols and Derivatives
Ref: F. Chaprndn et al, JCS 1949, 1635-36 & in Vol 1, p A253
CA 44, 1411 (1950)
a-Hydroxypropylethylperoxide (a-Oxypropyl-
Hydroxymethylhydroperoxide, Methvlolhydro- athyl-peroxyd- in Ger). Cz H~ CH(OH)OOC2 H~;
peroxide or Methylhydroperoxide. (Called mw 120.15, OB -173Yo; non-viscous oil; d 0.974
Oxymethylperoxyd or Mono-oxymethyl- at 21°; bp 50–52° at 50mm; RI 1.4021 at
peroxyd- in Ger). HOCHZ 00H; mw 64.01; 21.4°. May be prepd by treating propionic
Oil of medium consistency; fairly stable in aldehyde with ethylhydroperoxide, Cz H5 OOH.
storage;: RI 1.4205 at 16°. May be prepd by Explodes on heating
treating anhydrous formaldehyde in dry ether Refs: 1) Beil, not found 2) A. Rieche & F. Hitz,
with anhydrous H2 02; Ber 63,2648 (1930); CA ref not found
CH2 O + Hz 02 = HOCH200H
Easily sol in w, ale, eth, acetone & dioxane; S1sol Hydroxypropyl-3-oxy-1,2-propanedioltrinitrate.
in chlf & petroleum ether; insol in benz See under Hydroxyethyl-3-oxy-1,2-propanediol-
It is an explosive which is not sensitive to trinitrate in this Vol
friction but explodes with extreme violence
when heated in a flame. Its higher homologs
are not explosive (Ref 4)
 H 249

2-Hydroxypyridine, 3,5-Dinitro (Called 3,5- mw 145.15, N 9.65%; monoclinic ndls, mp 201°,

Dinitro-oxy-pyridin in Ger). difficult to stiblime; sol in warm water & ale;
02N N02 S1sol in eth or benz. Prepd by heating 2-
n formaminoacetophenone in aq NaOH
Refi Beil 21, 83
8-Hydroxyquinoline or 8-Quinolinol, oxyquinoline
mw 185.10, N 22.70Y0, OB -56.2!ZO; yellow ndls or Oxine (Called 8-Oxy-chinolin or Chinophenol
(from eth), mp 133°, sol in benz, alc or warm in Ger).
watter. Prepd by mixed acid nitration of 2-
hydroxy-pyridine. Explodes weakly on heating
above mp. Its alkali-salts are very explosive
The 3,S Dinitro-4-hydroxy-pyridine, mp
325°, on the other hand, or its alkali salts are
not explosive mw 145.15, N 9.65%; prisms (from ale), mp 75–76°,
Refi Beil 21, 48 & [33 & 35] ‘ bp 267°, sublimes readily. Prepd by heating acidi-
fied 2-Amino-phenol with 2-Nitrophenol, glycerin
Hydroxypyruvic Acid (Oxypyruvic Acid). & coned sulfuric acid
C3m Oq; mw 104.06. One of the products of Refi Beil 21, 91
the alkaline saponification of NC and nitro-
The mononitro derivatives of the 2-hydroxy
oxycellulose (Ref 1). Berl and Smith (Ref 3)
& 8-hydroxy quinolines are stable (Beil 21, 99-
obtained it, calling it oxypyruvic acid, by
100). The di & tri-nitro derivatives are less stable
the alkaline hydrolysis, not only of NC, but also
but not really explosive. These are described
of nitrates of glucose and levulose
below
This sustance may be present as an impurity
in commercial NC 5,7 Dinitro-2-hydroxyquinoline;

m
Refs: 1) W. Will, Ber, 24, 400 & 3831 (1891) o~
2) Marshall, 1, (1917), 192 3) E. Berl & W.
Smith, JSCI, 27, 534 (1908)
N02 OH

HYDROXYQUINOLINE and DERIVATIVES mw 235.15, N 17.87%, OB -104.2%; golden-yel

Many hydroxyquinoline isomers are known. leaflets, mp 267” (with decomposition); insol
Only the 2-hydroxy or 8-hydroxy quinolines in most solvents. Prepd by nitrating 2-hydroxy-
appear to have nitro derivatives that are near quinoline with cone nitric acid
explosive Refi Beil 21, 100, (220) & [58]
2-Hydroxyquinoline or Quinolone (Called 2- 3, 6-Dinitro-4-hydroxyquinoline.
Oxy-chinolin in Ger). nu11

QT
02 N N02
OH
m N
,N”
mw 145.15, N 9.65%; prisms (from ale), mp
199–200°, v d sol in w; sol in ale. Prepd by mw 235.15, N 17.87%, OB -104.2%; mp 352–4°
heating 2-Acetaminobenzaldehyde with NaOH (decomp). Prepd by mixed acid nitration of
in aq alcohol 4-hydroxyquinoline
Refi Beil 21, 77 Refs: 1) J.C.E. Simpson,& P.H. Wright, JChem
SOC 1948, 2023 & CA 43, 3002 (1949) 2)
4-Hydroxyquinoline (Called 4-Oxy-chinolin in
S.P. Findlay & L.F. Small, JACS 72, 3247
Ger). OH
(1950) & CA 44, 10722 (1950)

m N
 H 250

5, 7-Dinitro-8-hydroxyquinoline, strong H2 SOq & HN03, soln with excess of

KN03 & long boiling. On cooling, the salt
m crystallizes out in fine yellow needles. Dinitro-
3,5-dihydroxyquinone diazide is prepd in the
same way from mono- or di-nitroaminophloro-
glucinol
mw 235.15, N 17.8770, OB - 104.2%; yel!ow trysts
Rej E. von Herz, BritP 207563 (1922) & CA
(from ale), mp 276° (Ref 1), mp 276-79° (from
18, 1573 (1924)
ethyleneglycol) with decomposition (Ref 3), mp
320° (decomp) (Ref 2). Prepd by coned nitric m-Hydroxytetryl. Same as 2,4,6-Trinitro-3-
acid nitration of 8-hydroxyquinoline methylnitraminophenol described under,
Refs: 1) J.W. Airan & D.S. Wagle, JUnivBombay Methylaminophenol and Derivatives
23, Part 3, Sec A (36), 29 (1954) & CA 49,
10273 (1955) 2) S. Carboni, GazzChimItal 85, a-Hydroxytoluene. See Benzyl Alcohol in Vol
1194 (1955) & CA 50, 9403 (1956) 3) T. Nogradi 2 of Encycl, p B91-L
et al, ActaChimAcadSciHung 6, 287 (1955) &
CA 51, 5078 (1957) 2-Hydroxytoluene. See o-Cresol in Vol 3 of
3,5,8 Trinitro-2-hydroxyquinoline, Encycl, p C556-L

02NmN02 3-Hydroxytoluene. See m-Cresol in Vol 3 of

<.,AN> OH Encycl, p C556-L
N02
4-Hydroxytoluene. See p-Cresol in Vol 3 of I
mw 280.15, N 20.00!ZO,OB -76.8Yo; bright yellow Encycl, p C556-L
needles (from xylene), mp 182° (decomp).
Prepd by coned nitric acid nitration of 2- Hydroxy-tetrazole. See Tetrazolol and Derivatives.
hydroxyquinoline These include:
Rej BeiI 21, (220) l-Hydroxytetrazole
3,6,8 Trinitro-4-hydroxyquinoline or 3,6,8-Tri- l-Hydroxy-5-azidotetrazole
nitro-4quinolinol. 5-Hydroxytetrazole
Hydroxytetrazoly lmethanol
02NmN02 Hydroxytetrazoly lmethanol Nitrate

Hydroxy-triazole Derivatives. See Triazole

mw 280.15, N 20.00%, OB -76.8%; yel prisms, Derivatives. These include:
mp 296° with decomposition. Prepd by mixed 3-Hydroxyasym-tnazole
acid nitration of 3-nitro-4-hydroxy quinoline Hydroxybenzotriazole, Chloro Derivatives
(Ref 1); or reaction of AcON02 with quinoline l-Hydroxy-4-benzoyl-5-methyl-sym-triazole
N-oxide in AC20 (Ref 2) 1-Hydroxy+,5dicarboxy lic acid-sym-tnazole
Refs: 1) G. Bendz et al, JChemSoc 1950, 1130 [2~Hydroxynaphthyl] -l~azo-3-[5-azido-asym-
& CA 44, 1072 (1950) 2) E. Ochiai & C. tnazole]
Kaneko, PharmBull (Tokyo) 5, 56 (1957) & 4-Hydroxymethyl-5-hydroxy-sym-benzo triazole
CA 52, 1165 (1958) 5-Hydroxy-l-(p-n itrophenyl)-3-carbonyl azide-
asym-triazole
Hydroxyquinone Diazides, Dinitro Derivatives of. l-Hydroxy-5-phenyl-tetrazole
Percussion caps or detonators are loaded with l-Hydroxy-sym-triazolopyrimidine
one or more of the ortho- or para-nitrated
quinone diazides of the polymeric phenols or Hygiene-Industrial, in War Plants. The reader is
their metallic salts. The K salt of dinitro-m- referred to the following lectures & reviews:
hydroxyquinone diazide is obtained from “Industrial Hygiene at work in the national
nitraminoresorcinol by treatment of the hot defense program” (Ref 1); “Mobilization of
 H 25 1

Industrial hygiene for national defense” (Ref 2); designed to determine the relative hygro-
“Industrial hygiene at work in defense industries” scopicity of various substances
(Ref 3); “Industrial hygiene support in a missile Some of these tests applicable to explosives
program” (Ref 4) and propellants are as follows:
Rejk:l) A lecture by J.J. Blootileld, Ann Intern 1) Desiccator test.
Med Phys 15, 165 (1941 )& CA 36,5915 (1942) a) Using an analytical balance, weigh a large
(no summary) 2) Lecture by W.J. McConnell, flat weighing dish provided with a glass stopper
JAmPubl Health 32, 9 (1942) & CA 36, 1693
(w, )
(1942) (no summary) 3) W.A. Cook, Metal b) Weigh separately in a scoop, on a rough
Finishing 40, 19 (1942) & CA 36, 2039 (1942) balance, 5- 10g of a‘ test sample (of known
(no summary) 4) A review by C.B. Truman, moisture content) and introduce it into the
Ann Ind Hyg Assoc J 25 (6), 607 (1964) & weighing dish. Stopper and reweigh (Wz )
CA 63, 8952 (1965) c) Remove the stopper and place the dish
in a desiccator containing a saturated solution
Hygrometric Tests: Tests designed to determine
of potassium” riitrate containing a few crystals
hygroscopicity (see under Hygroscopicity Tests) d) After leaving it in the desiccator for 24
or 48 hours, reweigh the dish (W3 )
Hygroscopicity. Hygroscopicity is the property
possessedby some substances of readily absorb- % Moisture absorbed= ‘3 - ‘2 x 100
ing atmospheric moisture. Some explosives, as W2 - WI
Note: Instead of using the potassium nitrate
well as substances serving as ingredients of ex-
plosive mixtures, are hydroscopic. Most nitrated solution, Wilson (Ref 1) recommends the use of
organic compounds per se are only slightly aqueous solutions of sulfuric acid. The following
hydroscopic, but the materials added as oxidizers, table gives the strength of Hz S04 required to
such as NaN03, NHq N03 etc, or as explosion give different relative humidities (RH) at various
temperatures suppressors, such as NaCl etc, are temperatures
very hydroscopic
‘% Sulfuric Acid Required
Hygroscopicity is a property which is very
undesirable in explosives, because moisture %RH 0° 25° 50° 75°c
lowers their power, brisance and sensitivity. 10 63.1 64.8 66.6 68.3
Moisture also lowers” the ballistic potential 25 54.3 55.9 57.5 59.0
of propellants. For this reason, it is advisable to 35 49.4 50.9 52.5 54.0
keep explosive mixtures as non-hydroscopic as 50 42.1 43.4 44.8 46.2
possible. This may be done either by excluding 65 34.8 36.0 37.1 38.3
hydroscopic ingredients or by coating these 75 29.4 30.4 31.4 32.5
ingredients with substances such as vaselin, 90 17.8 18.5 19.2 20.0
parraffin, wax, oils, rosin etc. Nitrocellulose is A chart giving a detailed relation between relative
made non-hydroscopic by gelatinization with vapor pressures, ‘ZOH2S04 and density of solutions
solvents. Hydroscopic dynamites are protected is given on p 328 of Ref 1
from atmospheric moisture by enclosing them 2] British Hygroscopicity Test for Black Powder.
in paraffin coated paper cartridges Put about 65g of powder (of known moisture
content) into a tared small tray with a bottom
Hygroscopicity Tests. Hygroscopicity is the of fine gauze and reweigh. Place it inside a box
affinity of a substance for water vapor. It is a over a tray containing a saturated solution of
complex phenomenon which is controlled by KN03. Allow it to remain there either 24 hours
the rate of diffusion of water across the vapor- for small grain powders, or for 48 hours for
liquid interface. This rate depends on tempera- large grain powders. Reweigh the tray and de-
ture, surface area, liquid depth, and liquid and termine the percentage of weight gain. Add to
vapor film coefficients. Inasmuch as it is im- this the percentage of moisture originally pres-
practical to measure the effect of all these ent to obtain the hygroscopicity of the powder
variables, simplified empirical tests have been (Ref 2)
3) Hygroscopicity Test at 15” in a moisture- tube containing the sample
saturated atmosphere. A sample of 10- 10Og of c) Weigh the tube containing the sample every
dried material is placed in a constant temperature few hours until constant weight is reached (W3)
room at 15° saturated with moisture. The sample d) Disconnect the tube with the sample and
is reweighed periodically until constant weight pass a stream of warm air (50 to 125°) through
is attained (Ref 4) it. This air stream is predried by passing it thru
4) US Armed Forces Test at 30° and 90% RH a U-tube containing Pz 05, until constant weight
a) Transfer a sample of about 10Og to a in the sample tube is reached (Wq)
tared (W1) wide glass weighing dish with a The ‘%. “equilibrium moisture content” of the
ground glass cover. Weigh tare & sample on an sample at the temperature and humidity of the
analytical balance (W2 ) test, and calculated on the dry weight of the
b) Remove the cover and place the dish in sample. is equal to: W3 - W4, where (Wl ) is
a humidor containing 1 liter of a sulfuric- W4 - WI
water mixture (18.6 * 0.5% Hz S04 ), which will the weight of the empty tube, (W3) the weight
maintain a relative humidity of 90 t 0.25’% at of the tube plus humid sample and (W4) the
30°. The humidor shall have a total capacity of weight of tube plus dry sample
about 10 liters and should be capable of being In order to make certain that equilibrium
sealed hermetically has been reached in any given case, it is always
c) Place the humidor in an oven maintained desirable to approach it from both the dry and
at 30 i 2° and leave it there for 3 days the moist sides. The simplest and quickest way
d) On the fourth day, remove the dish, to accomplish this with a single sample is to
stopper it and weigh (W3 ) pass dry air through the sample at the start and
e) Repeat the weighings every day thereafter then determine the equilibrium weights at 10,
until the sample ceases to gain weight, indi- 25, 50, 75 and 90% humidity. After this, satu-
cating that the powder has reached equilibrium rated air (100% humidity, obtained by bubbling
with 90% RH (Wn) air through water) is passed for a short time
Wn - W2 thru the sample and the same points redeter-
% Gain = x 100 = YoG, where mined in the reverse order. Finally, dry hot air
W2 - WI
Wz - W1 is usually 100g is passed thru in order to obtain the dry weight
This figure has to be added to the total Alternate means of controlling humidity by
moisture content (YoM) as determined on an- using saturated solutions of salts have been
proposed (Ref 7). For instance; at 30° a satu-
other sample of 100-200g and the sum gives the
rated solution of KN03 gives about 92% RH;
% hygroscopicity (%H) = %G + %M (Ref 3)
Total moisture content is determined on a KC1 = 84.5%; NaCl = 75.5%; Ca(N03)2 .4H20 =
separate 100 to 200g sample by distilling it in about 50$10etc
a 500rnl flask with 200ml of dry CCLI 6) French test (LeRoux)
5) HumidiW Equilibrium Method (Ref 1) Fifty grams of a previously dried explosive
a) Set up an apparatus consisting of 3 large sample is placed in a closed container above
bubbler bottles, containing aqueous solutions of 2’10 B( sulfuric acid. The % moisture pick-up’
Hz S04 of the desired humidity at the tempera- of the explosive is determined daily and plotted
ture of the test connected to a wide tube on a chart (Ref, 9)
containing glass wool or cotton and to a tared In addition to the general tests listed above
(w, ) straight or U-tube containing 20-60g of a number of studies & tests for specific ingre-
loose powder without any cotton or glass wool. dients have’ been published. These data for
The weight of the tube with the sample is propellants, NC and for ammonium nitrate (AN)
designated as Wz and both weighings should are summarized below:
be done on an analytical balance The hygroscopicity of a propellant is detd
b) Pass a slow current of compressed air (50 rapidly in an apparatus consisting of 2 identical
to 500cc per rnin, using the higher rates at gas washing bottles provided with fritted glass
lower temperatures) through the bubbler bottles plates near the bottom. The outlets at the /
and then through the glass wool tube into the bottom are connected through a diaphragm pump
 H 253

having a capacity of 400 l/hr. The top outlets the calcium carbonate content if the latter is
are connected to complete the path for air circu- similar in grain size to the AN. Kaolin can be
lation. In one flask is placed 50g of the propel, used almost as effectively as calcium carbonate
lant in the form of shavings O.lmm thick. In the (Ref 14)
other is a soln of CaC12 of such concn that the AN starts to pick up moisture at 55% RH.
vapor pressure of water over it at 20° is 0.75 of With the addition of 1.12% Pz 05 or 1.73%
that of pure water. The entire apparatus is Ca(N03)2 these humidities decrease to 45 &
immersed in a thermostat at 20°. The moist air 33% RH respectively. AN begins to dissolve at
is circulated until equil is attained, which requires 63-67% RH (Ref 13)
‘1% hrs, as measured by increase in wt of the Effect of surface-active agents & mineral
sample. The method may be used for materials additions on the hydroscopic nature & caking
other than propellants (Ref 15) tendency of ammonium nitrate was examined
Various attempts have been made to relate in the following lab experiments in order to
the hygroscopicity of NC to its nitrogen con- improve the storage properties of AN: (a) AN
tent. For uncolloided NC at 30 to 70% RH was crystal from satd solns contg O-1.0% of
the % moisture cl 4.6-%N. Thus for “pyro cationic, anionic or nonionic surfactants; (b)
cotton” (12.6’%oN)talc YOmoist = obs moist = granules of AN (0.5-1 .Omm) were contacted
2% & for guncotton talc moist = 1.2 ~ obs with a satd NW N03 soln contg varying amts
moist = 1.370 (Ref 6). For colloided NC the of surfactants; (c) granules of NHON03 were
above formula has been modified to YO moist = wetted by mineral oil, excess of oil removed,
14.6-%N-O.4, but the talc moistures based on & the granules coated with talc or clay. The
this modification do not always agree with effect of the concn of several surfactants on
experiment (Ref 6) caking tendency & hygroscopicity, under
The linear (inverse) relation between NC varying pressures & relative humidity, was
moisture content and NC nitrogen content was detd & the results related to those obtained
also noted in Ref 5 with untreated AN. According to process (a),
Urbaiiski (Ref 12) gives the moisture con- caking tendency decreased 2.5 fold & hygro-
tents of 13%N & 12.5%N as 1 to 1.5% & 1.5 scopicit y decreased 2.0 fold; according to (b),
to 2% respectively these decreases were 4 & 5 times respectively
Tavernier (Ref 10) discusses the effects of when 0.170 of Dispergator NF or 0.2% of
hygroscopicity (and several other factors) on the carboxymethylcellulose was used; and according
ballistic props of colloided double base propel- to (c) these decreases were 4 & 1.5 times
lants and incompletely gelatinized oxidizer- respectively (Ref 17)
containing propellants. The studies of Ficheroulle To extend the shelf life of explosives contg
& Kovache (Ref 8) on effects of hygroscopicity NHq N03, it is important to minimize its hygro-
(and several other factors) on the potential use- scopicity. Sampleswere tested for hygroscopicity
fulness of substances as priming explosives should at relative humidity levels of 60, 70, 80 & 90%
also be mentioned, although NC is not one of & between 28-30°. Most of the samples were
the substances examined coated; some were manufd by a process pro-
Because of its importance in commercial ex- ducing prills; clay material was added in 2 cases.
plosives, and because it is highly hydroscopic, the The results indicated that the NW N03 which
hygroscopicit y of AN has been studied intensively: contained the least amt of impurities or addi-
Equilibrium moistures (hydroscopic points) in tives was also the least hydroscopic (Ref 18)
AN determined by static or flow methods do Laboratory investigations of Igdanit (ammo-
not agree. In general, flow methods are recom- nium nitrate–fuel- oil explosives). Flaked &
mended. To increase the rate of moisture ex- prilled Igdanit, differing in particle-size distri-
change (at a given RH) the temp of system bution, d, & amt & kind of coating agent or
should be raised (Ref 11) additive were obtained from 8 sources. Hygro-
The hygroscopicity of AN can be decreased scopicities, relative rates of drying & ease of
by the addition of calcium carbonate. The fracture of the dried particles after wetting
reduction in hygroscopicity is proportional to were detd (Ref 16)
 H 254

Refs: 1) R.E. Wilson, IEC 13, 326 (1921) 2) impingement angle, mixture ratio and temp
Marshall 2, 417 3) US Spec JAN-P-270, p 4 (Ref 1). For combinations “of HN03 with
4) H. Kast & L. Metz, Chemische Untersuchung aniline, furfuryl ale, and mixts of aniline and
der Spreng- und Ziindstoffe, Braunschweig (1931), furfuryl ale, ignition lags ranged from 10 to
p 274 5) P, dePauw, SS 34, 69 (1939) & CA 400 msec depending upon temp, acid compn,
33, 4424 (1939) 6) Ordn Proof Manual 7-26 fuel compn and metallic additives (Ref 2).
(1945) p 28 7) F.E. OBrien, “The Control of Wetting agents significantly decrease ignition
Humidity by Saturated Salt Solutions,” JSci lag of HN03 combinations with furfuryl
Instruments 73-76 (1948) 8) H. Ficheroulle & alcohol dicyclopentadiene. Oleamide, trietha-
A. Kovache, MP 31, 7 (1949) & CA 46, 11686 nolamine oleate, glyceryl oleate, sodium sul-
(1952) 9) A. tiROUX, MP 32, 129 (1950) 10) foricinate and alkyl-aryl sodium sulfate were
P. Tavernier, MP 36, 231 (1954) & CA 50, 2979 most effective (Ref 3). Ignitability and delay
(1956) 11) V.V. Boldyrev et al, Trudy Tomsk times were also clearly related to chemical
Gosudarst Univ, Ser Khim 145, 155 (1954) & structure of the fuel. Comparisons have been
CA 54, 9463 (1960) 12) “T. Urbafiski, Chemia made between hyperbolic characteristics of
i Technologia Materia16w Wybuchowych, Warsaw, primary, secondary, and tertiary amines as
(1955), v 3, p 361 13) N.I. Krylova et al, well as the effeit of substituent groups such
Izvest Akad Nauk Uzbek SSR No 10, 29 (1955) as methyl, hydroxy, and phenyl on the a- and
& CA 53, 2547 (1959) 14) K. Kuleliev & D. P-carbon atoms of various arnines with white
Shishkov, Khim i tnd (Sofia) 29 (l), 16 (1957) fuming nitric acid oxidizer (Ref 4). With
& CA 52, 15849 (1958) 15) M. Parpaillon, MP highly reactive combinations such as Nz ~ –
40, 247 (1958) & CA 55, 18112 (1961) 16) Hz 02, Nz ~ and Nz ~ –NH3 mixtures with
B.D. Rossi & V.A. Usachev, Vzroyvchatye RFNA (red fuming nitric acid) and WFNA
Veshchestra Prosteishego Sostara, Inst Corn Dela, (white fuming nitric acid) the mixing time is
Akad Nauk SSSR, Sb Statei i Materialov, 20, the rate-controlling step in the process and
(1960) & CA 57, 2484 (1962) 17) V.L. ignition delays in the order of a millisecond
Maksimov et al, Tr Mosk Khim Technol Inst, are observed (“Ref 5). The National Advisory
54, 96 (1967) & CA 68, 31620 (1968) 18) Committee for Aeronautics extensively studied
J. Harris (Picatinny), US Clearinghouse Fed Sci ignition delays of nitric acid oxidants. Their
Tech Inform, AD 1970, No 869315 & CA 75, noteworthy conclusions are summarized in
65761 (1971) Ref 6
The ignition delay phenomena have been
Hypercompression of Explosives. See Vol 3, p extensively studied for hyperbolic combinations I
J
D20-R under Dead-Pressed Explosives of Nz Od with various fuels because of the
almost exclusive use of this oxidizer in the
Hypergolic Propellants. Hyperbolic propellant upper stages of the US military and civilian
I
systems are those which ignite spontaneously space program. Propellant combinations used
on mixing. Those which do not are called non- in specific launch vehicles are given in Ref
hyperbolic. Of course, the real difference be- 34. A summary of a literature and industry
tween hyperbolic and non-hyperbolic systems survey of the hyperbolic ignition spike phenom- /
lies in the rates of chemical reactions at the ena is given in Ref 35. The physics of spray
mixing temperatures. Hyperbolic propellants formation, chemistry of combustion, physico-
react quickly enough at ambient temperatures chemistry, gas dynamics, and transport are
to liberate heat so that they therefore ignite dealt with. Ignition limits have been detd for
spontaneously. Ignition delay measurements various combinations of Nz Oq and Nz ~ under
normally are indicative of rates of reaction and press and temp conditions of space chambers
so much work has been done in this area of varying sizes. Vapor phase and condensed
Ignition Delay. Ignition delays in the range phases were investigated (Ref 36). The rea-
of 39-80 msec were measured by the impinge- ctivity of Nz Oq with Aerozine–50 (50/50
ment method for 80~0 Hz Oz and mixts of hydrazine/unsym dimethylhydrazine) was detd
Nz ~, CH3 OH and Hz O. Delay varied with at pressures from 10-s to 1 atm. At pressures
 H 255

below 0.01 atm explosions and detonations (Ref 8, 10, 14, 17); ethylenediamine (Ref 8);
occurred under certain specified conditions diethylenetriarnine (Ref 8); UDMH (Ref 8, 14);
(Ref 37). Various physical pehnomena UDMH 50% & N2~ 50% (Ref 8, 10,14, 18)
influencing ignition delay of HN03 and Nz (lQ Oxygen with: Nz m (Ref 10); UDMH 50%
oxidizers and rnixts include diameter of injec- & Nz ~ 50% (Ref 10); pentaborane (Ref 10,
tion tube, stream velocity, mixing ratio, 20); triethyhduminum (Ref 21); t rimethyl-
chamber pressure, fuel & oxidizer temps, water alurninum (Ref 22); boranes & derivatives (Ref
content of fuel & oxidizer. Fuel mixts investi- 19)
gated include furfuryl alc & primary amines, Ozone with: diethylenetriamine (Ref 10);
UDMH (unsym dimethylhydrazine) and phenyl- Nz ~ (Ref 10); hydrogen (Ref 10); pentaborane
acetylene (Ref 38). Ignition delay data are (Ref 10); UDMH (Ref 10); trimethykduminum
given in Ref 39 for fuels made hyperbolic by (Ref 19); morpholines (Ref 24); polyamides
addition of UDMH. Included are alkanes, (Ref 23)
aldehydes, alcohols, esters, Cc Hb and deriva- H202 with: UDMH (Ref 10); UDMH 50%
tives, olefins, naphthalene & derivatives, furan & Nz Hq 50% (Ref 8); diethylenetriamine (Ref
& derivatives, cyclohexane & derivs, and methyl- 8); ethylenediamine (Ref 8); UDMH 60% &
cyclopentane & derivs. The amount of UDMH diethylenetriamine 40% (Ref 8); pentaborane
required decreased with increasing chain length. (Ref 8); triethylaluminum (Ref 19); triethyl-
Oxidizers included HN03, Nz 08, Hz SOQand borane and other borane derivatives (Ref 19);
Hz 02. A mathematical model for the hyperbolic N2~ (Ref 8, 25); MMH (Ref 8, 17)
ignition in space for Nz OQ/MMH (monomethyl hy - Fluorine with: N2H4 (Ref 10); Hz (Ref 10,
drazine) and Nz Oa /UDMH has been developed. 14); MMH (Ref 10, 17); pentaborane (Ref 10);
It predicts ignition delay times for space rocket triethylaluminum (Ref 14); triethylboron &
engines and ignition pressure spikes (Ref 40) other borane derivatives (Ref 19)
The vacuum ignition characteristics of flex/ Oxygen/Fluorine (FLOX) with: ethylene
diborane (flex is a mixt of Fz & liq 02) and (Ref 26); methane (Ref 26); propane (Ref 26);
oxygen difluoride/diborane were investigated in propylene (Ref 26); diborane (Ref 27)
100-lb thrust rocket engines for possible use in C1F3 with: N2~ (Ref 8, 10, 16, 28); Hz
space engines. Variables tested included hardware (Ref 10); MMH (Ref 8, 17); pentaborane (Ref
temp, propellant temp, oxidizer leading or lagging 8, 10); UDMH (Ref 8); diethylenetriamine (Ref
fuel, chamber press and injector configuration 8); ethylenediamine (Ref 8); UDMH 60% &
(Ref 41) diethylenetriamine 40% (Ref 8); kerosene (Ref
Hyperbolic Oxidizer and Fuel Mixtures. A 19); triethylaluminum (Ref 19); triethylboron
list of oxidizers and fuels which are hyperbolic (Ref 19); diborane (Ref 19); UDMH 50% &
follows: RFNA with: aniline (Ref 7); Nz Ho Nz ~ 50% (Ref 8, 10); PBAA (polybutadiene/
(Refs 8 & 9); H, (Ref 10); toluene (Ref 11); acrylic acid/acrylonitrile) + NH4 C104 + Al (Ref
diethylenetriamine (Ref 8); MMH (Ref 8); 29); polysulfide + NH4C104 + Al (Ref 29);
UDMH 50% & Nz ~ 50% (Ref 8); ethylene- polyurethane + N~ CIOQ + Al (Ref 29);
diarnine (Ref 8); UDMH 60% & diethylenetri- double-base propellant (Ref 29)
amine 40% (Ref 8), pentaborane (Ref 8); C103F with: UDMH 50% & Nz~ 50% (Ref
triethylaluminum (Ref 12); diethylzinc (Ref 8); diethylenetriamine (Ref 8); ethylenediamine
12); trimethylaluminum (Ref 12); diborane (Ref 8); pentaborane (Ref 8); N, m (Ref 8, 10);
(Ref 12) Hz (Ref 10); MMH (Ref 8, 10); UDMH (Ref 8,
WFNA with: aniline (Ref 2); N2~ (Ref 10); UDMH 60% & diethylenetriamine (DETA)
8); MMH (Ref 8); UDMH (Ref 8); UDMH 50% 40% (Ref 8, 10)
& N2 ~ 50% (Ref 8); diethylenetriamine (Ref N2 Fq with: NH3 36% & Nz Ha 64% (Ref
8); UDMH 60% & diethylenetriamine 40% (Ref 10); Nz~ (Ref 10); Hz (Ref 10)
8); pentaborane (Ref 8); amines (Ref 4); JP-4 Oxygen difluoride with: diborane (Ref 27);
& dicyclopentadienyliron (Ref 13) Hz (Ref 10); UDMH 60% & diethylenetriamine
N2 Od with: Hz (Ref 10, 14); pentaborane 40% (Ref 10); MMH (Ref 10); RP-1 fuel (Ref
(Ref 8, 10); N,~ (Ref 8, 10, 15, 16); MMH 10)
 H 256

BrF5 with: Nz ~ (Ref 8); MMH (Ref 8); detonation wave as a reaction model. Theoreti-
UDMH (Ref 8); UDMH 50% & N2HA 50% (Ref cal analysis compared favorably with exptl data
8); diethylenetriamine (Ref 8); ethylenediamine from the literature on Nz 00 -HN03 /N2 I& rocket
(Ref 8); UDMH 60% & diethylenetriamine 40% motor firings
(Ref 8); pentaborane (Ref 8) TNT equivalent blast yields and fireball di-
C1F5 with: N2~ (Ref 30, 31} Li, Ca, Na, mensions were detd experimentally for the
NaK and K (Ref 32) hyperbolic propellant N2 Oq/Aerozine 50 (Ref
Physical F?-operties. Physical properties and 53, 54). Explosive reactions have been reported
handling hazards for the following hyperbolic for C1F3 with methane and propane (Ref 55).
propellant fuels and oxidizers are given in Ref Violent reactions occur between N2 Od and
42: alkyl borane, aniline, C1F3, F2, N2 m, Hz, many halogenated hydrocarbon solvents (Ref
Hz 02, MMH, RFNA, N2 04, 02, pentaborane, 56). Most reactive are the partly chlorinated
C103F, and UDMH compds of C2H6, C2~ & CHQ. Explosive sen-
Thermochemical and Thermodynamic hoper: sitivity decreases in solvents: 1) with greater
ties. The heat release rate for the liq phase re- ratios of Cl: H atoms; 2) that are symmetrical;
action of N2 OQ & Nz ~ was measured and 3) with no double bonds and 4) with more F
found to be equal to that for HN03 /Nz m than Cl atoms
determined by Somogyi & Feiler (Ref 43). Both Propellant Performance Data. Specific impulse
heat & gas release were detd for liq H2 Oq with and chamber temperature for a number of more
N2 l&, MMH, and UDMH which were mixed by common hyperbolic propellant combinations are
free jets impinging and quenched. Calorimetric in the following table. The values are based on
and PVT measurements established total heat shifting equilibrium conditions with a chamber
and gas release. Reactibility increases in order pressure of 1000 psia. Data are from Ref 33
of: Nz ~, UDMH, and MMH (Ref 44). Enthalpy,
entropy, phase compn, press, temp, and SP VO1
Chlorine Trifluoride (ClF3 )
for Aerozine 50 (50% N, w & 50% UDMH)
have been detd and charted (Ref 45). Significant Heat of formation, liquid, AH;= -44.4 kcal/mole
them species and reactions in propellant exhausts Density of liquid, 1.81 g/rrrl at 298°K
containing C, H, O, N, F, Cl, and either Al, Be, Melting point, -82.6°C
B or L1 were detd for use in nonequil performance Boiling point, 11.3°C
talcs. Propellant systems included hyperbolic liquid Maximum Specific Impulse (1000 + 14.7 psia)
propellants and hybrid propellants (Ref 46). Im-
Wt %
portant c.hem reactions in the following propellant
mixts were used to describe the kinetics of non- Fuel Oxidizer Tc> ‘K p(g/cc) Isp(Sec)
equil expansion and calculated theoretical sp imp: H2 92 3403 0.612 318
02/H2; F2/Hz; N20Q/A50 (49% UDMH & 51% N2 ~ 73 3882 1.48 293
N2~); ClF3/N2H4 ; 0F2/B2H6; ~ /Nz~ ; FLOX B5 Hg 88 4487 1.47 290 ‘
(69.3% F, & 30.7% 0,)/RP-l; liq O,/RP-l (Ref UDMH 75 3794 1.37 280
47). Theoreticrd performance talcs have been Polyethylene 77 3541 1.48 257
made for 02, Fz /beryllium; lithium hydride/H2 CH3 N2 H3 74 3647 1.42 283
(Ref 48); aviation gasoline/fuming nitric acid DETA 75 3599 1.47 267
(Ref 49); and oxygen diflouride/diborane pro- !/
pellants (Ref 50)
Explosion Properties. Occurence of detonation Bromine Pentafluoride (BrF5)
wi;hin rocket engines employing certain aminated
fuels ‘and nitric acid propellants are related to Heat of formation, liquid, AH;= -132 kcal/mole
the formation of amine or hydrazine nitrates Density of liquid, 2.466 g/ml at 298°K
which tend to decompose explosively under the Melting point, -62.5°C
influence of sudderi temp or pressure rises (Ref Boiling point, 40.3°C
51). Tangential-mode rocket motor instabilities
were analyzed using 1-dimensional, 2-phase
 H 257

Maximum Specific Impulse (1000 + 14.7 psia) Maximum Specific Impulse (1000+ 14.7 psia)
Wt % Wt %
Fuel Oxidizer Tc,
——“K p(g/cc) Isp(Sec) Fuel Oxidizer Tc, ‘K P(g/cc) lsp(Sec)
CH3N2H3 78 3264 1.76 235 Hz 84 2660 0.352 342
B5Hg 92 4380 1.99 246 B5Hg 77 4266 1.10 306
Nz I& 77 3323 1.85 244 Nz ~ 57 3257 1.21 291
UDMH 78 3215 1.68 231 UDMH 72 3429 1.16 286
DETA 78 3042 1.84 220 Polyethylene 80 3444 1.29 276
CH3N2 H3 68.5 3390 1.19 288
DETA 74 3369 1.27 278
Hydrogen Peroxide (H2O2) 100%
Heat of formation, A~f = -44.84 kcal/mole
liquid,
Density of liquid, 1.443 g/ml at 298°K Red Fuming Nitric Acid (RFNA)

Red fuming nitric acid contains 2 weight percent H20,

Maximum Specific Impulse (1000 + 14.7 psia)
84.6% HN03 and 13.4% N204
Wt %
Fuel Oxidizer Tc, “K P(g/CC)
—
Isp(Sec)
~
Heat of formation, liquid, AH;= 41.0 kcal/mole
Hz 88
Density of liquid, 1.57 g/cc at 298°K
2404 0.435 322
Melting point, -49°C
B5Hg 73 3400 .06 316
Nz& 67 Boiling point, 66°C
2923 .26 286
UDMH 81 3008 .25 283 Maximum Specific Impulse (1000 +14.7 psia)
Polyethylene 86.5 2999 .30 277 Wt %
Fuel Oxidizer ~ p(g/cc)
— Isp(Sec)
—
B5Hg 77 3486 1.17 298
Fluorine (F2)
N2 ~ 60 3003 1.28 278
Heat of formation, liquid, -3.47 kcal/mole at 85 .2°K CH3 Nz H3 71 3191 1.28 278
Density of liquid, 1.51 g/cc at 85.2°K UDMH 76 3008 1.27 272
Melting point, -219 .6°C Polyethylene 83 3230 1.39 268
Boiling point, -188°C
Maximum Specific Impulse (1000 + 14.7 psia)
Written by E. L. CAPENER
Wt %
Fuel Oxidizer Tc, “K p(g/cc) Isp(Sec) Refs: 1) J.D. Broatch, Fuel, 24-5, 106 (1950)
2) S.V. Gunn, JAmerRocketSoc 22, 33 (1952)
Hz 89 3964 0.468 410
& CA 47, 8341 (1953) 3) M.L.J. Bernard,
Nz I& 69 4688 1.31 363
FifthSymp(Intrnl)Comb, 217, Reinhold, NY
B5Hg 82 5101 1.20 360
(1955) 4) L.R. Rapp & M.P. Strier,, JetPropul-
UDMH 71 4342 1.19 344
sion 27, No 4, 401 (1957) & CA 51, 8405
Polyethylene 72.5 4382 1.28 325
(1957) 5) M. Kilpatrick & L. Baker, Jr, Fifth
NH3 77 4543 1.15 357
SympComb, Reinhold, NY (1955) 6) G. Morrell,
“Summary of NACA research on ignition lag of
Nitrogen Tetroxide (N2O4) self-igniting fuel-nitric acid propellants,” NAC~
RM E57G19 (Ott 3, 1957) 7) R.P. Rastogi
Heat of formation, liquid, AH;= -5.4 kcal/mole
et al, IndianJChem 2, No 8, 301 (1964) & CA
Density of liquid, 1.43 g/cc at 298°K
61, 14453 (1964) 8) A.F. Duncan et al, “A
Melting point, -1 1.2°C
study of hyperbolic bipropellant mass explosion
Boiling point, 2 1‘C
for attitude control of spacecraft:’ Final Rept
No 5915 (Jan 15-Aug 31, 1962), Marquardt
 H 258

Corp, Van Nuys, Calif (Aug 1964) (AD-450 Western, States Sect Combust Inst; Paper, WSCI
129) 9) J.J. Chilenski,, USP 3120738 (1964) 65-23 (1965) 27) G.R. Mistier & T.F. Seamans,
& CA 60, 15676 (1964) 10) J. Tubeuf & “Vacuum ignition characteristics of flex/diborane
J. Bedel, “Considerations on rocket propulsion and oxygen difluoride{diborane,” NASA Con-
for an aerospace vehicle,” Paper presented at tract Report 1969, NASA-CR-1 00678. Avail
Eurospace Conf, Brussels, Jan 23-24, 1964 CFSTI. From SciTechAeiosp Rep 7 (12), 2196
(NASA N 65-24027) 11) G. Hennings & G. (1969) 28) W.B. Powell et al, “ClF3-N2H4
Morrell, “Preliminary investigation of a chemi- liquid propellant evaluation and rocket motor
cal starting technique for acid-gasoline rocket development,” TechRept 32-305, Jet Propulsion
propellant system;’ Res Memo E52K21, Natl Lab, Calif Inst Tech, Pasadena, Ca, (May 1963)
Advisory Committee for Aeronautics, Wash, DC (NASA N63-21722) 29) H. Allen, Jr & Pinna,
(Jan 1953) 12) B. Lewis, USP 3177652 (1965) “Relative ignitability of typical solid propellants
& CA 63, 5442 (1965) 13) C.J. Pedersen, USP with C1F3;’ NASA TN-D-1533, NASA, Wash,
3038299 (1965) & CA 57, 10094 (1962) 14) DC, (Jan 1963) (NASA N63-1 1616) 30) R.F.
A. Corbett et al, “Hyperbolic ignition at reduced Sawyer et al, AMA J, 6, 11, 2111 (1968) &
pressure,” Rept No AFPRL-TR-64-1 75, (May 1- CA 70, 13118 (1969) 31) M.C. Branch &
Sept 30, 1964), Thiokol Chem Corp, Denville, R.F. Sawyer, JSpacecraft & Rockets 6, 11,
NJ, (1964) (AD-61O 144) 15) R. Friedman et al, 1322 (1968) & CA 72, 45648 (1970) 32)
“A study of explosions induced by contact of R.A. Rhein, JSpacecraft & Rockets 6, 11,
hydrazine-t ype fuels with N204 ,“ Final Rept No 1328 (1968) & CA 72, 45648 (1970) 33)
ASDTDR-62-685, (June 1, 1961-May 31, 1962), Propellant Performance Data, Callery Chemical
ARC, Alexandria, VA (1962) (NASA N 63- Co (1961) 34) Aviation Week & Space Tech-
17985) 16) J.J. Chilenski7 USP 3120738 (1964) nology (March 19, 1973) 115 35) H.E. Perlee
& CA 60, 15676 (1964) 17) O.A. Knight, Jr, & T. Christos, “Summary of literature survey
Petrol Refiner 41, No 2, 179 (1962) 18) A.B. of hyperbolic ignition spike phenomena, Phase
Willoughby et al, “Summary of existing infor- I,” NASA Accession No N66-397 12, Rept No
mation concerning the explosive potential of the NASA-CR-78986, SciTechAerosp Rept” 4 (24)
hyperbolic propellant combination N2 Oa/50% 4813 (1966) & CA 66; li7:0 (1967) 36)
UDMH-50% Nz H4 ,“ Rept No AFRPL-TR-65- R.L. Chuan & P.C. Wilber, JSpacecraft &
27, United Research Services Corp, Burlingame, Rockets 4 (2), 282 (1967) & CA 66, 97058
Ca, April 1965 (AD464 339) 19) B. Lewis, (1967), 37) J.A. Simmons et al, AIAA J,
USP 3117652 (1965) & CA 63, 5443 (1965) 6 (5), 887 (1968) & CA 69, 4076 (1968)
20) H.C. Baden et al, JPhysChem 62, 331 (1958) 38) G. Spengler et al, “Measurements of igni-
& CA 52, 11425 (1959) 21) J.W. Gregory & tion delays of hyperbolic liq rocket propel-
D.M. Straight, “Ignition of hydrogen-oxygen lants,” NASA Accession No N64-24376, Rept
rocket combuster with C1F3 & triethylaluminum,” WSS/Cl 64-12, avail CFSTI (1964) 39) G.
NASA TN-D-684, NASA, Washington, DC, April Spengler & J. Bauer, Brenstoff-Chem 46 (4),
1961 22) C.F. Cullis et al, ProcRoySoc (London) 117 (1965) & CA 63, 4087 (1965) 40) T.F.
289, 413 (1965) & CA 64, 4899 (1966) 23) Seamans et al, “A fundamental model of
Anon, Brit P 804590 (1958) & CA 53, 9620 hyperbolic ignition in space-ambient engines,” ‘“
(1959) 24) C.R. Scott & A.L. Ayers, USP IAA Accession No A67- 12284, Avail AIAA,
2771738 (1956) & CA 51, 3969 (1957) 25) Paper No 66-950 (1966) & CA 67, 34559
M. Kilpatrick & L.L. Baker, Jr, “A study of (1967) 41) G.R. Mistier & T.F. Seamans,
fast reactions in fuel-oxidant systems,’: FifthSymp “Vacuum ignition characteristics of flex/
Comb, Reinhold, NY, (1955) 26) S.A. Masier diborane & oxygen difluoride/diborane,” NASA
et al, “Hyperbolic ignition of light hydrocarbon Rept No NASA-CR-100678, Sci Tech Aersp
fuels with fluorine-oxygen (FLOX) mixtures,” Rept 7 (12), 2196 (1969) & CA 71, 72501
 H 259

(1969) 42) “The Handling and Storage of 78, 32298 (1973) 53) R.E. Pesante et al,
Liquid Propellants:’ Office of the Director of “Blast and fueball comparison of oxygenic .
Defense Research and Engineering, Wash, DC, and hyperbolic propellants,” NASA final rpt
Covt Printing Office, Jan 1963 43) B.R. Lauvel NASA-CR-69088 (1964) 54) R.E. Pesante
& E.A. Tkachenko, “Heat-release rate for ,the liq et al, “Blast and Fireball comparison of cryo-
nitrogen tetroxide/hydrogen reaction by Somogyi genic and hyperbolic propellants with simulated
& Feiler’s method;’ NASA Rept NASA-CR- tankage,” NASA rept NASA-CR-69114 (1964)
73608, avail CFSTI, SciTechAerosp Rept 7 (6), 55) C.B. Baddiel & C.F. Cullis, Eighth Symp
946 (1969) 44) S.E. Rodriguez, “Heat & gas Comb, 1089, Williams & Wilkins, Baltimore,
release mess on Iiq hyperbolic propellants,” Md, (1962) 56) R.E. Turley, ChemEngrNews
(paper) West States See/Comb Inst, 70-26 42 (47), 53 (1964) & CA 62, 2661 (1965)
(1970) & CA 74, 77953 (1971) 45) J.P.
Copeland & J.A. Simmons, “Determination of Hyperol or Perhydrate. A tradenarne for the
thermodynamic properties of Aerozine-50,” compound of hydrogen peroxide and urea.
NASA rept NASA-CR-92463 & NASA-CR- 0C(NH2)2 .H2 Oz, solid, decomp above 82° (Ref
92464, avail CFSTI, SciTechAerosp Rep 7 (6), 2). It is claimed to be an advantageous replace-
1058 (1969) & CA 71, 72488 (1969) 46) ment for hydrogen. peroxide in chemical analyses
P.I. Gold, “Chemical species and chemical re- (Ref 1)
Refs: 1) J.R. Booer, Chem & Indust 44, 1137
actions of importance in nonequilibrium pro-
(1925) & CA 20, 158 (1926) 2) E. Janecke,
pellant performance calculations,” NASA Acces-
RecTravChim 51, 579 (1932) & CA ’26, 4747
sion No N66-337 14, Rept No NASA-CR-65442, (1932)
avail CFSTI, SciTechAerosp Rept 4 (19), 3722
(1966) & CA 67, 4484 (1967) 47) S.S. Cherry Hypervelocity Gun. A patent by Clark & Boltz
& L.J. van Nice, Pyrodynamics 6 (34), 275 (1959) claims a device consisting of a compres-
(1969) & CA 70, 98394 (1969) 48) R. E., Lo, sion chamber & piston energy absorber that
“Theoretical performance of the multicompo- produces shear projectiles at velocities of 10,000
nent rocket propellant system (oxygen, fluorine/ to 15,000 ft/sec which is claimed to be 5 times
beryllium, lithium hydride)/hydrogen,” Deut sche greater than velocities that are produced by
Versuchsanst Luft- und Raumfehri Rept! 1968, impact. Applications for this device include sim-
DLR-Mht-68-21 (Ger), avail CFSTI, SciTech ulation of possible effects of meteor particles
on missiles in outer space and general studies
Aerosp Rept 7 (l), 161 (1969) & CA 71,
of high-velocity particles colliding with various
72491 (1969) 49) S.E. Flygar, “Thermo-
materials
chemical calculations for rocket motors using Hypervelocity firings into mixtures of hydro-
the components aviation gasoline MC 77 and gen with air or with oxygen were studied by
fuming nitric acid;’ US AT Energy Comm H. Behrens et al and reported at 10th Symp
1967, FOA-2-A-249 1-42 (Swedish), avail CFSTI, Cornbstn (1964), pp 245-52
SciTechAerosp Rept 7 (6),” 841 (1969) & CA Refs: 1) A.B.J. Clark & P.T. Boltz, USP 2882796
71, 72492 (1969) 50) D.A. Bittker, “Theoreti- (1959)
cal nonequilibrium performance of oxygen 2) Anon, Ordnance 44, 468 (1959)
difluoride-diborane rocket propellant;’ NASA
Hypervelocity Impact: Dependence of Crater
Tech Note NASA-TW-D-4992 (1969), avail
Dimensions on Impact Velocity. Craters in
CFSTI, SciTechAerospRept 7 (6), 1058 (1969)
copper and lead, produced by hypervelocity
& CA 71, 72494 (1969) 51) M.L.J. Bernard impact, were measured and the dimensions
& J. Dufour, Eighth Symp (Intl) on Comb, correlated with impact vel. The results indicate
1074, Williams & Wilkins Co, Baltimore, Md, that craters scale with ca the 1.7 power of vel,
(1962) 52) P. Shen & T.C. Adamson, Jr, in agreement with computer physics results
Astronaut Acts 17 (4-5), 715 (1972) & CA based upon hydrodynamic calculations
 H 260

Rejl J.H. Kineke Jr, BRL Memo Rept 1652 acid, free from metals and protected from strong
(May 1965) (Title as above) light, may be stored for a day without important
loss. Solutions up to 20% may be kept for a
short time at room temp, and 3070 solutions
HYPOCHLOROUS ACID AND HYPOCHLORITES may be kept for a long time at -20° (Ref 3,
Hypoc/.dorcxm Acid (Unterchlorige Siure in p 694)
Ger), HC1O or HOC1; known only in aq solutions. For more information on the properties of
Although chlorine water was prepd as early as hypochlorous acid, see Refs 1 & 2
1774 by C. W. Scheele (Ref 1; p 243), it was Hypochlorites. The combination of the hypo-
not known that chlorine reacted with water, chlorite ion with a metallic ion or organic
Clz + H2 O = HC1O + HCI, forming a new acid, radical is called a hypochlorite. The inorganic
HC1O. A. J. Balard first identified it; he prepd compounds are called salts, while organic hypo-
not only an aq solution of the acid, but also chlorites are esters
isolated the anhydride, chlorine monoxide The first hypochlorites (those of sodium and
In the preparation of hypochlorous acid from potassium) were prepd in solution, in 1788, by
chlorine and water, the yield is very low, on C. L. Berthollet by treating solutions of the
account of the small volubility of chlorine in corresponding hydroxides with chlorine; 2NaOH
water. The ‘yield of HC1O can be increased + C12 = NaCl + NaCIO + H20
either by adding an insoluble oxide or carbo- In 1834, A. J. Balard prepd solutions of
nat e which forms a sparingly soluble chloride. various hypochlorites by mixing aq hypochlorous
For instance, on adding mercuric oxide, the acid with alkalies, magnesium, copper oxide,
reaction proceeds; 2C12 + H2 O + HgO = HgC12 zinc oxide etc, avoiding an excess of acid
2HC1O, and with silver carbonate; 2C12 + Hz O * J. L. Gay-Lussac dissolved two mols of
Agz C03 = 2 AgCl + 2HC1O + C02 chlorine monoxide, C12O, in a solution con-
Another way to increase the yield is to pass taining 1 mol of K2 O and then evaporated the
additional chlorine into soda or lime solutions resulting solution in vacuo. This gave solid
of chlorine; Clz + Na2C03 + Hz O = NaCIO + potassium hypochlorite
NaCl + Hz C03, followed by acidification with The following inorganic hypochlorites are
Hz SO., and distillation of the liberated HC1O described in literature; aluminum (very unstable),
The acid can also be made by the action of ammonium (very unstable), barium, calcium,
water on chlorine monoxide, C12O. This reaction cupric, lithium, magnesium, potassium, silver
is accompanied by the evolution of 4 kcal of (unstable), sodium, strontium and zinc. None
heat per mol of these salts is used in explosives or is ex-
Hypochlorous acid is a weak acid with a dis- plosive per se, but some of them are used in
sociation constant equal to 3 to 4 x 10-8, which industry
is about l/600th the strength of acetic acid. When However, when small amounts of damp S and
it is stored it slowly decomposes according to the calcium hypochlorite are mixed, a brilliant crirn
following equations: son flash is observed accompanied by the
2HOC1 = 2HC1 + 02 or 3HC1O = 2HC1 + scattering of molten burning S (Ref 9)
HC103. Both reactions are greatly accelerated by Mso, according to J. Weichherz, Chem Ztg,
light. The first of these reactions makes hypo- 52, 729-30 (1928), a mixture of Ca hypochlorite
chlorous acid a strong oxidizing agent with combustibles explodes on heating (See also
Hypochlorous acid reacts with inorganic bases Ref 2)
with the formation of salts, called hypochlorites. Calcium hypochlorite has been used to neu-
In reactions with organic compounds, the acid tralize toxic explosion gas in mining (Ref 8):
may act not only as an oxidizer (see above) but Explosion of 1 kg detonite 10A & ammonite
also as a chlorinating agent (in the case of satu- No 6ZhB yields 42-56, and 58-81 1 poisonous
rated compounds) or the addition of HO-Cl to gases, respectively. Use of ampules containing
the double linkage C=C to form a chlorhydrin; pyrolusite, NaHC03, or Ca hypochlorite (15-
R, C = CR2 + HO-Cl = RI C(OH).C(C1)RZ 25% of the explosive wt) .as neutralizing sub-
Solutions carrying up to 1% hypochlorous stances neutralized 505Z0of the poisonous gases &
 H 261

decreased by 30% the required ventilation time Organic Hypochlorites (Esters of Hypochlorous
of the mine galleries. Hydrogen peroxide (3%), Acid). Methods of preparing alkyl esters of
Ca hypochlorite, or water were introduced in hypochlorous acid are given under individual
polyethylene ampules (vol 250m3) into the compounds, but a general method, recently pro-
bore hole, whose opening was hermetically posed, is via the reaction of HC1O with the
sealed by a “hydroseal,” and water was intro- appropriate alcohol in solution (preferably in
duced into the bore hole under pressure freon but pet ether, carbon disulfide or benzene
can also be used)(Ref 8). The lower members
Analysis of Hypochlorites.
are unstable, mobile, yellow oils and most of
Methods of determination of hypochlorous
them explode when brought into contact with
acid and hypoch.lorites are given in Ref 2, pp
a flame or when exposed to bright light. In the
292-296
absence of a flame or light, all of them, except
According to Scott (Ref 5, p 262), hypo-
the tertiary compounds, decompose spontaneously
chlorites decolonize indigo, but do not decolonize
on standing (Ref 8). According to Comastri (Ref
KMnOa solutions. If arsenous acid is present,
6), they are much more stable if any HC1, formed
indigo is not decolonized until all the arsenous
as a result of the reaction, is immediately re-
acid has been oxidized to the arsenic form
moved by neutralization with NaHC03 (See also
(distinction from chlorous acid and chlorates).
under Ethyl Hypochlorite)
A quantitative method of determination of
The decomposition reactions of the primary,
hypochlorites in the presence of chlorine by
secondary and tertiary hypochlorites are as
using the KI method, is given in Scott (Ref 5,
follows:
p 274)
1) RCH2 OC1 RCHO + HC1
Feigl (Ref 6) gives a spot test for hypohalo-
2) RRI CHOC1 RRI CO + HC1
genates using benzidine reagent and Welcher
3) RRI Rz COCI RRI CO + R2C1
(Ref 7) gives several qualitative and quantitative
In reaction (1), an aldehyde is formed, in (2),
tests
a ketone and in (3) a ketone and an alkyl chlor-
Refs: 1) Mellor 2, (1922), 243-81 2) Gmelins ide. Reaction (3) only proceeds on heating
Handbuch, Syst No 6, pp 249-96 3) Kirk& Othmer,
In general, the esters are strong oxidizing and
3, pp 681-696 (1948) (Includes 43 refs on chlorinating agents and they explode on contact
hypochlorous acid and hypochlorites) 4) Ull- with copper powder
mann (2nd cd), 3, 345 (1951) 5) W.W. Scott Some aliphatic hypochlorites are described
& N.H. Furman, Standard Methods of Chem below:
Analysis, Van Nostrand, NY (1939), 1, pp 262
& 274 6) F. Feigl, “Qualitative Analysis by Amyl Hypochlorites. CSHI 1C1O; yellow oils; may
Spot Tests;’ Elsevier, Amsterdam (1946), p be prepd by bubbling chlorine through an aq
emulsion of the corresponding alcohol, or by
242 (A drop of 2% solution of benzidine in dil
shaking a CClq solution of an alcohol with an aq
AcOH is mixed with a drop of neutral (or acetic
solution of HC1O (Refs 2, 4 & 5)
acid) solution of the sample on a spot plate. All
hypohalogenates give a blue color, due to the All of these esters, especially the isoamyl-
oxidation of benzidine) 7) F. J. Welcher, Or- are unstable; the ester of the tertiary alcohol,
ganic Analytical Reagents, Van Nostrand, NY (CH3 )2 C(CIO)CZ H~, is more stable than the
others; it boils at 76° at 752mm and decom-
(1947), 1, p 150 (determination of hypochlorites
by the phenol method); 2, p 434 (by the m- poses in sunlight, but keeps fairly well in the
phenylenediarnine method); 2, p 438 (by the dark.
p-phenylenediamine method); 4, p 241 (by the Refi Beil 1,423 & [433]
codeine method); 4, p 390 (by the resorufin Butyl Hypochlorites, Co Hg C1O; yellow oils;, may
method) and 4, p 510 (by the indigo carmine be prepd by methods similar to those for the
method) 8) V.E. Brylyakov et al, Corn Zh amyl hypochlorites. These esters, especially that
1966 (12) 55 & CA 66, 57689 (1967) 9) S.A. of isobutyl alcohol, are unstable
Katz & D.M. Scheiner, Chem Eng News, 46, The esters of n-butyl- and sec-butyl- alcohols
(29), 6 (1968) & CA 69, 64247 (1968) explode when exposed to light. The tertiary
 H 262

butyl hypochlorite, (CH3 )3 C(OC1), is more stable Pentyl Hypochlorites. Same as Amyl Hypo-
than the others. Its bp is 79.6° at 750mm and chlorites
d is 0.9583 at 18° (Refs 1, 4 & 5) (Beil 1, Propyl Hypochlorites. CoH, C1O; yellow oily
[396] –the primary hypochlorite, CH,(CH, ), substances. May be prepd by methods similar
(OC1), [402]; sec-butylhypochlorite, C, H, CH to the ones mentioned under Amyl Hypochlor-
(CH, )OC1 and [415] -tertiary compound; [411] ites (see above)
Ethyl Hypochlorite. CH3CH2C1; mw 80.52, OB All the propyl hypochlorites, especially the
to C02 and Clz -109.3%, d=l.013 at 6°, bp 36° isopropyl, are unstable. n-Propyl-, as well as
at 758mm. Yellow, volatile, oily liquid; was prepd the isopropyl hypochlorites, explode when ex-
in 1885 by Sandmeyer (Ref 3) by bubbling CK)2 posed to light (Refs 2, 4 & 5) (Beil 1, [368]
through cold ethanol or by mixing a cold aq, -n-propylester; [381] -isopropylester)
solution of HC1O with cold ethanol Refs: 1) Beil, 1 (see under the individual com-
Other methods of preparation are given in pounds) 2) Gmelins Handbuch, Syst No 6, p
Refs 1 to 5 264 3) T. Sandmeyer, Ber 18, 1767 (1885);
Comastri (Ref 6) gives the following method 19, 857 (1886) 4) F.D. Chattaway & O.G.
of preparation; Place in a separator funnel a Backeberg, JCS 123, 3001 (1923) & 125, 1097
solution containing 23g of NaOH in 23g of etha- (1924) 5) M.C. Taylor et al, JACS 47, 397
nol and 200ml Hz O. Cool in an ice-salt bath (1925) 5a) J. Durand & R.. Naves, BullSocCkm
and pass in chlorine through a tube reaching to de France (4), 37, 719 & 1154 (1925) 6) H.T.
the bottom of the container. The resulting ethyl Comastri, Anales A Soc Quim Argentina 27, 41
hypochlorite collects in the form of an oil layer (1939) & CA 33, 6793 (1939) 7) N.V. Sidgwick,
on the surface of the liquid and may be sepa- Chemical Elements and Their Compounds,
rated easily. It is washed with a cold saturated Clarendon Press, Oxford, England (1950), v 2,
solution of NaCl, followed by a cold satd pp 1217-1219 8) R. Fort & L. Denivelle,
NaHC03 solution, and immediately dried (while BullSocChim, France 1954, 1109 ‘& CA 49,
cold) over CaC12. The yield is about 72% of 12271 (1956)
theory. The following reaction takes place:
C2H5 OH + 2HC1O = Cz H5 CIO + HC1+ Hz O Hypophosphites are saltsof hypophosphorous
Comastri”claims that, contrary to the litera- acid, H(HZ P02 )3 or .O. ..
ture, the action of light on Cz H5 C1O is inap- H: P:O:H
.. ..
preciable and the material can be kept for H
several hours at room temp, provided that all They are generally prepared by the action of
HC1 (formed as result of the above reaction) is phosphorous on the corresponding salt in
promptly neutralized with NaHC03 solution. alkaline solution. The free acid is prepd by
If the HC1 is not removed, the hypochlorite de- treating Ba-hypophosphite with sulfuric acid.
composes (or even explodes) spontaneously in a It is monobasic and is a strong reducing agent
few minutes, on account of the following (Ref 6)
reaction; Hypophosphites have been claimed as ingre-
HC1 + CZH5 CIO +Clz + Cz H5 OH dients of priming compositions: Lead hypophos-
Ethylhypochlorite is insol in w; sol in bz, phite/MF/Dinitrophenylazide/K2 Ba(NO ~q &
chlf and eth. It explodes violently on heating Sb2S3 (Ref 2); alkali, alkaline earth,
or by the action of direct sunlight (Beil 1, NH4 & Mn hypophosphites mixed with oxidizers
324 (164) and [325] ) such as Pb or Ca nitrate (Ref 4); complex salt
hypophosphites suitable for use in detonators are
Methyl Hypochlorite. CH3C10; mw 66.49; bp claimed to be formed from equimolar amounts
12° at 726mm. Gaseous substance; was prepd of normal or basic Pb styphnate and Pb hypo-
by Sandmeyer (Refs 2 & 3) by bubbling phosphite (Ref 5)
chlorine through a cold solution of NaOH in An early French patent” claims the manu-
methanol. Explodes on contact with flame facture of explosives based on hypophosphites
(Bed 1, 282 and [271]) mixed with oxidizers (Ref 1)
 H 263

Burrows has claimed that the double salt of Hyporka. A glass fiber insulation used in rockets
Pb hypophosphite and Pb nitrate is a suitable Ret A.J. Zachringer, “Solid Propellant Rockets,”
ignition composition around the bridge wire Wyandotte, Mich (1955), p 152
of a blasting cap. He also claimed such mixture
as Ca hypophosphite and K chlorate (Ref 3) “Hyros” Explosives. Prepd by nitrating a mixt
Refs: 1) Serrant & Boilleau, French Pat 397392 of resin, and cereal or flour, adding KC103 and
(1908) & CA 4, 2733 (1910) 2) V.J. Kelson, sufficient water to make a homogeneous paste.
Austral Pat 104189 (1938) & CA 32, 8782 A typical compn is resin 53, wheat flour 27 &
(1938) 3) L.A. Burrows, USP 2173270 (1939) nitric acid of 200B6 20%; the nitrated product
& CA 34, 627 (1940) 4) W. Bruen, USP 1p is mixed with KC103 3 parts & water to
2175826 (1939) & CA 34, 887 (1940) 5) make a paste which is molded into blocks
J.D. McNutt & S.D. Ehrlich, USP 2352964 Refi Leckzinski, FrP 395635 (1908) & CA 4,
(1944) & CA 38, 6098 (1944) 6) CondChem 2733 (1910)
Diet, 8th Edit (197 1), p 463
 I1

IASP. Initial Average Sustained Pressure (in . ‘ companies with major explosives interests of
rockets) is the average pressure during the first which “the most important are Canadian Indus-
part of the run, after full pressure is: reached. tries Limited (CIL), ICI Australia Ltd, Indian
IASP is illustrated in the following Fig Explosives Ltd and the Philippines Explosives
Corporation. ICI also has a substantial holding
llylP in African Explosives and Chemical Industries
,. Pressure Trace
P- Ltd, which operates the largest commercial
I explosives factory in the world at Modderfontein
,-Time Base ! (See Nobel’s Explosives Company in a future Vol)
s.-..--&====l=_==l ----- 1:.- - ------- -_-J-_______L__
-..___ T_______ T__=__--
41 S$P
v
E}P El ICT. Abbr for Igniter Composition for Tracers
DSI (qv)

Definition of Values Measured on Film Strips Ideal and Nonideal Detonations. See Detonations,
Ideal and Nonideal in Vol 4, pp D389-R-
Refi F. Bellinger et al, IEC 38, 166 & 167 D390-R
(1946)

ICC. Interstate Commerce Commission (qv) IDENTIFICATION OF AMMUNITION

AND EXPLOSIVE DEVICES
Ice Blasting by Means In order to
of- Explosives. The identification of ammunition is a very
prevent ice jams in rivers and keep them flowing complex art. It may be accomplished in any
during the thawing ,period, it is often necessary one of a number of methods such as examina-
to help nature by using explosives. Considerable tion of physical size, shape, color markings, ~~
damage can be done to bridges, boats, piers, stenciled markings, metal stampings, and data
etc if the ice jams are not removed at the right written on the packaging material
time. Ice jams also produce flooding Historically speaking, early types of ammuni-
An interesting description of breaking up the tion were identified solely by size and shape.
ice jams in the Raritan river in New Jersey is As the art of waging war became more complex
given by Berliner and sophisticated, logistics support to the field
Refi Berliner, Expls (1953), pp 24-28 also became more complicated. It was dis-
covered that some means other than size and
ICI. Imperial Chemical Industries Ltd of Lon- shape would be necessary for rapid identifica-
don, England, has extensive equity holdings in tion of ammunition on the battlefield. Ac-
the commercial explosives industry throughout cording to available information the first dis-
the world. When ICI was formed in 1926 one tinctive identification of ammunition was
party to the merger was Nobel Industries Ltd developed by the French. This method was
which involved major British explosives interests the application of paint to cannon projectiles
and particularly the factory set up by Alfred to designate the various types used on board
Nobel in 1871 at Ardeer, Stevenston in Scotland ship. This practjce was abandoned prior to
Nobel’s Explosives Company Ltd (NEC) with 1803 because of the lack of a ,suitable colored
its headquarters at Stevenston, is a wholly owned lacquer or paint which would ,hold its color
subsidiary of ICI and has been given responsi- and rem~n on the projectiles during shipboard
bility for the explosives interests of that company. storage at sea .
NEC operates a complete industrial explosives By 1803, the B7itish had adopted an identifi-
industry in Great Britain and operates plants cation system consisting of various colored
and services in other countries as well as letters and numbers applied to the ends of
supplying explosives arid accessories to many powder barrels to designate the type of propel-
customers throughout the world lant, the size of grin, special ingredients used
ICI has a majority shareholding in other in its manufacture, and method of processing.
 12

By the 1850’s, the British had a standardized facturer’s name was applied to the cartridge
color code for identifying smooth bore artillery case base. Later, as it became necessary to
projectiles. This code consisted of a black body better identify ammunition components because
color with white, red and/or yellow bands to of mishaps or malfunctions in the field, both
designate various loadings metal stampings and/or ink stencil marks were
An, all whjte body denoted steel shot and a applied to every component that had a surface
“black body with one white band designated large enough to accept such a mark without
chilled iron shot. About the time of the detrimental distortion occurring
American Civil War the US Navy adopted a By the outbreak of World War I practically
similar code for the rapid identification of pro- every major power in the world had one or more
jectiles aboard ship. Black, white, red, yellow color code systems to identify their projectiles
and blue were used to permit rapid identifica- By this time the art of pyrotechny was so
tion of different projectile loadings or func- well advanced that many different types of
tional features. In this same time period, in signals were being employed. Because of the
both the American and British service, metal vast number of different signaling devices de-
stampings were applied to the exterior surface veloped, various identification systems were
of projectile bodies as proof of acceptance by developed by the major powers, which con-
the inspectors and to identify the manufacturer. sisted of colors, raised dots and milled case
With the introduction of studded projectiles edges and stenciling. In addition, when
in the British Land Service, metal stampings special purpose small arms cartridges were de-
were employed to indicate various arsenal modi- veloped, some means of identification had to be
fications to the projectiles. The painting system developed. Colored bullet tips, partially or
employed for smooth bore projectiles was re- completely blackened cartridge cases and metal
tained and modified to allow for various new stamp base markings were employed for small
types. One example was a black body with one arms ammunition identification
blue band to designate a ring projectile Aircraft bombs were introduced in World
With the advent of breech loading artillery, War I, and soon, various special purpose types
the British retained the same basic black pro- were developed. Therefore, a color code was
jectile body color with colored bands until new developed. Again each service (land and sea)
special types of projectiles were introduced. of the major powers developed their own
An example of this was a yellow body with a identification system consisting of colored bodies,
red band on the nose to denote high explosive, colored bands, metal stampings and ink stencil
“lyddite” (Picric Acid) filled projectiles. When markings
plaster kits were assembled to these projectiles In the same time period, specialized fuzes for
a wide brown band was painted on ‘the pro- both artillery projectiles and bombs were de-
jectile nose and one narrow red band painted veloped. To designate differences in delay or
underneath it. In addition to the color markings, weapon to be used with, artille~ fuzes were
metal stamp and stencil markings were also color coded for rapid identification in the field
employed for identification purposes In the early 1960’s, a concerted effort was
The US Army did not adopt a standardized undertaken by the NATO countries for the es-
color code for artillery projectiles until the turn tablishment of a standardized color code for the
of the 20th century. At this time, there was identification of ammunition of rdl types except
one color code system for mobile army ammu- small arms ammunition below 20mm in caliber.
nition, one for seacoast ammunition and one The following color code was adopted and is
for navy ammunition. Each color code was being used by most NATO countries. The colors
distinctively different, because there was no adopted and their significance are as follows:
attempt to standardize identification among Color Significance
the then three services
By this time, breech loading weapans had Yellow 1) HE ammunition
been improved by development of the brass 2) Presence of explosive
cartridge case, the base of which provided a a. sufficient for HE function
good surface for placing information. At first, b. particularly hazardous to
only the weapon bore size and/or the marm- user
 13

Color Significance OP 4 Ammunition Instructions for the

Naval Service May 1943
Brown 1) Rocket motors
2) Presence of explosives TM 9-1900 Ammu,tition General, 1941
a. sufficient for low- Ammunition General, 1942
explosive function Ammunition General, 1945
b. particularly hazardous to Ammunition. General, 1956
user V650 Ammunitionsregister f6rArm6n
Gray Ammunition containing toxic Best”tilles hos KATF/TFB,
or irritant agents. Presence of Stockholm 80, 1960
high or low explosive compo- TM 9-1901 Artillery Ammunition, 1944
nents is indicated by yellow or Artillery Ammunition, 1950
brown bands Artillery Ammunition, 1967
Gray with red Ammunition containing irritant TM 9-1980 Bombs for Aircraft, 1942
band or bands agents Bombs for Aircraft, 1944
Gray with dark Ammunition containing toxic Bombs for Aircraft, 1950
green bmd or agents TM 9-1985-1 British Explosive Ordnance, 1953
bands Supplement to British Navy Projectiles and Fuzes,
Black Armor defeating ammunition Intelligence June 1945
Silver or Countermeasure ammunition such Bulletin No 85
Aluminum as radar echo leaflets Bombs & Hand Grenades by
Light Green Smoke or marker ammunition. Bertram Smith, E.P. Dutton & Co
Presence of high or low explo- NY 1918
sive indicated by yellow or Catalogue of Enemy Ordnance
brown bands Materiel Vols 1 & 2, US Army
Light Red Incendiary ammunition or pre- Ordnance Depot 1 March 1945
sence of highly flammable ma- Catalog of Cartridge Manufac-
terial designed to produce turers and Base Markings by
damage by fire B.D. Munhall & H.P. White 1944
White Illuminating ammunition or TM 5-280 Foreign Mine Warfare Equipment,
colored lights April 1965
Light Blue Practice ammunition. Presence TM 5-280 Foreign Mine Warfare Equipment,
of high or low explosive com- July 1971
ponents indicated by yellow or French Grenades and Grenade Fuzes
brown band Minist~ of War, 15 Dec 1930
Orange Ammunition used for tracking TM 9-1985-2 German Explosive Ordnance, 1953
and recovery in tests or in
training operations TM 9-1985-3 German Explosive Ordnance, 1953

Bronze Dummy and training ammunition PATR 2510 German Explosives, 1958
PATR 2145 Russian Explosives, 1955
List of a Few of the Publications Which Contain
Additional Information on the Identification of German Intelligence Data Sheets
Ammunition and Explosive Devices on World War I Chemical Am-
Aircraft Bombs, Fuzes & Asso- munition British, French, Italian,
0P2216
Russian, 1918
ciated Components
~.Dv. 454/6b Geschosszunder Beschreibungen
26/Manuals/ 1473 Ammunition Handbook for the
RoyaJ Army Service Corps 1936 und Zeichnungen, July 3, 1938–
Berlin, i938
 I4

OPNAV 30-3M Handbook of Japanese Explosive SS 420 Notes on German Shells (second
Ordnance, 15 August 1945 edition) General Staff (Intelli-
gence) General Headquarters,
Kemp D&PS Handbook of German Aircraft 1 May 1918
Ammunition by Bross & D&PS D 460/9+ IUngbuck fiir Zunder, Band II,
Aberdeen PG, Md, 1956 5 June 1941
Handbook of Enemy Ammuni- D 460/8+ Ringbuck fur Ziinder, Band I,
tion Pamphlets, The War Office 5 June 1941
1940 thru 1945, London
Ordnance Magazine, Various
N 3353 Istruzione Piowisoria Sulle Editions, American Ordnance
Bornbe A Mano S.R.C.M. Association, Washington, DC
Breda–O.T.O. od 35, Roma 1938 TM 9-1950 Rockets, 1958
No 647 Istruzione Sulle Munizioni, FSTC-CW- Small Arms Ammunition Iden-
Parte I, Roma 1936 07-02-66 tification Guide, December, 1966
TM 9-1985-6‘ Italian & French Explosive The Bombardier & Pocket’
Ordnance, 1953 Gunner by Ralph Willett
TM 9-1985-4” Japanese Explosive Ordnance, 1953 Adye London 1803
TM 9-1985-5 Japanese Explosive Ordnance, 1953 Treatise on Ammunition, 6th
L’Artificiere D’Artiglieria, Edition, War Office, London, 1897
Caricamento Proiettili, 2nd Treatise on Ammunition 10th
Edition, 1936 Edition, War Office, London, 1915
L’Artificiere D’Artiglieria, 3rd Various German drawings of proj-
Edition, 1941 ectiles and fuzes 1939– 1945
Les Fust?esParis, 1918 C.W.S. Intelli- Markings of Japanese Chemical
gence Summary Warfare Munitions
Manuel Des Munitions–Impri-
No 12
m6rie Nationale, 1932
Written by John F.W. Pflueger
AOP-2 Method of Application of the
NATO Code of Colours for the
Identification of Ammunition Iditol. A synthetic resin obtained by the con-
(except Ammunition of a Calibre densation of phenol & formaldehyde. It is used
Below 20mm). Prepared by the as a binder in many Russian pyrotechnics
Department of National Defence, Rejl Gorst (1957), 162
Canada Ottawa 1966
TM 9-1981 Military Pyrotechnics, 1943 Ievler (or ‘Jewler) Explosives. Various Sprengel-
type explosive mixtures proposed in 1897-1900
TM 9-1981 Military Pyrotechnics, 1951
by Ievler of Russia, such as Prometh6es. Other
MIL-STD-709 Military Standard Ammunition explosives of this class consisted of liquids such
Color Coding, 27 June 1960 as nitrobehzene, methanol etc absorbed on
MIL-STD-709B Military Standard Ammunition potassium chlorate mixed with Portland cement
Color Coding, 13 October 1972 and/or copper oxide etc
Refi Daniel (1902), 328
R. Moh C.3 Normas para el p;ntado y marcado
de la munition de combate,
ejercicio e instruction, Buenos Igdanit. A Russian expiosive similar to ANFO.
It consists of a mixture of AN and 5 to 8%
Aires 1959
fuel oil. It is usually mixed just prior to use.
Bulletins Notes on Ammunition by Maj Max deton velocity is only 2000 m/see for
216-R2 & 287 Wm. C. Foote, C.A. Coast mixes with 5 to 6% oil (Ref),
Artillery School, Fort Monroe, See IGNADITY in Vol 5, pp D1744-R to
Va, Ott 31, 1918 D1 746-L
 15

Refi E.P. Maksimova, Vzryvchatyie Veshchestva somewhat like an incendiary missile. Marco
Prosteishego Sostava, Inst Gornago Dela, Akad Greco in his 9th to 10th century book entitled:
Nauk SSR, Sbornik Statei i Materialov 1960, “fiber Ignium ad Comburendos Hostes” gives
34-41 & CA 57, 7963 (1962) & Explosivst the composition as: sulfur 1 part, charcoal (of
1964, 20 linden, or willow trees) 2 parts, saltpeter (crude)
6 pa~ts
Igelit. Trade name for a polyvinyl plastic used Refi Daniel (1902), 382
as a binder in some Ger pyro compns, such as
listed in PATR 2510 (1958), p Ger 154-R Ignitacord. Thermalite Ignitacord is the Dupont
Inc name for a device for igniting safety fuse.
Igloo Magazines. Thk type of magazine is now It is cordlike in appearance and burns progres-
standard for storing ammunition of the US sively rdong its length with an external flame
Armed Forces because it permits considerable at the zone of burning. The flame is short and
saving in space over other types of magazines. quite hot, and offers a means of lighting a
An Igloo is a concrete building of semi-cylin- series of safety fuses in the desired rotation
drical shape with the axis on the ground and with the lighting time at the face being no
with earth covering the arched roof and piled greater than that necessary to light one fuse
up against the sides. This earth acts as a bar- The product is available in two burning
ricade and also serves to conceal the Igloo as speeds: namely, Type A Cord burning at the
much as possible from view approximate rate of 8 to 10 seconds per foot,
The usual sizes of igloos are: 26’6” x 60’8” and Type B Cord burning at approximately
and 13’ to the highest part of the roof, or 16 to 20 seconds per foot. Type A Cord is
36’ x 62’ and 11‘6” to the highest part of the intended for use in stoping rounds where the
roof blasts may contain a large number of holes or
Usually igloos are built in groups of seven, where the holes are normally collared from 2 to
so arranged that one is in the. center and six 4 feet apart. Type B Cord is better suited for
others around it as on the corners of a hexa- use in heading or development rounds where the
gon (Ref 1). Each igloo holds 143,000 lbs of holes may be collared much closer together.
explosives, making a total for the group of one Both types of cord are clearly marked at one
million pounds. With this arrangement, a 7- foot interwds so that the fuses may be easily
igloo group occupies a circle of 1000 ft diameter spaced to insure positive rotation. Metal con-
with about 1,920 ft between the nearest build- nectors are available for connecting safety fuse
ings of adjacent igloo groups, and occupies only to the cord. These connectors are crimped to
,about 3370 of the space required by older types the safety fuse at the same time that the caps
of magazines for the same amount of explosives are crimped, and are so constructed that they
According to Hall (Ref 2), the usual 800 protect the” end of the safety fuse from mois-
feet, which has been prescribed as intermagazine ture. They contain a small pressed charge of
distance for unbarricaded surface magazines con- an ignition compound which lights the fuse
taining 250,000 Ibs of explosives, may be re- when the cord burns through the connector
duced to as low as 185 feet in the case of Ignitacord is subject to ignition by open
igloos or underground magazines flame, sparks, friction or a sharp blow. The
Refs: 1) G.L. Schuyler, US Naval Inst Pro- connectors can be ignited by heavy impact; as,
ceedings, 56, No 323, pp 31-32 (Jan 1930) 2) for example, from falling rocks. Ignitacord must
D.C. ,Hall, Army Ordnance, 33, No 169, p 46 not be used as a substitute for safety fuse, or
(1948) 3) US Army, AMC Regulation AMCR in any place where an open flame i’s prohibited
385-100 (April 1970), “Safety Manual;’ pp 8- Refi Blasters’ Handbook (1958), pp 100 &
16, 17-6, 17-16 & 17-32 225-27 ,,

Ignis Volatilis. (Flying Fire) (Feu volant in IGNITERS

French). A kind of Greek fire used militarily, Igniter. My device serving to ignite either
explosives, propellants or pyrotechnic compo-
 16

sitions, may be called an igniter. The follow- Rejl duPont Co’s advertisement in Ordn 50,
ing igniters may be listed: safety fuse, for No 276, 583 (1966)
ignition of Black Powder and blasting caps;
igniter pad, for ignition of propellants in Igniter Cord. Extruded incendiary cords of
camon; electric igniters, quick and slow matches, thermoplastic consistency are prepd by com-
quills, squibs, miner’s squib igniter fuse, igniters bining powd oxidizing and reducing agents in
for pyrotechnic co,npositions, igniters for rockets, a plastic binder. Thus, 33 parts plasticized
igniters for tracers, etc. All of these devices are nitrocellulose (I) (consisting of high-N, 10w-’
briefly ‘described under their individual headings viscosity nitrocotton 50, di-Bu phthalate 48,
Phz NH 2, and citric acid 2 parts) was heated
Igniter Bag or Pad. Separate-loaded ammunition in a Werner-Pfeiderer mixer with 66 parts Si
used ‘in cannon of larger caliber, consists of a (specific surface 38,000 sq cm/cc) and 1 part
propellant charge loaded in cotton or rayon (for- N, N’-diethylcarbanilide (II). Another mixt contg
merly silk) bags, which are loaded directly be- I 14P Pb304 60.6, KC104 24.7, and II 0.7 parts
hind the projectile in the breach of the gun. At was prepd separately. The 2 mixts were rolled
the base of the bags, a flat pad in the shape of into sheets, diced to 3/16-in cubes, and fed
a disc (igniter pad or bag) made of closely- to a screw extruder in a 1:3 ratio. After
woven cloth and fdled with Black Powder, is extrusitm at 100° to a diam of 0.065 inY the
sewn or laced. The charge of this bag is ig threads were coated with a 0.004-in poly-
nited by means of a primer located in the ethylene film, giving a product with a burning
breach behind the powder and then the flame speed of 36 see/yard. 1 can be replaced by
is transmitted to the propellant charge (smoke- a 60:40 mixt of polystyrene (mol wt 80,000)
less powder) with di-Bu phthalate or a 40:60 mixt of
Sometimes, in addition to the igniter bag, a poly(methyl methacrylate) with di-Bu phthalate
charge of Black Powder running through the Refi K. J. Brirrdey, BritP 787411 (1956) &
propellant in the form of a “core” is also used CA 52, 7704 (1958)
Refs: 1) Hayes (1938), pp 34-35 ‘2) Ohart (1946),
pp 184 & 189 3) Also see Sect 3, Part D of Igniter Core. See Igniter Bag
Vol 4, pp D795-97
Igniters, Delay, Electric. Devices used for igniting
Igniter Bag (Used A flat bag fdled
in Rockets). Black Powder charges. They consist of
with Black Powder and placed near the pro- copper, other metal or plastic tubes provided
pellant about the middle of the rocket motor. with an ignition mixture (which can also be
This serves as an auxiliary igniter to the main Black Powder) in which is embedded a piece of
one (see Rocket Igniter), which is placed in the resistance wire (bridge), with two leads attached,
throat of the nozzle. For more information, see similar to electric blasting caps. Pieces of safety
Ohart, (1946), p 334 or books on rockets fuse of various lengths, to provide different de-
lays, may be attached to the closed end of tube,
Igniter Composition. See Ignition Composition and the loose ends of the fuses are then dipped
in wax for waterproofing
Igniter Cord. Called Pyrocore and developed by When ready for firing, a small section of the
the duPont Co, it consists of a small continuous fuse is cut away at the waxed end (to expose a
metal tubing contg a detonating (HE) ignition clean surface) and, imbedded in the main Black
core. The core is flame sensitive and promotes Powder charge to be used in the blast. When an
ignition at the speed of detonation. Upon electric current is passed through the bridge wire,
functioning, the “Pyrocore” produces high- the wire is heated to incandescence and ignites
velocity hot metal particles capable of igniting the flash powder in the igniter. The ignited
a variety of igniter and proplnt compositions. powder burns with sufficient intensity to rup-
One use of this device is in combustible ture the Cu tube, igniting the fuse (attached to
cartridge ammunition (see Vol 2, p C79, Ref it), which communicates the fire to the main
25), where instantaneous j~nition is required charge of Black Powder. See also Sect 1, Part
A in Vol 4, pp D733-34
 17

Igniters, Devices intended for firing

Electric. Safety fuse match lighter consists of a paper
explosives of the Black Powder type, primarily tube 1%“ long and of the same diameter as the
in commercial blasting. Their construction is fuse. One end of the tube is closed and coated
similar to that of electric blasting caps except with the same composition as Swedish (safety)
that the capsules (tubes, shells) can be made matches. The open end of the tube is slipped over
of wood, paper, cardboard, plastic, etc instead the freshly cut end of a fuse so that, the match
of metal, such as Al, Cu, gilding metal or composition is against the end of the fuse. By
German silver. As a fdler, these caps usually striking the match end of the tube against the
contained an igniting compound, such as mealed coated side of a safety-match box, the match is
powder fixed with guncotton, or other flash ignited and this in turn ignites the fuse. The
mixtures, packed around the bridge wire. See al- match end of the tube can also be ignited with
so description of Squibs in this section an ordinary match (Ref 4)
Ret Marshall 2, (1917), 545 The lead spitter, pull-wire & hot wire fuse
lighrers ,are described in Sect 1, Part A
Igniters for Firearms. (Historical) See Sect 2, of Vol 4, p“D733
Part C in Vol 4, pp D753-756 Closed Flame or Safety Igniters
A device invented by Lagot (1881), con-
Igniters for Fuses. Devices for igniting a safety sisting of a tube fdled with pieces of charcoal
fuse, which then explodes a blasting cap which impregnated with a compound (such as nitrate)
in turn explodes the main charge, may be divided which permits the charcoal to burn in absence
into the ones intended for use in blasting of air and without producing flame. The tube
operations where an open flame or a spark is of has an opening just large enough for the in-
no danger (such as quarries, non-gaseous mines, sertion of the end of a fuse to be ignited (Ref 1)
etc) and those for use in gassy or dusty-coal Master fuse lighter consists of a waterproof
mines, where no open flame or spark should be fiber shell. covered with flexible rubber sheeting.
allowed. The” last named igniters may be called A charge of ignition composition is placed in
safety igniters (allumeurs de sdletf in French) the base of the shell and a freshly cut “pilot
Open Flame Igniters fuse” and six fuses leading to boreholes are in-
Amadou or tinder igniter is the oldest of serted through the rubber covering. The pilot
these devices, in which the heat produced by a fuse is ignited from the outside and it ignites
glowing tinder was utiIized to ignite the core the ignition composition inside the shell which
of a fuse. The tinder itself was ignited by means then simultaneously ignites the other fuses
of sparks produced on striking flint with steel The use of this lighter insures better results
Wick igniter utilized the heat produced by a in rotation firing and allows more time for. the
slowly burning special wick, which was ignited blaster to retire before the detonation of the
by flint-steel, as above first charge, since he has only the pilot fuse
Ordinary mOtCheSare most frequently used to light. The use of this type of fuse has the
at the present time, but they are not satis- disadvantage of requiring large amounts of
factory in wind or rain. Neither is it convenient fuse (Ref 4)
to use them for lighting a number of fuses Heath and Frost proposed a modification of
trimmed to fire in rotation because these must the miner’s safety lamp so that it was possible
be lighted quickly, surely and in a specified to use it to heat a small piece of iron to in-
order (Ref 4) candescence which could then be touched to
In order to get better results when using the open end of a fuse. This operation was
ordinary matches, the free end of the fuse is done in such a manner that no flame or spark
slit open (about l/4’~ lengthwise) and the head was produced outside the enclosure of the lamp
of a match is inserted in this slit so that it (Ref 1)
touches the core of the fuse. After this, the Bickford’s Collier Safety Lighter, invented in
head is lighted by another ordinary match; by 1889, consists of a tube (tinned-iron or steel)
this means the fuse is ignited more readily than closed at one end and containing a mixture of
by a single match KC103 and sugar, pressed into a pellet not
 18

..
exceeding 100mg in weight. This is placed in . fuse was achieved (Ref 1) ..’.
close contact with a hermetically sealed glass “. Hargreaves patented a device in which the
capsule containing coned Hz SOq. A length of ‘;, fuse was ignited by friction (Ref 3)
specially prepd and waterproofed safety fuse is ~ Most of the devices described above are no
fitted into the open end of the tube, the joint longer used and are only of historical interest
being cementedwith tape to form a closed Today, in gassy mines” in the US, the ex-
chamber. By squeezing the tube with pliers, the plosive cartridges are detonated directly with
glass ampule is broken. This brings the H2 SOq electric blasting caps (Refs 4 & 5), without the
into contact with KC103 + sugar, ignites the use of safety fuse
mixture which in turn ignites the fuse (Refs 1 &2) However, safety fuses are still used in some
This device “may be considered as a modifi- norugassy mines, in agricultural blasting, etc
cation and improvement of the devices proposed Refs: 1) Daniel (1902), pp 10-14 (under
by Roth and by Zschokke. In the latter, ”a glass “Allumeurs”) 2) Marshall, 2, pp 537-9 (1917)
capsule containing Hz S04 was wrapped in a 3) A. F. Hargreaves, BritP 13880 (1913) 4)
piece of cloth impregnated with a concentrated DuPont, Blasters’ Handbook (1950), pp 80-81
solution of KCIOS + sugar (Ref 1) ‘‘ and 92-94 5) Olin Industries Inc, Explosive
Mortier used a small piece of metallic Products, 2nd ed, p 38 6) DuPont, Blasters’ Hand-
sodium coming in contact with a drop of water book (1958), pp 97-102& (1969), pp 98-102
to ignite fuses (Ref 1)
Muller, about 1880, invented a device which Igniter Pad. See Igniter Bag
was essentially as follows: the cut end of a fuse
was inserted into a tightly-fitting priming cap, Igniters for Propellants. Devices acting as inter-
which in turn was placed inside a special, her- mediates between priming charges and pro-
metically sealed pistol. The cap was fired when pellant charges and serving to produce a flame
struck by the pistol firing pin and this ignited larger than the one produced by a priming cap
the fuse. The flame produced by the priming In small arms cartridges, where the propel-
cap remained inside the pistol (Ref 1) lant grains are of small dimensions and the
A similar device was proposed by Hohendahl charge itself is small, proper ignition may be
in 1896 achieved by a primer cap without introducing
The Miner’s safety match was patented by any. auxiliary device, such as an igniter
Pope and manufactured during the latter part of On the other hand, in guns, where the pro-
the 19th century by William Bennett Sons & pellant charge and the grain size of the powder
Co of Camborne, England. It consisted of a are both large, it is impossible to achieve
slightly tapered metallic tube, the narrow end proper ignition unless either the size of the
of which was closed. A small quantity of priming primer is increased considerably or an inter-
composition was placed inside the tube and mediate charge of easily ignitable material is
then a tightly fitting fuse was inserted so that introduced. Of these two methods, the former
the open end of the fuse touched the priming is undesirable because the use of large primers
composition. By rubbing the closed end of is not only dangerous but is also much more
the tube against a surface covered with a expensive. Thus it is the latter method that is
friction compound, sufficient heat was produced commonly employed, provided a proper sub-
to ignite the priming composition inside the stance is used in the igniters. The usual pro-
tube and that, in turn, ignited the fuse (Ref 1) pellant igniter is Black Powder because it is
A device invented’ by Meinhard consisted of easier to ignite than smokeless powder and be-
a metallic tube, 20cm in length, closed at one cause it produces a large flame of uniform in-
end. Inside the tube was’ placed a smrdl tensity independent of “the pressure developed
quantity of priming explosive and on top of in the barrel of the gun
it the fuse was inserted so that it fitted tightly Igniters used for separate loaded ammuni-
On striking the end containing the priming tion of larger caliber cannons are called “Igniter
mixture with a hammer, or other object, ig- Bags” and were described above. Igniters used
nition of the priming mixture as well as of the in fixed ammunition of cannons of medium and
small caliber consist of a long, narrow, per-
 19

forated tube filled with grains of Black Powder, it is heated to incandescence and ignites the
closed at one end and attached to the per- flash powder. The ignited powder burns with
cussion primer at the other end. The tube sufficient intensity to rupture the Al shell and
penetrates the propellant charge to as much as the flash thus produced ignites the next element
3/4 the length of the cartridge. In this arrange- in the train, which can be either a Black-Powder
ment, the percussion primer is struck by a blow charge, a slow-burning fuse or a flash-initiated
of a firing pin.l%k sets the priming charge detonator (Refs 1 & 2)
afire, which then ignites the Black Powder in the Electric squibs will ignite pelletted Black
perforated tube. The flame of burning Black Powder which is too wet to be fired with a
Powder shoots through the perforations and ig safety fuse. In blasting operations they permit
nites large areas of the propellant powder, in- tight tamping of the bore hole, the ignition of
suring proper propulsive action. When the igniter the powder charge at any desired point, the
and percussion primer are assembled as one unit, tiring of a number of shots at the same time
the ensemble is called a combination pn”mer, or and definite control of the time of firing the
primer-igniter. The function & location of primer- charge. Electric squibs are considered ,the safest
igniters in artillery ammunition is described in and most effective means of firing black
Sec 3, Part D in Vol 4, pp D777-803 blasting or pellet powder (Ref 3)
Igniter, @rotechnics. Any device used for Electric squibs may also be of the delay
igniting pyrotechnic compositions, such as ‘ type, varying in length from 3-1/8 to 5-1/8”,
illuminating, smoke, tracer, flare, photoflash depending on the delay time (Ref 1)
mixtures, etc may be called “pyrotechnic igniter” Refs: 1) Ohart (1946), p 59 2) Olin Industries,
and the compositions used in such igniters are Inc, “Explosives Products,” Pamphlet, 2nd
called “igniting mixtures” or “igniting charges” edition, p 38 3) DuPont Blasters’ Handbook
Igniter, Rocket. There are generally two (1949), p 80
igniters in a rocket motor, the main and auxil-
iary. The main igniter consists of a primer and Igniter Tests. Assembled electric igniters intended
a charge of Black Powder, or other igniting for military use are usually subjected to the follow-
mixture, contained in a plastic body (generally ing tests, after selecting 10 samples for each test:
ethyl cellulose) and placed in the throat of the 1) Material and Workmanship. All materials
nozzle of the motor. The primer is fired by the shall be of high grade and all parts free from
heat generated in a wire by means of electric chips, dirt, grease and other foreign matter.
current, thus igniting the Black Powder of the The seal between the two wires and the cup,
igniter, which in turn ignites the propelling tube, etc shall be continuous. If the seal is
charge, usually consisting of grains of double- questionable, it is subjected to a pneumatic
base powder (Ref 1, p 333-34) test by introducing an internal air pressure of
In addition to the main igniter, there is an 4 psi, held for 3 seconds
auxiliary one, described under Igniter Bag for 2) Continuity of Circuit and Resistance is
Rockets to be determined by means of a Wheatstone
igniter Squibs. The squibs are essentially bridge
electric detonators except that’ they produce a 3) Waterproofness( Water Submersion Test).
flash & not an explosion. The commercial type Ten igniters are kept under water for 18 to 48
squib, which is also used for military purposes, hours (depending on specification requirements)
consists of an rduminum shell 7/8 to 1-1/2” at 70-75° F and then fired immediately
long with the flash charge in the bottom of the 4) Current and Functioning. The terminals of
closed end. It contains an electrical firing each of 10 igniters shall be connected, one at
element in the form of a bridge wire and two a time, in series with an ammeter, a rheostat
lead wires sealed in the other end with water- and a source of direct current (new dry cell).
proofing compound or a deformable plug that Move the rheostat until the igniter is tired and
is crimped into the open end of the shell. About note the current (amperes) required for it. Note
0.5 ampere is required to fire the squib; when also if the igniters function pr~perly on firing;
the current is passed through the bridge wire, the metallic (or plastic) shell should be ruptured
 I 10

but the sealing plug should not be blown out During WWI, in the so-called “perforated
Note: Sometimes, requirements call for luminous ball cartridges, ” fired from airplane
conditioning the igniters at high temperatures, machine guns, the Germans used two charges,
say 150°, for 1 hour before firing besides the propelling charge: an illuminating
5) Igrrition [email protected] the igniter is of the charge consisting of Mg 64.7, Sr(N03 )Z 19.3,
delay type, it is necessary to determine the time Ca(OH)2 11.7 and resinous matter 4.3%; and
elapsed from the start of current flow to the above it, an igniter charge consisting of KMn04
rupture of the igniter case. For instance, the 54.9 and iron powder 45.1% (Ref 3, v 1, p 192)
M12 electric igniter has an ignition delay not During WWII, the Germans developed two
exceeding 100 milliseconds (Ref 2) types of igniter mixtures:
6) Detailed Examination of Parts. Sometimes a) Barium peroxide t metallic magnesium +
it is necessary to take the igniter apart and binder;
submit the shell (metal or plastic), the wires, b) Barium nitrate + metallic magnesium +
sealing compound and igniter compound to a binder (some compositions also contained
physical and chemical examination. The dis- Styphnic Acid)
assembly operation should be carried out behind The barium peroxide mixtures were similar to
a barricade, preferably by remote control. The the American “Igniter K“
tests are usually different for each type of Examples of type a):
igniter and are described in the corresponding 1) Ba02 78.4, Mg 19.1, binder 2.5%. A quan-
specifications tity equal to 0.67g was used in each 20mm HE
Refs; 1) US Army Spec 50-49-1 2) US Army self-destroying projectile
Spec 50-49-2 3) US Army Spec 50-12-14B 4) 2) BaOz 75.0, Mg 22.0, binder 3.0%. A quan-
US Army Spec 50-78-7 tity equal to 0.30g was used for each 37mm
Igniters for Tkacers and their Compositions APHV shell
Igniter compositions for Tracers 3) BaOz 69.7, BaC03 13.5, Mg 14.2, binder
are designed to be nearly gasless and to have 2.6%. A quantity equal to 3.Og was used for
low ignition temps. Some of these compositions each 88mm AP shell
are described in Vol 4, Sect 3, Part C, p D774. Examples of type b):
They are usually pressed into a cavity at the 1) Ba(N03)z 32.7, Mg 36.7, Na Picrate 11.9,
rear portion of a projectile after first loading binder 18.7%. A quantity equal to 0.30g was
most of this cavity with a tracer composition. used for each 20mm APHV shell
See Fig 30 in Vol 4, p D744 2) Ba(N03 )Z 41.7, Mg 30.0, Sr Picrate 12.8,
A tracer composition difficult to ignite binder 15.5%. A quantity equal to 0.20g was
consists of Sr(N03 )2 65, Mg (powder) 30 and used for each 50mm APHV short-case shell
binder 5 Heiskell claims a tracer unit for a projectile,
This composition has to be ignited by a corn. suitable for improving daylight visibility & having
pound which developes an extremely high tem- a non-flash slow-burning compn which delays
perature, such as Ba02 78, magnesium powder ignition of the tracer compn for a predetermined
20 and calcium resinate 2%. Unfortunately, this time (Ref 5)
composition develops a very bright light which One of the Italian igniter compositions con-
might blind the gunners during night firing. In tained Ba02 75.0, Mg 23.0, binder 2.0% and
order to avoid this possibilityy, an additional 0.9g was used for each 47mm AP Round Nose
charge, consisting of Ba02 78, manganese pow- Shell (Ref 2)
waler20 and calcium resinate 2, is placed on top One of the Russian igniter compounds con-
of the above composition. This mixture is tained Ba02 60.0, Mg 13.6, binder (resin) 26.4%;
easily ignited, but it does not burn with as hot 0.65g was used for each 76mm APHE shell (Ref
or bright a flame as the magnesium mixture. 2)
In this kind of loading, the manganese mixture Refs: 1) Faber (1919), vols 1 & 2 2) D. Hart,
is called the “igniter. mixture,” while the mag- PATR 1335, 6 (Sept 1943) 3) “Data on Ameri-
nesium mixture is called the “Subigniter mix- can & Foreign Explosives,” PB 11544 (1944)
ture” or “Subigniter” 4) Ohart (1946), pp 61-63 & 77 5) R.H.
Heiskell, USP 2899291 & CA 53, 19391 (1958)
 I 11

IGNITION site. Such reactions are said to be diffusion-

Ignition is the act of kindling or setting on controlled
fire any combustible substance. High explosives Combustible systems can be ignited by sparks,
as well as Black Powder, Nitrocellulose, smoke- hot wires, flames, hot particles, heated surfaces
less powder and pyrotechnic compositions can and many other sources. Ignition by sparks &
undergo ignition (burn) without detonating hot wires are of particular interest in connection
The consequences of ignition, ie burning or with explosives and we will therefore consider
combustion, are described under “Burning & them in more detail below
Combustion” in Vol 2, pp B343-B357, under
“Combustion” in Vol 3, pp C425-C433 and Ignition by Sparks. (See also Electricity, Extra-
“Detonation-Development from Burning or De- neous and Hazards Associated with it in Vol 5,
flagration” in Vol 4, pp D245-D252. For further pp E36-E46). In spark ignition the duration of
discussion of the ignition of explosives, the stimulus energy is very short, It is possible to
reader is referred to High Explosives, Hot Spots, pass small electric sparks through an explosive
Hyperbolic Propellants & Initiation Mechanisms gas or explosive dust cloud without producing
in this Vol and to Thermal Explosions in Vol 9 ignition. When the spark energy is increased, a
Some discussion of Ignition, Igniters etc is also threshold energy is eventually obtained at which
presented under Detonators, Igniters & Primers the spark becomes incendiary, in the sense that
in Vol 4, pp D757-D807 a combustion wave propagates from the spark
For convenience, we will divide the subject through the volume of gas. This minimum igni-
of Ignition into the following sections which tion energy is a function of experimental vari-
treat different aspects of the general problem: ables such as the parameters of the explosive
1) Elementary Theory of Ignition 2) Ignition gas and the configuration of the spark gap
Cartridge 3) Ignition Compositions for use A versatile apparatus for determining mini-
with Pyrotechnics 5) Ignition of Firedamp & mum energies for electric-spark ignition of
Coal Dust 6) Ignition–Spontaneous 7) Ignition, gases and dust clouds, developed by Blanc et al
Test for 8) Ignition Theory of Explosives (Ref 1), is shown below
Ilowlbs. c

@lF-
Cemem

1) Elementary Theory of Ignition Inwl

POW1 “ml
;

Introduction UWlt
+0-?4 ktlmvlt d c. (Mails.1 @s
Ila”gea dedloaa
A highly simplified diagrammatic representa- *
tion of ignition is shown in the following

h
Static wltm.ter

““e:
..
TOIVCmtUrC diftcrcncc
&

2
Rotary duwu Micrometer

Since heat loss varies essentially linearly with Ou Ihlet

temperature difference, it predominates at Many data have been obtained with this &
small temp differences. Above some temp TI, similar apparatus (see Ref 7)
heat generation which varies exponentially with Lewis & Von Elbe (Ref 7), in discussing the
temp difference becomes larger than heat loss. theoretical aspects of spark ignition, start with
In this sketch T1 can be considered to be the the supposition that a spark instantly establishes
ignition temperature of the system, although, a small volume of gas within which the tempera-
more accurately, T, = ign temp – initial temp ture is very high. The temperature within the
This simple model represents most of the spark volume decreases rapidly due to the flow
situations of interest for explosives & propellants. of heat to the ambient unburned gas. In the
For dust and gas explosions, however, heat adjacent layer of ambient gas the temperature
generation, ie reaction rate, may be controlled rises and induces chemical reaction, so that a
by the availability of oxygen at the reaction, combustion wave is formed which propagates
 I 12

outward with approximately spherical symmetry. Further development of their model is summa-
Whether the wave develops to the steady state rized in their diagram of a minimal flame
depends on the size to which the inflamed shown below Tu - surface
volume has grown at the time when the tem- T, - surfoce

perature at the origin has decreased to the

Tb-s~face
order of the normal flame temperature. In (I+

order to continue to propagate, the flame should

at that time have grown to at least such size
that the temperature gradient between the burned
gas in the core and the outer unburned gas has .

approximately the same slope as the tempera-

ture gradient in the steady-state wave. If the
— —
size is too small, viz, if the gradient is too steep, ! m. -C
~:’
the rate of heat liberation within the inner more
g.;
or less spherical zone of chemical reaction is in-
sufficient to compensate for the rate of heat loss —0
to the outer zone of preheated unburned gas. In
that case the loss of heat to the unburned gas Note that the temperature profile differs
continuously exceeds the gain of heat by chem- from the total heat profile because the heat
ical reaction, so that the temperature decreases per unit volume depends not only on the local
throughout the reacting” volume, the reaction temperature but also on the local density of
gradually ceases, and the combustion wave be- the flame gas. In the preheat zone the profde
comes extinct after only a small amount of gas of conducted heat coincides with the profde
around the original spark has burned of total heat, whereas in the reaction zone the
Quantitative development of the above model conducted heat gradually drops to zero. The
of the ignition process is overwhelmingly com- difference between total heat and conducted
plicated. Lewis & Von Elbe therefore chose to heat represents the heat gained by chemical
attempt correlation of experimental minimum reaction. The volume integral of the total heat
ignition energies with some energy functions com- is approximately H’, and the volume integral of
puted from minimal flame parameters the conducted heat is approximately H“
One such energy value, denoted by H’, is This model is claimed to agree with experi-
obtained by computing the sensible heat in a ment in that experimentally determined min
sphere of diameter d, assuming that the content ign energies are smaller than either H’ or H“,
of the sphere is completely burned so that its and generally, but not always, H’>H”. For
temperature is Tb and its density is Pb. The details, the reader is referred to Ref 7
heat contained in the sphere in excess of the Ignition of gases resulting in detonation is
heat at the initial temperature Tu is obtained treated in Vol 4, pp D732-32 under “Detonative
from the equation Combustion” & “Detonative Ignition of Gases”
H’ = ~d3cPpb(Tb–Tu) and also under “Detonation (and Deflagration)
in cases” and “Detonatio’n of Gases” etc; “De-
Another energy value which they use is denoted velopment from Burning” etc, pp D360-63.
by H“ and is given by the equation More recent developments in the study of DDT
H“ = nd2: (Tb–Tu) (Deflagration-to-Detonation Transition) will be
u described under Transition to Detonation
Ignition by Hot Wires. Now we turn to a dis-
cussion of ignition by hot wires, but we pur-
posely exclude studies on EEDs (See Vol 5, pp
E63-E68) or initiation of detonation by hot
wires (See Initiation, Hot Wire in this Vol). We
quote Lewis & Von Elbe:
 I 13

“Electric sparks are very hot and fast-acting period. The corresponding critical source tem-
ignition sources. Because the discharge time of perature has a value smaller than the flame
an electric spark is very short (of the order of temperature Tb. As the critical heating period
10-8 to 10-7 second), the energy that is im- is increased (and the current strength corres-
parted to the gas at the end of the discharge pondingly decreased) the critical source tempera-
period is highly concentrated, so that a very ture decreases and the critical source energy in-
steep temperature profde with a very high tem- creases. In terms of unit increase of critical
perature at the center is established. In this heating period, these changes are initially large,
initial stage of flame development the chemical as indicated in the figure, and gradually become
heat liberation is insufficient to maintain such smaller. The temperature curve finally becomes
steep temperature profiie, so that the profile quite flat; this corresponds to the rule, which
broadens and the temperature at the center is inherent in Arrhenius’ law, that at low tem-
decreases. Within a period of time which de- peratures a few degrees of temperature change
pends on the physical and chemical properties produce large changes in the rate of the chemi-
of the gas, and provided that the discharge cal reaction. In the present system this means
energy is sufficient, the profile develops to the that at low values of the critical source tem-
profile of the minimal flame and thence con- perature a few degrees of temperature change in
tinues to propagate as a steady-state wave, the reacting core of the heated volume change
while the temperature in the center settles the rate of heat liberation very greatly. Hence,
down to approximately the value of the flame relatively large changes of critical source energy,
temperature viz, critical heating period, which correspond
“If the same amount of source energy were to large changes of the reaction rate at the
delivered by, say, an electric current over a ignition threshold, produce only small changes
time larger than the time of development of a of critical source temperature”
minimal flame, the temperature at the core Figure 168 is an idealization because it does
would drop below the flame temperature, the not take into account the energy required to
heat liberation in the reaction zone would not heat the source, ie the wire, to some critical
attain a balance with the outflow of heat into temperature. This critical temperature should
the preheat zone, and the flame would become be close to ‘that of the flat portion of the lower
extinct. On the other hand, if the current flow curve of Fig 168. If one assumes that the criti-
were continued for a longer period, the temper- cal wire temperature remains constant in any
ature profile ultimately would become suffi- given ignition system, and allows for heat losses
ciently broad, and the temperature in the core by the wire:
sufficiently high, so that heat liberation within E= A+Bt (1)
the reaction zone overbalances the outflow of
where A is the minimum critical energy for
heat and ignition occurs
ignition and B is the combined rate of heat
“We single out three interdependent quantities
loss from the wire to its soldered ends & to
which characterize the ignition threshold of a
the medium in which the wire is imbedded.
slow source such as described. One is the total
heating time (the time during which the current
flows) which we sha~ call the critical heating
period. Another is the total energy delivered
during this time, which we shall call the critical
source energy, and which defines the current
strength. A third is the temperature Tc in the
core at the end of the heating period, which we
shall call the critical source temperature. The
general form of relation between these three _,.~
quantities is shown schematically in Fig 168.
Thus, the minimum ignition energy, which is Fig 168. Source energies and critical source
denoted of the symbol hc, corresponds tO a temperatures versus critical heating period.
very short (“zero”) value of the critical heating Schematic illustration
 I 14

Figure 1 shows Jones’ results (Ref 3) of his content of the wire per unit length. The second
study of critical firing energies for electric fuse- part should be equal to the product (Tc–Tu)ca,
heads (also known as matchheads). The data in where Tc and Tu are the critical and the ambi-
Fig 1 are for an 80/20 LMNR/KC103 ignition ent temperature, c is the heat capacity per unit
mixture (LMNR is Lead Mononitroresorcinate). volume of wire material, and a is the cross-
sectional area of the wire; it should therefore
vanish when the wire diameter is made vanish-
ingly small. The first part should not vanish

“~
a

2
!
e
Is

1
m
d
10
s.
Fig 1. Relation between ignition energy, mean
tiring current, and critical heating period kl
Ca@s8-’uuw w A’.mm ,%,6
0

The energy plot certainly agrees with the Fig 2. Relation between cross-sectional area of
requirements of Eq (l). Now it would be ex- wire and G= A/l (l=wire length) (Ref 3)
pected that both A & B of Eq (1) would
with wire diameter. The term G should there-
increase with wire length. That it is so is shown
fore be of the form
below (this Fig is also taken from Ref 3)
‘“~ ~“= G= K+La (4)
where K is that part of the minimum critical
energy per unit length of wire which is absorbed
by the medium, and L = (TC–TU)C is the heat
content per unit volume of the wire at the
critical temperature. Figure 2 shows values of
G obtained by Jones for wires of various
diameters. Each point is the minimum critical
energy per unit length of wire for zero critical
heating period and for a given wire diameter.
We may therefore write It is seen that the plot of the experimental
A=G1 (2) points versus the cross-sectional area yields a
where 1 is the wire length and G the minimum curve which is virtually a straight line. Thus,
critical energy per unit length. Further, it would seem that K is determined by the
point of intersection of the line with the G
B= H+JI (3)
axis, and L by the slope. This suggestion
where H is the rate of heat loss to the wire should be treated with some caution because
ends and J the rate of heat flow from the wire K, though not vanishing with wire diameter,
to the medium per unit length of wire. The nevertheless is certainly a function of the
corresponding amount of heat absorbed by the diameter. However, the error introduced by
medium per unit wire length is Jt. This does considering K as constant is not large
not represent the total heat absorbed by the The results of Jones (Ref 3) are in accord
medium, but rather the excess over the heat with the expression
absorbed when the critical energy for ignition
E = (K + La)l + (H + Jl)t (5)
is a minimum, ie when t-= o
It should thus be possible to divide the term which, at a constant wire length 1, is of the
G into two parts–one representing the heat per same form as Eq (1). In Eq (5) K & J should
unit wire length which is imparted to the ex- be functions only of the ignition composition
plosive medium when the critical energy is a and should not change when the wire material
minimum, and the other representing the heat is changed. Conversely Lu and H (at least for
 I 15

a
similar solder joints) should change with wire N= R
material but not with igniter composition. These () ~
expectations are in accord with the observations
of Jones (Ref 3). His experimental findings are Therefore, the rate law is
summarized in the tabulation below:
Values of Critical Temperature and Critical
Energy K for Various Matchhead Compositions
iv=!’
()1

Example 3: Sphere ignited at one point on

Composition LMNR/chlorate Copper acetylide
Critical temp, ‘C 380 440 its surface
Here the boundary between burned and un-
K, cal/cm 0.5 x 10-3 0.6 x 10-3
burned material is given by

Composition Charcoal/chlorate
Critical temp, “C 740
K, cal/cm 1.0 x 10-3 The fraction of material reacted is found by
fiopagation of Ignition. As mentioned at the a simple integration to be
beginning of this article, burning, ie the pro-
pagation of ignition throughout the combustible
medium, has been described in various articles
of this Encyclopedia. However, since an im- Therefore, the rate law is
portant burning mechanism, proposed by
Eyring et al (Ref 2), has not been described,
we present this mechanism below (direct” quote
‘=(:) ”P-’:]
The dependence of N on t has been plotted
“from Ref 2)
Rate Laws of Surface-Burning Reactions in the following figure for these three examples
It is of some interest to find the dependence
of extent of reaction on time, for topochemical
reactions of the surface-burning type, in which
the linear rate of burning is constant
Example 1: Sphere uniformly ignited over
its surface
Here the boundary between burned and un-
burned material is given by
Rlt
—= . .
R, r
and the fraction of material reacted is obviously
a
N=l– R
~’ ()
Therefore the rate law in its integrated form is
a
N=l– 1–; t/T
()

Example 2: Sphere ignited at its, center

Here the boundary between burned and un-
_/.
“ \
burned material i.s given by
R
–= ’1”
R, r
and the fraction of material reacted is obviously

..
 116

General Observations on Iwition of Explosives. Elbe, “Combustion, Flames and Explosions of

In the preceding paragraphs we considered the Gases;’ Chap V, Sects 13 & 14, Academic Press,
general subject of ignition and not necessarily NY (1961)
the ignition of explosives. Since the primary 2) Ignition Cartridge. Some mortar ammunition,
purpose of this Encyclopedia is the presentation eg, US Army 60 and 81 mm mortars, is pro-
of material relating to explosives, we present pelled by the so-called ignition cartridge (which
below a brief recapitulation of observations on resembles sporting cartridges in form). It is
the ignition of explosives placed in the fin stabilizer tube and additional
Primary explosives can be ignited and will’ propellant increments are fastened to the fins
burn without detonating if they are essentially by means of special wire holders. Charges in
unconfined (Refs 4 & 6). Lead Azide appears ignition cartridges (14.5 grains for 60mm and
to be an exception because its ignition results 24.0 grains for 81 mm mortar) usually consist
in detonation or at most a very short-lived of small grains of double-base proplnt, NC 57.75
combustion which almost instantaneously goes * 1.50% with N = 13.25 * 0.05%, NG 40.00 +
over into detonation (Ref 6). However, dextri- 1.50, K2SOa 1.50 * 0.50 & DPhA 0.75 *
nated Lead Azide can be made to flash without 0.10%
detonating (Ref 5) Grain dimensions are: diameter 0~035° and
In order to secure proper functioning of an thickness 0.00325” ~for the 60mm mortar, and
initiating compound, it is important that it can 0.059”1 diam and 0.0100’” thick for the 81 mm
be ignited with comparative ease. Some initiating mortar. The grains are ignited by means of a
substances, however, such as Lead Azide are Black Powder pellet which in turn is ignited by
difficult to ignite, and for this reason are either a percussion primer. The flame from the ignition
mixed with easily ignitable substances, such as cartridge ignites the propellant increments
Lead Styphnate etc, or are primed by small Refs: 1) Ohart (1946), pp 55 & 192 2) US
quantities (0.2g) of some easily ignitable sub- Specification MILC-20480A (July 1954) (.M3
stances as Lead Styphnate or Lead Mono- Ignition Cartridge for 81 mm Mortar Ammunition)
nitroresorcinate
Secondary explosives will burn without deto- 3) Ignition or Igniting Compositions for Use
nating if unconfined or lightly confined. Some With Explosives. substance or composition
Any
secondary explosives, such as PETN, are difficult intended to ignite (but not detonate or explode)
to ignite and propagate burning only at slightly an explosive belongs to this class. This should
elevated ambient pressures include not only all the primary ignition com-
Propellants are designed to burn stably. How- positions, but also any ignition leads which then
ever, ignition of unconsolidated propellants (high transmit the flame to other portions of the
porosity) or large masses of propellant can re- explosive device. It should be noted that, as
sult in detonation there is no strict distinction between priming
Black Powder does not detonate, but under (which can explode or detonate) and igniting
confinement it deflagrates (burns) so rapidly compositions, some of the mixtures given below
that its external effects are almost those of a might belong to either type
detonation (Ref 6) Numerous mixtures have been proposed for
Written by J. ROTH ignition of explosives. Of these, the most
Refs: 1) M.V. Blanc et al, JChemPhys 15, 798 commonly used are mealed gunpowder, finely
(1947) & CA 42, 762 (1947) 2) H. Eyring et al, grained Black Powder, nitrocellulose mixed with
ChemRev 45 (l), pp 164-5 (1949) 3) E. Jones, other substances & finely divided smokeless
ProcRoySoc (London) A198, 523 (1949) 4) powders mixed with other substances
J. Roth, Proc of Conference on Chemistry & For instance, for igniting propellant charges
Physics of Detonation (Jan 1951), p 51 5) J. of smokeless powder, grained Black Powder is
Roth, unpublished work (195 1) 6) F.P Bowden used, which in turn is ignited by means of a
& A.D. Yoffe, “Initiation and Growth of primary ignition composition
Explosion in Liquids and Solids,” Cambridge A primary igniting mixture of numerous US
University Press (1952) 7) B. Lewis & G. Von detonators consists of lead sulfocyanate 45*1
 i 17

and pot assium chlorate 55 tl ‘%0 E. Jones, 29, 8336 (1935); A safety igniter
The primary igniting mixture in the M19 suitable for use with burning (nondetonating)
electric igniter (used for simulating gunflash) explosives, comprised of an electric fuse head
contains dinitrodiazophenol 40t3, potassium (Zr + Pb-2-nitroresorcinate) and a combustible
chlorate 58*3 and nitrostarch 2+0.5$Z0.This material, such as a mixture of finely divided
mixture is ignited by heat produced by in- Pb-Si + Pb3Oq, or Ca silicide + PbCrOQ, or Zn
candescent resistance wire and in turn ignites + KMnOQ or Fe + KMnoq. Both fuse heads as
the charge of Black Powder placed next to it well as the combustible mixtures are of the
The following examples of igniting mixtures kind producing very little or no gas. They are
are taken from Chemical Abstracts and arranged sealed inside a metal container which does not
chronologically. Some of these compositions burst when the mixture is ignited, but is heated
may be also classified as priming compositions only on a portion of the surface to a tempera-
L. Fisher, 27, 1758 (1933); Igniter charge ture sufficient to ignite the blasting charge and
for blasting caps consisting of K3 Fe(CN)6 20-40 not sufficient to ignite the firedamp; BritP
with an oxidizer such as KC103 10 to 30 and 430750 (1935)
a nitrated carbohydrate such as NC 70-30; USP C. E. Sosson, 30, 1564 (1936); Ignition com-
1890112 (1932) position suitable for use in delay detonators:
H. A. Lewis, 27, 4931 (1933); Ignition com- zirconium 50 to 95 used with basic Lead-2-
position used as a top @rimary ignition) charge nitroresorcinate, 02 N. C6Hz (OH)2. COO(PbOH)
in blasting caps, comprising Pb thiocyanate, an (or other lead salts of nitrophenols) 50 to 5;
oxidizer such as KC103 and a solid low-ignition- USP 2027208 (1936)
point fuel, such as pyro smokeless powder. This E. Jones, 30, 4324 (1936); Safety igniter for
mixture ignited a priming charge of LA; USP explosives, consisting of a Cu. tube 33mm long,
1918920 (1933) 6mm in diameter and 0.2mm thick containing
H. A. Lewis, 28, 4235 and 5242 (1934); a charge of 0.75g of finely divided Zn and 40Y0
Ignition composition for blasting caps contains: KMnOa, loaded at a pressure of 60 psi. A fuse
K(SCN)2 30-70, KC103 30-60 and sulfur (as an head of metallic Zr and had Styphnate (LSt)
accelerant) 1 to 20%; USP 1964825 (1934) & is placed close to the composition; CanP 357600
CanPat 340569 (1934) (1936)
C. P. Spaeth, 29, 1252 (1935); Ignition charges J. Taylor & W. Young, 30, 4324 (1936); A
for electric blasting caps containing Tetramethylene complicated device suitable for igniting safety
diperoxide either alone or with various admixtures; blasting explosives without igniting firedamp;
USP 1984846 (1934) CanP 357532 (1935)
C. P. Spaeth, 29, 5660 (1935); Ignition com- A. Stettbacher, 30, 2387 (1936) and Nitro-
position for the top charge in blasting caps, com- cellulose, 6, 202 (1935); Chemical and mechani.
prised of NC impregnated with a liquid explosive cal delay igniters. A review, mainly of chemical
nitric ester, such as NC and KC103; USP 2007223 delay incendiary bombs
(1935) L. A. Burrows, 31, 6467 (1937); An ignition
O. A. Pickett, 29. 6062 (1935); A thermally composition in an electric blasting initiator, com-
fired igniter charge for detonator caps contained prising at least one of the compounds selected
zirconium mixed with KC103 and gum arabic or from the group consisting of the silver and
nit rostarch; USP 2008366 (1935) mercury derivatives of chlorinated azodicarbo-
C. E. Sosson, 29, 7078 (1935); An ignition namidine; USP 2086533 (1937)
composition for use in Iowtension electric fuse L. Burrows, W. Filbert & E. E. Reid, 32,
heads, comprised of a mixture of finely divided 2357 (1938); Ignition charge suitable for electric
metallic zirconium 35 to 39% and an easily ig- blasting caps and containing his- Triethyl Lead
nitable salt of nitrophenol or its derivatives, such Styphnate, C6H(N02)3 [OPb(C2 H5 )3 ]; USP
as Pb-2-nitroresorcinate, 65 to 61. The mixture 2105635 (1938)
may be used either in loose form around the B. Zielinski, 32, 3964 (1938); Ignition mixtures
electric bridge or may be agglomerated with NC suitable for percussion caps, primers, etc and
gel; BritP 428872 (1935) consisting of IS 20-50, Ba or Pb nitrate 30-50,
 I 18

Sbz S3 5 to 30, a friction producing agent such priming compn & other parts ot’ the device are
as glass up to 20% and a sensitizer such as described & illustrated: Britp 5740<’? (1 ~~~~
2,4,6 -Trinitro-l,3,5 -triazido-benzene 0.25to 10%; G6velot & Gaupilat, 47, 8374 (1953); Claim
USP 2111719 (1938) an ignition compn for electrical primers, con-
W. F. Filbert & W. E. Lawson, 32, 5630 sisting of a mixture of dissolved Guncotton with
(1,938); An ignition composition suitable for Pb02 (60%), Pb3 Oq (65%) or KMnOQ (50%).
use in electric blasting initiators, contains the Addition of Sbz S3, C, KC103 or KCIOQ modifies
nitrated product of Pb-diphenylolpropane mixed ignition props of above mixture; FrP 881262
with Zr, KC103 and nitrostarch; USP 2118501 (1943)
(1938) F. B. Clay & R. A. Sahlin, 49, 14326
E. Jones, 32, 8147 (1938); A safety igniter (1955); Igniter comps for tracer projectiles
suitable for blasting charges resembling the one which include a Ca silicide fuel as a partial
described in CA 29, 8336(1935); USP 2127603 or complete replacement for Mg burn in such
(1938) a manner as to give a dim or invisible trace
C. G. Storm, 34, 7605 (1940) and Army to a min distance of 25 yds & a bright &
Ordnance, 21,20-30 (1940); Methods ofim- properly colored trace at greater distances. A
proving ignition of propellant charges are typical igniter comp is Sr02 78, Ba02 4,
discussed Pb02 4, Ca silicide 7 and Ca resinate 7%; USP
L. Burrows&C. Van Winter, 35, 2722 (1941); 2709129 (1955)
A slow ignition charge, comprised either of R. H. Heiskell, 50, 5293 (1956); Claims a
smokeless powder and an oxidizer, such as KC103 pyrotechnic compn as follows: A dark-burning,
or KN03 with or without a metal, such as Al, nonflash igniter mixt suitable to ignite the
Te, Mg, Se or Zr, or a mixture of smokeless tracer compn within a projectile is composed
powders. It is suitable for electric squibs. The of CUO 50, Mn 49, graphite or stearic acid
mixture is heated by means of a bridge wire of 1% to act as binder. Other possible O-bearing
Ni-Cr alloy with “a diam of at least 0.0022’5”, compds include BaOz, Sb205, PbOz & PbCr04.
whereby certainty of firing is assured under con- Another igniter mixt is composed of 80% Ba02
ditions prevailing in series firing; USP 2228339 & 20% sulfide from the group CaS, Cr3 SQ &
(1941) SeS, & a small amt of graphite or stearic acid;
E. I. duPont de Nemours & Co, 36, 274 USP 2726943 (1955) & USP 2726944/ (1956)
(1942); Ignition composition for use in electric R. H. Heiskell, 50, 8208 (1956); Claims
blasting caps, consists of or includes .a double highly stable, dark-burning igniter compns con-
salt of Pb(N03 )Z with a Pb salt of dinitro- taining Biz 03 45-85, Mn 15-55, stearic acid
phenofi BritP 519749 (1940) binder up to 10, and graphite lubricant up to
L. A. Burrows & G. A. Noddin, 36, 2725 10%; USP 2716599 (1955)& USP 2726944 (1956)
(1942); Ignition composition suitable for blasting R. H. Heiskell, 50, 8208 (1956); Claims a
explosives comprised of finely divided colloided nonluminous igniter for initiating ignition of
smokeless powder mixed with 15-25% of the the burster charge of a projectile, consisting. of
Pb salt of a dinitrophenol such as 4,6-dinitio- Ba02 60-7, Sb2S3 21.3-35, asphaltum 1-4 &
cresol-[CH3 .C6 HZ(N02)2 O] * Pb; USP 2268372 graphite 1-4%; USP 2714061 (1955)
(1941) T. J. Mulqueeny, 50,9742 (1956); Claims:
J. Giliies, 41, “6724 (1947); A primary igni- Ignition comps of the Pb-Se type, where the
tion composition for igniting purposes, yielding PbO is produced in situ, ‘were prepd &
little or no volatile matter among the pro~ucts evaluated for use in blasting caps & detonators.
of its combustion, consists of a mixture of This type of mixt afforded less erratic firing
CaSiz and MN02 with or without CUO; BritP times than when the PbO was mechanically
575506 (1946) incorporated. The Pb is oxidized by heating
E. “Jones, 42, 7532 (1 948); Claims ignition in an internally baffled rotating drum in an
device for use in military land mines, contg a oxidizing atm; USP 2740703 (1956)
priming compn consisting of a mixt of HgFul- J. H. McLain & T. A. Ruble, 51, 12494
minate, Sbz S3 & KC103. The container for the (1957); ,An improved fuse for use in firing gas
 I 19

grenades, smoke candles, etc, iS provided by volatile compds 2.0 max, ether extractable
placing a standard primer (I), a first fire charge compds 2.75% max, and Nitrocellulose (12.0
(II), a delay charge (III), & an ignition mixt to 12.7%N) the balance. The av firing times
(IV) in a fuse body. II, which is relatively in- in millisec for caps charged with the various
sensitive to frictional impact, stable, substantially mixes are: 50/50 Hg fuhninate/propellant
gasless, easily ignited, & has a high burning ignition 3.6, total 10.9; 40/60 mix, 3.9 and
temp so as to act as a relay between I & 111, 13.2; 30/70 mix, 5.3 and 18.0; USP 2825639
is composed of Pb30a t 2, Si (V) 33.7 ~ 2, (1958)
Mn 11.2 * 1, celluloid (VI) 1.8 f 0.2%. III, D. T. Zebree, 53, 17514 (1959); Claims an
which has Substidntia]ly the same characteristics improved delay fuse for igniting primary explo-
as H except that on burning it produces a plug- sive compositions in detonators & squibs. The
forming residue to prevent backfiring, is com- preferred delay mixture consists of 60% Ba02,
posed of PbO 76.9, V 19.3, Fuller’s earth 1.5, Se (75/25) & 40% Pb-Sn alloy (85/1 5). Ingre-
VI 1.8 & graphite 0.5%. IV which has substan- dients should be in the 1-701J particle size range;
tially the same characteristics as 11 except that USP 2892695
it gives a large flash & produces a large VOI of H. H. Williams & W. A. Gey, 53, 22957
gas, consists of PbCrOQ 59 f 5, V 19.6 t 3, (1959); Claim an igniter material for ignition
Mg 19.6 I 3 & VI 1.8 t 0.2%. In practice a of solid propellants in a stable, reproducible
small pellet of 11 at about 0.188 inch diam & manner, which builds up pressure gradually so
0.2 inch height & weighing 0.3-O.4g & a ‘pellet as not to cause the propellant grain to chip or
of 111of about 0.188 inch diam & 0.3 inch crack, consists of a mixt of polytrifluorethylene
height & weighing 0.6g are pressed in beneath (I), B, & NH. CIO,. The 1, mol wt 500,000-
the primer under a load pressure of 400-600 1,000,000, serves as a binder for the other 2
lb, another pellet of 111is similarly incorporated. materials & as an oxidizer for the metal. The
The cavity is filled with loose IV, & the whole particle size of the NHOC104 is 1-5P. The compn
is sealed with a crimped-in closure plug; USP is 5.5-7.5% B & the remainder NHOC104 & I in
2792294 (1957) substantially equal amts; USP 2900242 (1959)
Th. Goldschmidt, 52, 3346 (1958); Safety D. T. Zebree, 54, 2745 (1960); Claims an
igniter for miner’s lamps prepd from Al-bearing initiating device having a delay fuse element &
Ce alloys; GerP 926654 (1955) a loose ignition mixt (Pb 72.4/Se 27.6% by
W. J. H. Schneider, 52, 5825 (1958); Claims wt) in contact. Incorporation of 1-570 Si, which
an igniter composition consisting of Tribasic increases the heat of combustion of this mixt,
Pb picrate, Pb(C6Hz07N3)2 .3 Pb0.2.5H20, compensates for deteriorations which occur in
having an explosion point of 160-80°, and an ignition mixts, esp useful for blasting caps;
ignition delay of 0.6, 1.5, and 4.7 sec at 260, USP 2908559 (1959)
250, and 240°, resp, is prepd by reaction while W. E. Schulz, 55, 3062 (1961); Claims ig-
hot of a sol Pb salt and a picric acid (1) soln niting comp, a mixt of Mg, Te & TeOz loosely
contg 7.3-7.5 moles NaOH per mole of I; FrP packed for use in elec actuated squibs. The
1026869 (1953) ignition temp of this mixt is higher than that
Mulqueeny & F. R. Seavey, 52, 7704 of other squib compns; a 3-5 amp, or larger,
(1958); An explosive train for elec detonators firing current is typically desirable. Ignition
and blasting caps is described having a cyclonite time, functioning at low & high temps & at
base charge, a Pb azide initiating charge, and low pressures, storage stability etc are good.
an ignition charge; the initiating charge is Typical comps are: 5/88/7; 16/78/6; 27/67/6;
placed between the, ignition and base charges. & 36/59 /5% by wt Mg, Te & TeOz resp in
The ignition compn consists of 30-50% loose, each case; USP 2953447 (1960)
dry Hg fulminate’ (40-90% through 200-mesh E. J. Walden, 55, 25258 (1961); Claims
sieve) mixed with 50-7070 ground, dense pro- ignition delays at -65° F of a rocket propellant
pellant (100% through 60-rnesh sieve). The from NH4 N03’ &, a butadiene-methyvinylpy ridine ,
propellant compn is diphenylamine 0.3-1.2, - copolymer (90: 10) are reduced 50% by the
graphite 5.0 max, ash 3..0 max, moisture & inclusion of pellets composed of KC104 26.5,
 I 20

Ba(N03)z 16.6, Zr-Ni alloy (50:50) 53.9,&Et to electrostatic discharges may be prepd from
cellulose 3.0% embedded in the ignition-sustaining amorphous B & Pb oxides in the following
material; USP 2990683 (1961) mixt ranges: B 1.5-2.5, PbO 97.5-98.5; B 8-
S. V. Peyton & E. Williams, 56, 14523 (1962); 30, PbO 70-92; & B 15-30, Pb3 Oq 70-85%.
Claim a compn for ignition by stab-pin or flash, Thus, 10g 90-7% pure amorphous B & 490g
containing Pb 2,4-rlinitroreso rcinate 50, Ba(N03 )2 51.L99% pure PbO are ball-milled with 0.7kg
45, & tetrazene 5$%by wt. It has very good thermal H20 for 16 hrs, dried at 212-25°F to <0.1%
stability, & its life in hot & moist storage is very Hz O, & passed through a 20-mesh screen. The
much longer than that of fulminate mixts. It screened particles are electrostatically grained
is highly compatible with Al, Cu, brass & Sn- by tumbling in a glass jar at 65 rpm for 2.25
plated Cu & also with Pb(N3 )2; BritP 892741 hrs. When incorporated into a cap, these compns
(1962) exhibit an a c breakdown voltage of 1.4-2 .2kv.
L. G. Herring, 56, 15720 (1962); Claims a They also show a consistent bridgewire sensi-
pelleted igniter made by mixing a mixt of tivity & burn in a gasless & non-violent manner;
powd Zr & Ni with a powdered inorg oxidant USP 3317360 (1967)
& a small amt of Et cellulose; this mixt is D. H. Lee & D. D. Evans, 66, 67510 (1967);
pelleted & dried to remove excess solvent; USP Claim a simple, efficient means of ignition of
3017300 (1962) the monopropellant Nz Hq, provided by use of
J. D. Clark, 60, 7864 (1964); Claims an a fluid bed consisting of carrier pellets of A1203
igniter for a rocket propellant consisting of a impregnated conventionally with a Nz Ho -decompn
HN.03 soln of an amine nitrate, such as diiso- catalyst such as a mixt of the oxides of Fe, Ni
propylamine nitrate, is provided by a dough- & Co, a layer of the pellets L 0.25 in thick at
like mixt of about 85% of a metal hydride, the Nz Ha feed end of the bed being coated
such as LiH or LiAlH4, mixed with about 1570 with a powerful, Hz O-soluble, solid oxidizer
of a dry rubber cement. The igniter presents such as KMn04, KC103, or, preferably, 1205
a large contact surface & is supported within which causes ignition of the initial Nz ~. The
the rocket chamber in such a manner that, heat thus developed raising the temp of the
when the monopropellant is allowed to im- bed sufficiently to self-sustain Nz ~ decompn;
pinge on it, as through a spray nozzle, the USP 3298182 (1967)
heat of reaction increases the monopropellant 4) Ignition Compositions for Use With Pyro-
to the ignition temp & heat of combustion technics. This subject was treated in consider-
causes decomp of the igniter; USP 3115005 able detail in Vol 4 under Detonator, Igniters
(1963) and Primers, Sect 3, Part B & Ignition Train
R. L. Shimpaugh, 62, 12969 (1965); Claims Used in ~rotechnics, pp D759-768, with the
,an ignition compn consisting of Ba chromate, following additional reference:
boron & lead dioxide for use in electric deto- Gordon & Campbell studied preignition &
nators; USP 3123367 (1965) ignition reactions of the pyrotechnic system
W. A. Proell, 64, 12454 (1966); Claims a mixt Zn–C6 CIG–KCIOO. They found the following
of Black Powders 30-50 & smokeless powder reactions to be responsible for preignition, ig-
50-70%, compressed into a coherent cake to, be nition, and combustion phases of this system:
used for igniting propellants; USP 3234059 (I) 3Zn + C,C16 + 3ZnCl, + C; (II) 4C + KC1O,
(1966) + KC1 + 4CO(+COZ ); (III) 4Zn + KCIOq + KC1
(No author cited), 67, 10158 (1967); + 4Zn0. Reaction I is exothermic and together
Claims an ignition compn having excellent low with reaction 11 raises the temp of the system
pressure ignition properties, consisting of a to >500°. At temps above 4210 the preigni-
monovalent or polyvalent metal powder, eg tion reaction III becomes highly exothermic
Al, Cu or Mg; a metal oxide, eg Pb02 or and propagation ensues in the neighborhood
Ba02; & 15% B as an activator; GerP 1243067 of 520°
(1967) Refl S. Gordon & C. Campbell, 5th Symp on
G. B. Young & S. J. Lubinski, 67, 55840 Combustion (1955), p 277 & CA 50, 573 (1956)
(1967); Claim a new ignition charge resistant
 I 21

5) Ignition of Firedamp and Coal Dust. Many Termination:

disastrous coal mine explosions have been caused e) OH + wall = destruction
by the ignition of firedamp (methane/air mix- f) CHO + 0, = CO + H02
tures) and/or coal dust. ,The subject of tiredamp- H02 + wall = destruction
coal dust explosions has been studied extensively. H2C0 + 02 + W~ = destruction of Hz CO
r Some of this extensive literature was reviewed Without going into details, it is clear that the
in Vol. 3 under Coal Mine Explosions, pp C360- overall oxidation reaction will be affected by the
378, & under Coal Mining Explosives, Non- fate of OH radicals (as well as other intermediates).
Permissible, pp C437-444, & Coal Mining Ex- For example, if the rate of step a) & d) exceeds
plosives, Permissible, pp 444-459. Below we give that of steps b) & d) the oxidation of methane
recent references on the ignition of firedamp will proceed & conversely. Further complication
and present a cursory discussion of the mecha- is introduced because step d) depends on the
nism of firedamp oxidation (ignition & com- relative rates of steps c) & f). Thus it is not
bustion). This complex mechanism tends to surprising that minor changes in reaction con-
explain the great variability in experimental ditions, which can affect different elementary
results on firedarn”p ignition & to furnish some reactions in different ways, can lead to major
excuse for the unfortunate fact that coal mine changes in overall reaction rate, and indeed be
explosions still occur even after almost a cen- the difference between ignition & non-ignition
tury of intensive international effort to elimi- The ignition of firedamp (coal-dust explo-
nate them sion are generally considered to be triggered
The oxidation of methane (as well as other by firedamp explosions, therefore we will make
hydrocarbons) proceeds via a chain branching few further comments about coal dust explo-
mechanism. Each of the stages of the chain sions) by explosives presents its own set of
branding mechanism: initiation, propagation & problems. Among these are the high tempera-
termination, may be affected to a different tures of detonation products, the possible
degree by relatively slight changes in ambient presence of radicals in these products which
conditions under which oxidation takes place. can promote ignition in the methane (as dis-
The cumulative effect of these “slight” changes cussed above), and the adiabatic compression
on the over-all reaction may be quite large and heating of firedamp pockets by the blast.
and lead to ignition or non-ignition under what Presumably all these possible ignition mecha-
appears to be very similar circumstances. Simi- nisms are minimized by proper stemming of
larly, once ignition has been effected, its pro- the bore-hole (Ref 2), the presumption being
pagation (burning and/or explosion) is also that the products and blast now emerging
subject to the variability described above from the bore-hole have been attenuated in
The following reaction scheme is taken from temperature, radical concentration & blast
Lewis & Von Elbe (Ref 1) to whom the reader pressure. Experience shows that, although
is referred for details: good stemming may be helpful in reducing
Initiation: the incidence of tiredamp ignition, it does
CH4 + 02 = CH300H not completely eiiminate ignitions. To some
CH300H = H2 CO+ H20 extent this may be due to fissures in the
coal seam, containing firedamp, crossing the
Propagation & Chain Branching bore-hole. Also the amount of stemming
a) H2 CO + 02 =. free radicals ~ OH required to obtain the necessary degree of
OH + CI-& = Hzo + CH3 attenuation may make its use uneconomical
CH3 + 02 = H2C0 + OH Two approaches are now used in attempts
b) OH + H2C0 = HZO + CHO to prevent fire damp ignition by explosives.
c)cHo+o~+M=cHo3+M The first attempts to reduce the temperature
d) CH03 + H2 CO = 2C0 + HZO + OH of detonation products of the explosive, and
(M is a third body) the second introduces flame-suppressing
materials at and near, the face where blasting
 I 22

operations are carried out. The first scheme nition of firedamp by these explosives
involves “sheathing” the explosive or incorpo- 4) H. G. Wolfhard & M. Vanp6e, “Ignition
rating into it materials that act as “heat sinks.” of Fuel-Air Mixtures by Hot Gases and Its
This has been discussed in Vol 3, pp C437- Relationship to Firedamp Explosions,” pp
444 & pp 444-459. The most widely used 446-53 in 7th Symp Combstn (1959)
practical application of scheme two is “rock-
dusting,” ie dusting the inside of the mine 5) R. W. Van Dolah. et al, US Bur of Mines,
with fine limestone.. Rock-dusting appears to RI 5863 (1961) & CA 55, 27886 (1961)
be quite effective in preventing coal-dust “Relative efficacy of stemming materials in re-
explosion but is not so effective in preventing ducing incendivity of permissible explosives.”
methane-air explosions. Other dusts, such as Stemming, used to confine explosives in shot
lithium halides, appear to be more effective holes in underground coal mines, minimizes
than limestone, but their use is not economical the chance of ignition of firedamp or coal
dust by the detonation products. Tests by the
Modern coal-mining practice tends towards
the use of mechanical devices, such as Gzrdox, Bureau of Mines indicate that NaCl, pure Hz O,
Hydrox & Mechanical Miners rather than ex- gelled water (3% carboxymethyl cellulose), and
plosives. This will not necessarily reduce the a coned salt-H2 O soln are more effective than
number of coal mine explosions because these an equal wt of wet or dry tleclay. The Hz O,
may be, and indeed are known to be; initiated gelled Hz O, and salt-Hz O soln are equally
by other means such as faulty electrical equip- effective. The approved stemming device is
ment, breakage of electrical cables or other distinctly inferior to 1 lb of dry fireclay
means of producing a hot spark or arc 6) N. E. Hanna et al, US Bur Mines RI 5867
Written by J. ROTH (1961) & CA 55, 27886 (1961). “Factors
Refs: 1) B. Lewis & G. Von Elbe, “Combustion affecting the incendivity of permissible explo-
Flames & Explosion of Gases,” Academic Press, sives. Ammonium Nitrate and carbonaceous
NY (1961), pp 91-110 2) R. W. Van Dolah material.” Analysis of 15 specially prepd
et al, US Bur of Mines, RI 5863 (1961) & CA explosives, with 3 particle-size ranges of
55, 27886 (1961) NHQN03 and 5 types of carbonaceous material,
showed that the particle size of NH4 N03 in
References, & brief abstracts when available, permissible-type formulations had a highly
to studi’es of firedamp and/or coal dust ignitions significant effect on the incendivity of the
& explosions, not listed in previous Encyclo- explosive to firedamp, with coarse N~ N03
pedia Vols are given below: producing less incendive explosives than the
1) S. “Shaw & D. Woodhead, “Igniters for Experi- fine. The type of carbonaceous material had
mental Coal Dust Explosions,” a review of the no significant effect on the incendivity
use of gaseous & solid initiators, gunpowder & 7) W. J. Montgomery, CanMiningMetBull 55,
cannon & low-concussion igniters (22 refs). 765 (1962) & CA 61, 11840 (1964). Review
Ministry of Fuel & Power, Safety in Mines article on the explosive capacity of various dusts
Res Establ, Research Rept No 69 (1953) & (coal & ore dust, esp sulfides). Measures for the
CA 48, 9694 (1954) prevention of explosions are described
2) Anon, “ignition of Explosive Gas Mixtures 8) J. Nagy & D. W. Mitchess, US Bur Mines
by Friction,” booklet by Ministry of Fuel & RI No 6344 (1963) & CA 60, 6667 (1964).,
Power (London) (1954) Data are given to assist in interpreting obser-
3) N. E. Hanna et al, US Bur Mines RI No vations made after an explosion in an operating
5463 (1959) & CA 53, 14517 (1959). The coal mine when evidence is collected to estab-
effect of O, 3.6, 6.6 & 9.5% NaCl on the lish the cause & factors affecting ignition &
incendivity of permissible. explosives was propagation of the explosion
studied by the Bruceton up-and-down technique 9) R. W. Va.nDolah et al, US Bur Mines RI
in gallery tests. The study showed that the No 6340 (1963) & CA 60, 6691 (1964).
addn of relatively small quantities of NaCl “lgnitibility of gallery atmospheres.” Experi-
tends to reduce but does not eliminate ig- ments show that a variation in the natural gas
 I 23

content in the gallery can have a great effect practically zero velocity up to a speed of about
on the ignitability of the gallery atm; max 120 m/see, followed by an increasing accelera-
ignitability of the atm by permissible explosives tion of the flame front. The initial acceleration
occurs with %3.170 natural gas. For similar ex- is detd wholly by the effect of the igniter on
plosives, incendivity increases with detonation the dust deposit and is made evident by
velocity or bulk strength plotting the square of the flame arrival time
10) D. V. Stoyanov, Vuglishta (Sofia) 19 (9), against distance, but the subsequent increasing
acceleration is due to the flame of the explo-
25 (1964) &CA 62, 10257 (1965). The
sion. This behavior is found also in other
factors affecting the explosive properties of
exptl galleries where the ignition zone is
coal dust are the them compn of the coal,
the dispersion compn & cone of the coal dust, short and where the main fuel in the ignition
zone is the same as in the deposit in the rest
the compn of the mine atm, the source of the
flame, the natural ash content, the moisture of the gallery. The violence of an explosion
content & the volatile content of the coal. A can be characterized by the initial acceleration,
nomogram is given by means of which the min which can be used to compare explosions. in
different galleries. The min acceleration that
amt of inert matter to be added to prevent an
will sustain an explosion without oscillation
explosion can be determined from the natural
of the flame along the gallery is inversely
ash content
proportional to the length of the gallery, ex-
11) J. Nagy et al, US Bur Mines RI No 6597 plosions in long underground roadways can
(3) (1965) & CA 62, 11591 (1965). “Explosi- accelerate more slowly without suffering oscil -
bility of carbonaceous dusts.” Activated carbons lations than those in short exptl galleries, and
& charcoals were tested. In general only dusts this may be important in the siting of explo-
having > 8% volatile matter do not present an sion barriers
explosion hazard. Carbon black presented a fire
rather than explosion hazard. All bituminous 14) R. W. VanDohh et al, US Bur Mines RI
No 7195 (1968) & CA 70, 13126 (1969).
coal dusts are explosion hazards. In the 119
samples tested none with <1370 volatile content “Development of Slurry Explosives for Use in
ignited by spark. Dusts having a 30% volatile Potentially Flammable Gas Atmospheres,” In
content had 50% probability of ignition by this rept expts with 23 AN-based slurry expls
spark. AH dusts with > 40% volatile content showed that it is possible to have them cap-
ignited by spark sensitive and relatively nonincendive. All slurries
that used flaked Al were sensitive to No 6
12) G. Yoshikawa et al, Kogyo Kayako Kyokai- EBC (electric blasting cap) except one contg
shi 27 (6), 360 (1966) (Eng/Japan) & CA 67, AN 47.2, NaCl 10, water 30, Al (particle size
75024 (1967). Based on high-speed motion pic- 12~) 8, sugar 3.5, guar gum 1.0 & buffer 0.3%.
tures of firedamp ignition by typical coal-mine Buffer (consisting of NaOH & KH2POq in
dynamite shots, hydrodynamic-thermodynamic 1:29 ratio) was added to hold the pH at 4.5-
analysis is made on the expanding flow of 5.5
gaseous detonation products with salts disper-
ing in them. Detonation products attained 15) V. P. Gorkovenko et al, VzryvnoyeDelo
highest velocity at a distance from the charge 1970 (68/25), pp 116-22 & CA 73, 89710
at twice its diam, set up a shock wave in the (1970). Evahration of the permissibility of AN-
surrounding firedamp atm, & decreased in based expls was conducted by comparing
velocity as expansion proceeded oscillograms of light emitted during explns.
13) D. Rae, Safety in Mines Res Estab, Res The amplitude and time of light emissions,
Rept 253 (1967) & CA 69, 1140 (1968). “The dependence betw their values, and the prob-
main characteristics of slow coal-dust explosions ability of ignition of methane-air mixts were
and their relation to the testing of barriers.” detd
The main characteristics of slow coal-dust ex- 16) B. N. Kukib & B. D. Rossi, Ibid 1970
plosions in the new gallery at Buxton are a (68/25), 123-27 & CA 73, 89703 (1970). Com-
const initial flame front’ acceleration from parison of, permissibility of various expls was
 I 24

done by detg the “selectivity index;’ S = acid (and nitrous acid) and a rise in tempera-
(Vl –V, )/V,, where V’s are volumes of gaseous ture. As these nitrogen compounds act auto-
expln products (Vl, obtd on expln in a steel catalytically, the temperature and rate of de-
tube and a sand wad in. the Dolgov Bomb; V2, composition increase progressively until a point
obtd on expln in a free space in the Dolgov is reached at which the powder ignites spon-
Bomb; and V3, calculated taneously, ie without any external stimulus
17) L. V. Dubnov & A. I. Romanov, Ibid 1970 For underoxidized compositions, stored in
(68/25), 127-31 & CA 73, 89721 (1970). Tech- closed containers, the combustion process fol-
niques for evaluating the combustion tendency lowing spontaneous ignition may be incomplete.
of permissible expls, is discussed. The value v = However, gases generated by this process will
(S2–S, )/S,, where S, is av (50%) transmission generally burst the container and after-burning
distance in air (gap) of initiation of deton and may occur and contribute to the general con-
S2 is av (50%) transmission distance of combstn, flagration which in turn can lead to explosion
is taken as a basis for evaluation of the combstn of any remaining unreacted material some of
tendency. The”’ transmission distance was detd by which ignited spontaneously or of other nearby
expln of a composite cartridge consisting of explosive charges
active and passive segments with air gaps between Propellants were especially susceptible to spon-
them taneous ignition before it was learned how to
stabilize the NC. This was done by including sub-
18) Anon (US Dept Intr) Fed Regist 28 Aug
stances called stabilizers in the propellant
1971, 36, 17336 & CA 75, 14265” (1971).
formulations. These substances,
Standards for preventing explosions from explo-
such as diphenylamine, centrality etc absorb the
sive gases other than methane & procedures for
nitrogen oxides as they are formed, thus re-
testing “accumulations of such gases: the follow-
moving them from the sphere of reaction. This
ing gases shall not be allowed to accumulate
prevents further decomposition and the rise in
in underground coal mines in excess of the
temperature which decomposition produces.
cones (vol%) listed: CO 2.5; H 0.8; Hz S 0.8;
For similar reasons, it is advisable to keep the
Cz Hz 0.4; C3 H8 0.4; & MAPP (methylacetylne-
storage magazines cool and, in fact, since the
propylene-propadiene) 0.3
catastrophe aboard the French battleship J6na,
Recent review articles are: occurring in 1907, nearly all countries intro-
1) H. Kaffanke; Maitrise Degagement Grisouteux, duced refrigerating systems for cooling the
Amelior Climat Mines, Journees Inform, (Luxern magazines on ships
bourg), 1971, 217 & CA 76, 144547 (1972); Many disastrous explosions occurred at the
prediction of firedamp emissions end of tlie 19th and beginning of the 20th
2) M. Boutonnat et al, Ibid, 355& CA 76, century, which were’ caused by spontaneous
144545 (1972); equipment for measurement of ignition of propellants either containing
firedamp & ventilation control no stabilizers or containing those which were
ineffective, such as amyl alcohol used in some
3) H. Eicker, Ibid, 373 & CA 76, 144544
French powders
(1972); maintenance of firedamp meters &
transmission of measured values Among the disasters caused by spontaneous
ignition of propellants may be cited:
6) Ignition, Spontaneous, of Explosives.
Japanese battleship, Mikasa, destroyed in
This section presents some historical examples
1905 with 599 men lost
of spontaneous ignition. A more technical dis-
cussion of spontaneous ignition will be given Brazilian warship, Aquidaban, destroyed in
under Thermal Explosion, Chtalytic Effects in 1906 with 213 I’ives lost
a future Vol French battleship, Jt%a, exploded in 1907
Explosives containing improperly stabilized with 114 lives lost
ingredients such as NC or NC, decompose in Japanese ship, Matsoshima, destroyed in
storage, especially at tropical temperatures, with 1908 with 114 men killed
evolution of nitrogen oxides, formation of nitric
Land magazine of Batuco, in Chile, in 1908
 I 25

In view of the above the following ignition

French battleship, Libertt$, destroyed in 1911
with 204 men killed tests & ignition temperature tests are primarily
of historical interest. They also serve to out-
Italian warship, Benedetto Brin, in 1915 line the difficulties encountered in trying to
The explosion of the Russian dreadnaught of characterize quantitatively the response of
the Black Sea Navy, Empress Marie, which explosives to heat. Quantitative treatment of
occurred during WWI, was probably due to the “explosion temperatures” and delay to explo-
same reason, although there is a chance that sion (induction time) and the parameters of
it might have been due to sabotage the explosive that affect these quantities will
Even as insensitive a material as Ammonium be presented in a future Vol under “Thermal
Nitrate, AN, may be subject to spontaneous Explosions”
ignition. The disastrous explosions of two A. Flame Tests
ships at Texas City in 1947 could have been The International Committee on Explosives
a consequence of the spontaneous ignition of and the German Railway Commission prescribed
paper-bagged fertilizer grade AN. The actual the following ignition tests, applied mostly to
ignition may have occurred during rail ship- safety explosives. It is advisable to conduct these
ment and later developed into a full-scale tests behind a protecting barricade
deflagration and subsequent detonation in the a) Fuse Test. Place 3g of powdered explosive
hold of SS Grandcamp. Spontaneous ignition in a short glass or paper tube, about 2cm in
may have resulted from the AN being bagged diameter, and tap it gently to give the explo-
while it was too hot and/or improper removal sive an even surface. Introduce a slow burning
of acid from the AN. Both these conditions fuse (rate lcm/see) and ignite it. If the explo-
could lead to autocatalytic decomposition sive ignites, it is classified as a deflagrating
which can result in spontaneous ignition. For or readily inflammable explosive. Also observe
alternate explanations of possible causes of whether the explosive burns partly or com-
the fire that resulted in the Texas City pletely and note the time elapsed between
disaster see Vol 1, A 358-362 lighting the fuse and ignition of the test sample
Refs: l) Marsha112(1917), p632 2) R. Oelmann, b) Red Hot Iron Basin Test. If the explosive
SS 4,265 (1909) 3) Capt Persius, SS 10, passed test a) without igniting, it is submitted
276 (1915) in the following test to a much higher tem-
perature in order to be sure that it is not
7) Ignition Tests are historically divided into
liable to explode when exposed to fire
two categories:
By means of a burner, heat to red heat a
A. Those testing the response of a substance
hemispherical iron basin 12cm in diameter and
to an open flame; ie determination of the
1mm thick and introduce a small quantity, not
flame temperature at whcih a substance ignites
more than 0.5g, of the explosive to be tested.
and remains burning. Usually this temp is a
If no explosion takes place, introduce more of
few degrees higher than the so-called flash the explosive, gradually increasing the quantity
point of the substance until a weight of 5g is reached and repeat the
B. Those testing the behavior of materials test with 5 g three times. Observe the manner
exposed to high temperatures in the absence in which the explosive burns and the time
of an open flame. These tests are used to that elapses between adding the explosive to
determine so-called ignition o; explosion tem- the basin to the extinction of the flame
peratures. Ignition or explosion temperature is c) Red Hot Iron Test. This test is designed
an indefinite quantity since its evaluation de- to ascertain the inability of safety explosives
pends strongly on the conditions of measure- to explode on heating or to burn continuously
ment. As an example of this variability and Heat the end of an iron bar, 15mm in
dependence on test conditions, the “explosion diameter, for a length of 10cm to a cherry red
temperatures” for as standard an explosive as heat (about 900°) and plunge it into a small
TNT are quoted from 290 to 570°f (Ref 16) quantity of explosive placed on a sheet of asbes-
C. Measurement of times to ignition of tos. If the explosive does not ignite or is diffi-
explosive exposed to hot flames. cult to ignite, and burns slowly without explosion,
 I 26

and the flame dies the moment the hot bar is Lead Azide Distances from Fuse (inches)
withdrawn, continue testing fresh portions of ‘% 4 12 16 20 22
it, gradually increasing the amount of sample Dextrinated 100% 20 0 – – –
up to 100g. If the explosive still behaves as Pure 100 100 100 80 0 –
described’ above, it is considered to have passed PVA 100 100 100 60 40 0
the test Refs: 1) Marshall 2 (1917), pp 437–38 2) Reilly
This test is not mentioned among German (1938),’ p 66 3) J. Fleischer & J. B. Burtle,
Railway Commission tests, instead, the following USP 2421778 (1947) & CA 41, 5724 (1947)
two tests are prescribed:
d) Iron Basin with Wood’s Metal Test. Fill B. Ignition Temperature of Explosives, Tests.
an iron basin, 14cm diam and 7cm high, to (Verpuffungstempuratur or Entziindungspuntke,
within 2cm of the top with molten Wood’s in German and Inflammation, in French). When
metal and insert an armored thermometer or an explosive is heated by means other than an
a thermocouple in the middle of the molten open flame, a temperature is reached at which
mass. Heat the basin and, as soon as the tem- the sample ignites and burns or deflagrates pro-
perature reaches 100°, place 3 test tubes (15 ducing a flame or fumes off without any loud
mm id and 120mm long) containing 0.2-O.5g report, or finally explodes or detonates with a
of powdered explosive about 50mm away from loud report. This test should not be confused
the thermometer, spaced about 100m apart with either the “flash point” or “ignition point”
and immersed 20mm into the bath. Raise the test (see Sect A) in which a substance, pre-
temperature of the bath at the rate of 20° per heated to a certain temperature, is ignited by
minute until ignition occurs or until the tem- means of an open flame, whereas in the “ig-
perature reaches 320° nition temperature” test no outside flame is
Note: The test may also be conducted by used
raising the temperature 50/rein (Ref 2) Numerous tests exist for determining ignition
temperature, but few of them give the same
e) Iron Box Test. Place 0.5 to 1kg of the
result. Results may vary as much as 100° de-
explosive to be tested in a sheet iron, riveted
pending on the method used, on the rate of
box Imm thick and 85, x 85 x 85mm in size.
heating, on the size of the sample used, on
Fasten the lid by means of iron wire, bound
the state of division etc. See Thermal Explo-
crosswise around the box and place the box
sions for a discussion of why measurement
in a brisk wood fire (by means of a mechanical
variables affect ignition temp results
device operated by remote control). The explo-
One of the most reproducible of these tests
sive is considered to have passed this test if it
is described under “Explosion Temperature
does not ignite or explode within 10 minutes.
Test,” an official test at Picatinny Arsenal
Notes: (Ref 15). This test is applicable to the de-
a. This test has to be carried out in the open termination of ignition point, decomposition
and not less than 100 meters from inhabited point, deflagration point etc for those ex-
buildings plosives which do not really explode under
b. If it is known that the explosive is not conditions of the test
sensitive, the box may be laid by hand pro- Some other “ignition temperature” tests are
vided it has been wrapped up well beforehand shown below:
in several layers of paper so that the explosive a) German Railway Commission Test (Refs
will not be ignited too soon 1, 2 & 3). A small sample of an explosive
Fleischer & Burtle (Ref 3) give results for a (0.1 g for all explosives; except Black Powder,
flame test for different types of Lead Azide. In NHQNOS, and chlorates, for which 0.50g is
this test a std safety fuse provides the flame used): is placed in a test tube, 125mm long,
and percent firing of the Lead Azides is recorded 15mm id and 0.5mm thick, which is tightly
as a function of distance from the fuse as corked and placed in a paraffin or Wood’s
shown in the tabulation below: metal bath provided with a stirrer and ther-
mometer and preheated to 100° Heating is
continued with stirring so that the temperature
 I 27

increases 5° per minute and the point is noted c) Methods of Direct Ignition of Kast (Ref
at which the sample ignites, fumes off etc 3). A small quantity of explosive (up to 0.5g)
A. P&ez Ara (Ref 3, p 109) gives the fol- is placed on a small iron plate and an attempt
lowing temperatures for explosives tested by is made to ignite it by the flame of a splint
thk method: of wood. Another small sample of explosive is
Black Powder 225 to 300, NC (13%N) 185, touched with a thin iron rod, preheated to red
smokeless powder 185, NC 160, Nit rostarch heat. Another small sample is thrown into an
170, NHa N03 225, Tetryl 190, Mercury Azide iron, dish of about 12cm diameter, preheated
200, Silver Azide 200, Lead Azide 34o to to red heat
350, Cuprous Azide 210 to 350, Cupric Azide d) Spa~ish Method (Ref 1, v 2, pp 435-6).
245, Mercuric Fulminate 160 to 200, Silver A long copper strip, 15mm thick and 80mm
Fulminate 200, Cheddite 200, blasting gelatin wide, is heated at one end with two gas
207 to 211 and Picric Acid 225 to 350° burners. The other end of the copper strip has
b) A Test Described by A. P6rez Ara (Ref 3) a circular holder with five holes containing
and Datta & Chatteq”ee (Ref 6). The above copper test tubes. The central test tube is
apparatus is used but the empty test tubes are fdled with mercury and contains a thermometer
preheated in the bath to different temperatures while the other four, placed around the first,
depending on the explosive to be tested. At contain 0.1 g samples of explosives. Heating is
this point, a small (O.10 to 0.50g) sample is continued until one of the samples in one of
added to one of the empty tubes and if no ig- the test tubes nearest the heated end ignites or
nition takes place the temperature is raised explodes and the temperature is noted. The re-
about 5° and a new sample is thrown into the maining samples ignite a bit later. The average
tube. The test is continued until the sample temperature of ignition of all the samples is
either ignites, fumes off or explodes. If the taken as the “ignition temperature”
sample ignites at the first trial, the temperature e) Ignition Temperature by Fisher-Johns
is lowered 5-10° and the test repeated and Apparatus, by Kojler Micro Hot Stage, by
continued at progressively lower temperatures Dennis Melting Point Apparatus or by the
until one is reached at which the sample does Maquenne Block. The first apparatus is des-
not ignite. After this, the temperature is raised cribed in Fisher’s Catalogue No 80, p 619,
again and the point is noted at which the No 12-142
sample ignites The second is shown in Arthur H. Thomas
Usually, this test gives higher results than Catalogue (1950 cd), pp 877-880
the method a) (Ref 3) The third and fourth devices are described
Note: Datta & Chatterjee used a KHS04 bath in R. L. Shriner & R. C. Fuson, “Systematic
which they heated up to 500°. Kast and Haid Identification of Organic Compounds,” J. Wiley,
tested a number of initiating explosives by both NY (1940), pp 88-89 (see also L. M. Dennis
methods (Ref 11) and found that, although & R. S. Shelton, JACS, 52, 3128 (1930) and
most explosives give higher results by method Arthur H. Thomas Catalogue (1950), p 818)
b), there are many cases in which both methods Essentially, all of these devices consist of a
give the same results, especially if heating is metallic block or bar heated either by gas (as
conducted at a rate of 20° per minute in in the Maquenne Block) or by an electric
method a) heater. The test may be conducted by placing
a few small grains of explosive on the pre-
Method a) Method b) heated block and noting the temperature at
Heating at which the sample ignites, deflagrates or ex-
20°/min plodes by means of a thermometer installed
Cyanuric Triazide 207° 205° inside the block
Lead Azide 339 360 Tests conducted at Picatinny Arsenal with
Mercuric Fulminate 172 215 these devices showed that fairly consistent re-
Mercuric .Fulminate sults may be obtained for a given explosive if
80+ KC103 20 170 215 all determinations are made under the same
Lead Styphnate 276 275 conditions (same rate of heating, size of grains,
 I 28

size of sample etc) of the bath during heating (on account of the
~ Method of $nelling and Storm. In this exothermic decomposition that takes place) but
method (Ref 5), a 2-3g sample of NG was sometimes it frdls again before ignition takes
heated in a test tube immersed in a paraffin place
bath provided with a thermometer. The tem- h) Koehler and Marqueyrol (Ref 8) deter-
perature of the NG inside the tube was mea- mined the ignition temperature of NC in
sured by means of a Cu-constantan thermo- vacuo, in air, and in an atmosphere ,of C02.
couple. The experiment is conducted behind a They ,came to the conclusion that the results
barricade. The following results are for a period are practically the same and are as follows:
of heating equal. to 5 minutes: Guncotton (CPl ) with N=l 3% 180 to 190°
Temperature of Collodion cotton (CPZ) with N=12% 186 to 189°
Bath Sample Poudre B 174 to 187°
At the start of heating the NG 80 49 i) Stettbacher (Ref 9) comments on the great
NG appears to boil owing to vaiiance of results for the ignition temperature
rapid evolution of water of NG, ranging from 180° by Nobel to 220-
and oxides of nitrogen 174 145 255° by Staudinger, and criticizes the various
Vigorous boiling (bubbling) methods of determination
of NG 186 165 j) Taylor and Rinkenbach (Ref 12) deter-
NG becomes thick & viscous 193 185 mined ignition points of various explosives by
Temperature of,sample rises dropping small portions onto a block of heated
faster than that of the bath 198 205 Wood’s ailoy:
Violent detonation .201.5 °215-218° Explosive Ign Temp
If the rise in temperature is slow, the’ sample Mercuric Fulminate 260°
decomposes and partly chars at temperatures MF + 10% KC103 240
above 180° without producing any explosion MF + 20% KC103 235
g) Method of Micewicz and Majko wski. This Silver Fulminate 245
method (Ref 14) may be considered to be a Lead Azide 383
modification of the Snelling and Storm’s method Silver Azide ~ 273
described above Mercurous Azide 298
M & M examined several high explosives Lead Styphnate 293
and found that in many cases the temperature Silver Acetylide 220-225
of the explosives rises considerably” above that Lead Picrate 281

The following table gives values for TNT, pA and Tetryl:

Time* of Temp of Bath Max Temp of Temp of

Explosive Heating at Ignition Explosive sample at Remarks
(rein) or Explosion reached Ignition
during Heating
TNT 11.55 294° 299° 248° Ignition
TNT 19.87 288 296 276 Ignition
TNT 39.58 283 294 284 Ignition
PA 13.25 289 305 243 Ignition
PA 17.17 289 301 281 Ignition
PA 19.25 293 296 247 Ignition.
PA 36.47 283 298 262 Ignition
Tetryl 18.43 189 202 202 Explosion
Tetryl 5.87 182 232 232 Explosion
Tetryl 5.27 189 214 214 Explosion
*Measured from the moment the bath reached 100°
 I 29

Silver Picrate 335 2191 (1923) 10) H. Kast, ZAngewChem, 36,

Barium Picrate 403 402 (1923) & CA 17, 3608 (1923) 11) H.
Copper Picrate 373 Kast & A. Haid, ZAngewChem, 38, 48 (1925)
Hexamethylenetriperoxidediamine 200 & CA 19, 1197 (1925) 12) C.A. Taylor &
Mannitol Hexanitrate 232 W.H. Rinkenbach, JFrankInst, 204, 369 (1927)
Dulcitol Hexanitrate 205 13) G. Tammann & G. Kr6ger, ZAnorgChem,
Cyanuric Triazide 252 169, pp 1-32 (1928) & CA 22, 2058 (1928)
14) S. Micewicz & K. Majkowski, SS, 23, 422
k) Tamrnann&Kr6ger (Ref 13) examined
numerous liquid and solid explosives and came (1928) 15) A.J. Clear, PATR 1401, Rev 1, (28
to the following conclusions: Feb 1950) & PATR 3278, Rev 1 (April 1970)
1) The explosion (ignition) temperature de- 16) Anon, NOLR 1111 (1952), pp 2-27 17)
V.M. Rogozhnikov & V.P. Lushkin, Vzryvnoe
creases with increasing size of sample and in-
Delo, 1970, No 68/25, 134 (Russ) & CA 73,
creases with rate of heating
100608 (1970)
2) With volatile explosives which melt before
exploding, the required explosive sample weights n) Ignition Temperature Test (Method of
are appreciably higher (20 to 10Omg) than with M. Kostevitch). In the methods described above
non- volatile explosives (0.4 to 1Omg) as well as in the method practiced at Picatinny
3) With volatile explosives giving gaseous prod- Arsenal (see Explosion Test in Vol 1, pp XVI
ucts of explosion, the substance evaporates or & XVII), in which an explosive is placed in
decomposes before the explosive limits are a blasting cap shell which is then put into
reached Wood’s metal preheated to a temperature close
4) The dependence of explosion temperature to the melting point of the explosive, the ex-
upon rate of heating is almost always linear, plosive itself cannot be seen during testing and
with the exception of potassium picrate any melting, decomposition or other phenome-
5) TNT begins, to decompose at 150° and non that takes place cannot be noted. In order
on long heating at constant temperature, the to observe all stages of behavior of an explo-
explosion temperature is raised by the forma- sive, Col Kostevitch proposed to use an all glass
tion of decomposition products apparatus, originally developed by the Imperial
1) Method employed at Picatinny Arsenal Russian Ordnance Dept in 1908 for the deter-
(Ref 15) is given under “Explosion Temperature” mination of melting points of high explosives,
m) A Manornetric-bomb Method for deter- such as TNT, PA etc. This apparatus is essen-
mination of the ignitability of an explosive is tially the same as that described in US Specifi-
described by Rogozhnikov et al (Ref 17). By cation MIL-T-248Aand used for the determination
this method, the rnin amt of igniter required of setting points of TNT and other high explo-
to initiate steady combustion (at increasing sives
pressure) of an explosive is determined; simul- It consists of h heavy-walled glass test tube,
taneously, the pressure increase with time is provided with a stopper and a thermometer.
measured. 20 explosive compns were tested. This tube is inserted by means of a rubber
The method is useful for investigation of the stopper into a 2nd test tube of larger diameter,
effects of various additives to the explosives serving as an air jacket. The ensemble is inserted,
on their ignitability by means of another stopper, into a beaker
Refs: 1) Marshall (1917) 2, “435 & 758; (1932) filled with a nonflammable, transparent, high
3, 130-135 2) Reilly (1938), p 66 3) A. boiling point liquid (eg dibutylphthalate or
P&ez Ara (1945), pp 108-9 4) G. Finzi, Gazz silicones) and provided with a thermometer and
Chim Ital, 39, 549 (1909) & SS, 5, 153 (1910) a mechanical or hand stirrer with a ring at the
5) W.O. Snelling & C.G. Storm, SS, 8, 1-4 lower end
(1913) & CA 7, 1416 (1913) 6) R.L. Datta In the Kostevitch method a sample of explo-
& N.R. Chatterjee, JCS, 115, 1006 (1919) 7) sive (about O.lg) is introduced into a small
A. Schrimpf, SS, 15, 93 (1920) 8) Koehler & glass bulb (volume=ca 3.5cc), resembling in ap-
Marqueyrol, MP, 18, 138 (1921) 9) A. Stett- pearance that used “for weighing fuming acids,
bacher, ZAngewChem, 36, 60 (1923) & CA 17, but made from. a larger diameter tube in order
 I 30

to facilitate the introduction of the explosive. maximum distance at which no ignition takes
The tube of the bulb is inserted in a hole place in ten trials. These values can be easily
drilled in the stopper of the outer test tube. converted to the duration of contact with
This stopper also contains a thermometer. The flame
bulb of the tube and that of the thermometer Refs: 1) Marshall 2 (1917), p 437 2) A.W.
are so arranged that they are on the same Cronquist, SS, 1, 106 (1906) 3) N.C. Hansen,
level. After the liquid is preheated to about SS, 8, 165 (1913)
100°, the bulb with the sample is introduced 8) Ignition Theory of Explosives.
and heating is continued in such a manner that Some of this material was presented in Sect ,
the rise of temperature is uniform, say 5° to 1 above. Other material will be described under
20° per minute. The behavior of the sample “Thermal Explosions” in a future Vol. lklow
is observed during the entire period of heating we list and abstract several references specifi-
and the temperatures are noted at which the cally directed to the theory and/or mechanism
sample begins to fume off, when the flash of ignition of explosives
appears and finally when the tube fills with On the basis of this study of the preignition,
black smoke ignition & combustion reactions of Black Powder
Refs: 1) M.M. Kostevitch, SS, 23, 156 (1928) by thermoanalytical techniques, Campbell and
& private communication 2) Reilly (1938), Weingarten (Ref 1) proposed that the preignition
p 144 3) US Specification M1L-T-248A (Ott 1963) reaction (1) is between S & KN03, which is
C. Ignition Times for Flame Exposures. sufficiently exothermal to activate the propa-
In order to measure the time required to gative combustion reaction between charcoal &
ignite explosives exposed to flames, several de- KN03 (2) : S + 2KN03 ~K2SOq + 2N0 (1) &
vices have been proposed. Among these the 3C + 2KNC)3 + K2C03 + Nz + C02 + CO (2). In
pendulum of Prof Cronquist of Sweden appears (1) the S is in a molten state & the KNO, is in
to be the simplest (Ref 2). It consists of a its thermally active trigonal form. In (2) the
metallic pendulum, 2.5-3m long, making a swing charcoal is in the solid state & the KN03 is
of 75cm at a rate of lcm in 1/50 second. A in a molten condition
small sample of explosive is attached to the Librovich (Ref 2) gives: A math treatment
lower end of the pendulum and, as the pendulum of the ignition of propellants and explosives.
swings, it passes through a row of 5 small flat It is assumed that ignition is caused by a stream
gas burners arranged in the form of an arch. of hot gases and that evapn of the condensed
Each burner has a flame 15cm long. If, for in- phase results entirely from the heat liberated at
stance, the explosive ignites after passing two the burning surface. Ethylene dinitrate is used
burners, the time is 15 x 2 x 1/50 = 0.6 seconds. as an example. With a surface temp of 473”K;
Cronquist gives the following results: Small grain 4.62 cal/cm2 is required for ignition
Black Powder 3.20 to 4.50 see; single-base smoke- Khlevnoi (Ref 3) analyzed the process of
less powder for small arms (nongraphited) 0.44 ignition of a nonmelting explosive by a hot
to 0.90 see; same, graphited 1.96 to 3.28; Cordite metal plate for model conditions (specified).
(old type) 0.16 to 0.30 and Ballistite 0.16 to Equations were derived describing the max temp
0.40 sec on the surface of the explosive, the temp dis-
N. C. Hansen of Denmark (Ref 3) proposed tribution in the explosive at the time of ignition,
an apparatus consisting of a pendulum 2.35 the criterion of ignition, etc
meters long swinging through a single gas Refs:\l ) C. Campbell & G. Weingarten, Trans
burner. The duration of contact with flame is FaradSoc 55, (12) 2221 (1959) & CA 54, 16136
regulated by starting the swing from different (1960) 2) V.B. Librovich, ZhPriklMekhan i Tekhn
positions–the greater the lateral displacement Fiz (1963) (6), 74 & CA 60, 14325 (1964) 3)
at the start of the swing, the shorter the dur- S.S. Khlevnoi, FizGoreniya Vzryva 1970, 6 (3),
ation of contact with the flame. Test results 295 & CA 74, 77969 (1971)
are expressed in centimeters from the start of
the swing to the center of the flame, eg the
 I 31

Illuminating Devices and Compositions. Any flares with reduced smoke output, special air-
pyrotechnic device or composition producing port flares and developing substitutes for
intense light and serving to illuminate various critical material. The use of Mg in illuminating
objects such as enemy territory at night, either mixtures is also mentioned by Reilly (Ref 2)
for observation or photography, or for locating Among the white pyrotechnic compositions
targets” for bombing etc, or illumination of air- used during WWII, the following may be cited:
fields for landing at night, in rain or fog White Flare Composition: Ba(N03 )2 66, Al
Among illuminating devices may be cited 26, sulfur 6, castor oil 2%. 500g of this powder
flares (ground or airplane), photoflash bombs, loaded at 6,000 psi burns for 65 seconds, de-
illuminating projectiles (star shells), position veloping 60,000 candlepower
lights etc During WWII, the Germans developed several
Illuminating devices generally produce either illuminating mixtures. containing 14-28% of
white or yellow-tinted light (idthough some polyvinylchloride (either additionally chlorinated
colored lights are also used) of great intensity, or not) together with 17-35% of magnesium
ranging from several tens to several hundreds of powder, 50-61 % of oxidizer and 1 to 5% of
thousands candle power per square inch vaseline or synthetic wax (Ref 3)
Among the older illuminating compositions used Research conducted at Picatinny Arsenal has
during WWl are: shown that for certain purposes yellow-tinted
White light mixture for airplane flares: Ba(N03 )2 lights are preferable to white ones. Therefore,
76, Al (powder) 9.75, Al (flake) 8.25, S (flour) compositions containing sodium salts, such as
4.0, castor oil or vaseline 2.0%; Intensity about sodium oxalate, were introduced, as for instance,
350,000 candle power (Ref 1, v 2, p 111) in the following:
White light for wing-tip jlares: Ba(N03 )2 81.0, Yellow-tinted flare: Ba(N03 )2 34, Mg (pre-
Al (flake) 13.7, sulfur 5.3% (Ibid p 225) coated with 6% linseed oil) 36, Al 8, Na
White light for position signals: Ba(N03 )Z 66.9, oxalate 20, linseed oil 1, castor oil 1%. 300g
Al (flake) 15.5, sulfur 16.7, SbjS3 0.6, stearin of this composition pressed at 3,600 psi burned
0.3% (Ibid p 206) for 280 seconds and developed 556,000
French white jire: KNO~ 57.1, Sb (metallic candlepower
powder) 19.1, Pb30Q (red lead) 17.5, sulfur 6.3% Faber (Ref 1, v 1, p 192) gives the following
(Ref 1, v 1, p 189) yellow Iight illuminating composition used by
German white illuminating compound: fired the French in WWI: Mg 67.9, Al @owder) 2.0,
from special pistols, contained Ba(N03 )2 61.5, Na oxalate 17.4, KC103 2.6, sawdust 9.6 &
Al @owder) 20 and sulfur 18.9% (Ibid p 191) shellac ().5’%0
After WWI, most of the research and devel- The use of sodium oxalate for yellow illumi-
opment in pyrotechnic compositions for the “US nating compositions was also recommended by
Army was carried out at Picatinny Arsenal, Reilly (Ref 2)
where the development of white light composi- Brock (Ref 6) claims that the luminosity of
tions proceeded rdong the following lines: 1) flares is increased by the addition of 1-5% MgO.
Mg metal was introduced in 1931 to replace For example a mixture consisting of Mg 50.0,
part or all of the Al in order to obtain higher NaN03 42.7, polyvinylacetate binder 4.5 & MgO
candlepower 2) Study of white light com- 2.8$Z0had a luminosity of 7.6 x 105 candlepower
positions in 1933 showed that a mixture of Ba and a burning time of 2.24 sees
and Sr nitrates was more efficient than the Ba A detailed discussion of the theoretical as-
salt alone or other oxidizing agents, such as pects of illumination and the evaluation of
KN03, KCIOq and NH4 CIOq. Furthermore, the several illuminating compositions is given by
addition of some Sr to the Ba salt overcame the Tavernier (Ref 5)
greenish tinge obtained with the use of the Ba Colored illuminating mixtures may also be
salt alone 3) Further work on white light used, but they do not produce light of such
compositions up to 1945 was concerned mainly intensity as do white lights. Several new formu-
with compositions for special tactical purposes lations were developed at Picatinny Arsenal be-
such as ground signals, mortar illuminating shells, fore and after WWII
 I 32

Some illuminating_ mixtures are listed in rate of burning. Sulfur was added sometimes to
Chemical Abstracts, for example, L. Bohner, make the mixture easier to ignite. These mix-
CA 32, 2754 (1938): German illuminating com- tures were ignited by means of a charge of
position used in compressed form as a charge Black Powder (Ref 1)
for “Very pistols” contained small amounts It should be noted that Ba nitrate is pre-
of cuprene in addition to the usurd components, ferable to K nitrate because the latter compound
such as magnesium powder, barium nitrate and a has a tendency to lower the temperature of
binding agent such as shellac combustion of the mixture
G. J. Schladt, CA 33, 4426 (1939): Comp- Some flares also had compositions similar to
osition consisting of Ba(N03 )2 36-40, Sr(N03 )2 that of star shells
6-8, Mg (powder) 50-54%, coated with a mixture More recently, an illuminating compn for
of linseed and castor oil projectiles was prepd by compressing a mixture
,Another colored composition which is wick- of pulverized A1/Mn alloy with basic Pb nitrate
less and burns, with a colored flame consists of: into a rigid coherent pellet. The pellet was in-
100 part metaldehyde, at least 5 part AN, and serted in the nose of a projectile (Ref 2)
at least 4 parts of a mixture of chlorates and Refs: 1) Marshall, 2, (1917), p 609 & 3, (1932),
nitrates of flame-coloring metals (Ref 5) p 196 2) W.H. Woodford et al, CanadP 394307
High luminous intensity & color purity pro- (1941) & CA 35, 2326 (1941) 3) Anon, “Mil-
duced by flames resulting from the combustion itary Pyrotechnic Series, Part I, Theory &
of Group II perchlorates mixed with alcohols or Application,” US Army Materiel Command
other org solvents was noted in a previous study Pamphlet AMCP 706-185 (April 1967), Chapter
made to adapt these mixes to markers & 6, Production of Light, pp 6-1 to 6-73
flares for aerial use. Tried to improve Marine
MK2-O Marker but concluded ~hat no improve- Image Converter Camera. See Encycl, Vol 2,
ment is possible unless MK2-O is redesigned p C 14-R & article on High Speed Photography
(Ref 7) in this Vol
Refs: 1) Faber, vols 1 & 2 2) J. Reilly, “Ex-
plosives, Matches & Fireworks,” Van Nostrand, Imatrex. A Swedish explosive consisting of K
NY (1938), p 149 3) T. Urbanski, “Progress chlorate of constant porosity which is impreg-
in the field of explosives during the past decade,” nated with a combustible oil, such as petroleum,
Przemysl Chemiczny, 27,(IV), No 10, p 487 Diesel oil or Brenn61 (d ca 0.8; bp 150-3300).
(1948) (Translated by Dr. Ivan Simon of Imatrex can be detonated by a blasting cap. Its \
Arthur D. Little, Inc) 4) Data on Foreign temp of explosion is ca 3600°; Q: 1163 kcal/kg,
Explosives, PB 11544 5) P. Tavemier, MP 31, specific vol 450-490 l/kg; deton velocity 3000-
309 (1949) & CA 46, 11686 (1952) 5) M. 4000 m/see, expln temp 370° (“Temperatur-
Wullschleger-Hirschi, SwissP 319241 (1957) empfindlichke!t”)
& CA 51, 15132 (1957) 6) J.A.M. Brock, Refi Dr. Langhans, Explosivst, 1962, 86
USP 2968542 (1961) & CA 55, 14918 (1961)
7) R.M. Blunt, US Govt Res Develop Rep (1968) 1. M. Filling. Jellied gasoline filling developed
68 (17) 142 & CA 70, 39425 (1969) during WWII by Standard Oil Co and used for
filling incendiary bombs: isobutyl methacrylate
Illuminating Projectiles or Light Rockets (Star polymer 5.0, fatty acids, such as stearic acid,
Shells). Thestar shells or light rockets, as used 2.5, naphthenic acid 2.5, aqueous solution (40%)
during WWI to light up the landscape, and of caustic soda 3.0, and gasoline 87
reveal the position of the enemy at night, con- Refi W. A. Noyes Jr, “Chemistry (Science in
sisted of a single star attached to a parachute. WWII),” Little, Brown & Co, Boston (1948),
The illuminating composition consisted of 1 part p 389
powdered Al, Mg or Mg-Al alloy, mixed with 2
parts of oxidizing material such as Ba(N03 )Z, Imidazole or Glyoxaline and Derivatives. See
NaN03, KN03 and KC103. Shellac or linseed oil 1,3-Diazole and Derivatives in Vol 5 of Encycl,
was used as a binding material: oil reduced the pp Dl 165-R & DI 166-L
 I 33

2-lmidazolidone or Diazacyclopentanone-1. If the nitration is carried out with one equivalent

See Ethyleneurea or Ethylenecarbamide in Vol of the nitric acid in acetic anhydride, the same
6, p E291-R product is obtained, but if nitric acid is used
in excess, the so-called 1,3-dinitroimidazolidone,

Imidazolines, Imidazolidines, Imidazolones, yH2” y;)

Imidazolidones; Their Derivatives and Nitrated CH2.N(N0 2), is obtained. It seems that the
Products. (Imidazolidine is also known as last reaction proceeds as follows:
1,3-Diazacyclopentane or Cyclotrimethylene- CH2
1,3-diamine) \ ~>CNHN02‘y
. . ~2-N~ C=N No21+~os
These compounds, cyclic derivatives of urea CH2.N(NO J CH .N(NO z)
or guanidine, are as follows: (/ltrimine)
2-Imidazoline, Hz C-N% CH2.N.NO 2

H*C–N’
I CNH2 ; ,>CO
AH2.N(NO 2)
H The 1-nitro-2-nitramino-A2 -imidazoline is an explo-
. .
2-Im~azolldtne, Hzc-N\c(NH2)2; sive comparable in brisance and power to RDX,
but it, is much more sensitive to impact. Its
H2C–N/ thermal stability is low, since 97% is destroyed
H by 5 minutes of boiling in water. When 1-nitro-
H 2-nitroaminoirnidazoline is dissolved in cold aq
2-Imidazolone (or glyoxalon), HC–N ammonia and then acidified a stable product
corresponding to the formula
II ‘C=o;
HC–N’ CH2.Ny - ~H2
\ &
H
N-’
CH z. (NO 2)~NH.N02 is obtained. It is
called 1-nitro-2-amino-2 -nitraminoimidazolidine
2-Imidazolidone (or imidiazolidinone or ethylene (Ref 1). ,Some 2-imidazoliqe compounds were
urea), H reported in Ref 2, and among them
‘1-Nitro-2-amino-2-imidazoline nitrate,
‘2y-N\c=o

[’ 1
CH2-N(NOJ +
H2c–N/
>C.NH z NO;, N=36.2%; mp 1610,
H
CH2–NH with decompn
These compounds per se are non-explosive, but
The l-substituted-2-nitramino-2-imidazoline
they can be nitrated to give explosive and/or
derivatives were prepd and investigated by M~Kay
thermally unstable nitramines”
et al (Ref 3). Nitration of these products
The following substances were prepared &
yielded l~substituted-2-nitrimino-3-nitroimidazoli-
studied by McKay & Wright (Ref 1) starting with
dines, which proved to be stable at room tem-
the reaction of nitroguanidine with ethylene-
perature. As examples of these compounds may
diamine to give 2-nitramino- A 2-imidazoline ( A2
be cited:
is used to indicate that a double bond is attached
l-~Nitroxyethyl-2-nitrimino-3-nitroimidazolidin e,
at position 2):
CH2.N% CH2.N(NQ )
CH2 .NH2
,HN\ CNH.N02+2NH3 >C.N.N02 ,-
C.NH.NH z +
CH2-NH’ CH2.N.C.H2.CH2 .O.NOZ ;’mw 264.16j N 31.8,2%;
CH2.NH2 H2N’
crystals; mp 115-160 with decomp
Nitration of this product with mixed nitric- l-(N-Nitroguanyl)-N-nitro-/.?aminoethyl)-2-nirn"mino-
sulfuric acid at – 10 gave l-nitro-2-nitramino- 3-nitroimidazolidine,
A2-imkiazoline, CH ~.N\ CH 2.N(N02)
[ ,CNH.NO, >C:N.N02
CH2.N(N02) CH2.N.CH #(N02)C(NH).NH.N02; mw 350.22,
 I 34

N 40.00%.; mp 161–62° with decompn. McKay JACS 76, 6374 (1954) &CA 49, 15861 (1955)
et al (Ref 3) do not mention that any of these’ 8) R.J.J. Simkins & G.F. Wright, JACS 77,
materials are explosive 3157 (1955) & CA 50, 3496 (1956)
Other reactions of the Imidazolidines are de-
scribed in Refs 4 & 5 and below
l-Nitroso-2-Iminoimidazolidine or 1-Nitroso-2- Imide. See Amides, lmides and Derivatives in
Imidazolidimone, mp 95–1 00° (with decomp) Vol 1, pp A 168–171 with the following addi-
(Ref 6) tional entry: Two instances of explosions of
1,3-Dinitro-imidazolidine or 1,3-Dinitro- 1,3- ammoniacal Ag solns are described. Both are
Diazacyclopentane, yo2 attributed to the formation and subsequent
H2C–N, explosion of Silver Imide, Ag2NH. In the first
CH2 instance, a marking ink consisting of a mixt of
H2C–~/ solns of AgN03, NH 40H, Na2C03 & gum arabic
exploded on warming. In the second occurrence,
N02 ;mw 162.11, Ag20 was precipitated by NaOH from an AgN03
N34.56%, OB–49.4%; decomposes without ig- sp?m; The precipitate was washed, dissolved in
nition at 205°; ignites immediately when dropped NH40H, and a few drops of AgN03 soln were
on a 350° surface. It is explosive & is claimed added until a permanent precipitate reappeared.
to be about as impact sensitive as Tetryl (Figure This soln was then stored in tightly-stoppered
of Insensitivity, FI, of 0.78). Its power is 13670 dark bottles. Two such bottles exploded, one
PA. It is prepd by nitration of diendomethylene- of them violently, after 10–14 days storage
tetrazacyclodecanemonohy drochloride, Explosion is ascribed to the formation of
Ag2NH via:
Ag(NH3)20H = Ag2NH + 3NH3 + 2H20
The silver imide, Ag2NH, in its amorphous
7N–CH ~ N~H z CHI ~; with
H2C– H2
98% nitric acid
form is claimed to be very sensitive to heat &
shock even when wet
in acetic anhydride (Ref 8) Rem: 1) H. Vasbinder, PharmWeekblad 87,
1,2-Dinitro-lminoimidazolidine, Silver Salt. (No 861 (1952) & CA 47,4083 (1953) 2) No
formula given). When 1,2-Dinitraminoimidazolidine, other refs to explosion or decompn of Imides or
Iyo2 Imidic Acid & Derivs were found in CA 1927–
H2C–N 1971

H2C–N >“NNO’
~ Iminobisaceticazide or Iminodiaceticazide or
is treated with aq alc AgNOs,
its silver salt is pre~ipitated. This salt exploded Iminodiaeetic Acid Diglycol-
Diazide. See
on a spatula over an open flame (Ref 7) amidic Diazide in Vol 5, p D1 262
Refs: 1) A.F. McKay & G.F. Wright, JACS 70,
3990–9 1 (1948) 2) A.F. McKay, J.E. Milk,
JACS 72, 1618 (1950) 3) A.F. McKay, J.R. Iminodiethanol-dinitrate. See Di(2-nitroxy-
Bryce & D.E. Rivington, CanadJChem 29, ethyl)-nitramine or DINA in Vol 5, pp D1240–
382–90 (1951) & CA 46, 7094 (1952) 1242
4) R.H. Hall, G.F. Wright, JACS 73, 2208–13
(1951) &CA 46, 1988 (1952) (Reactions of
l-nitro-2-nitramino-2 -propylaminoimidazolidtie Iminodihydropurines. See Aminopurines and
with acetyl ,chloride) ‘5) R.H. Hall, G.F. Derivatives in Vol 1, p Al 54-L
Wright, JACS 73, 2213–16 (1951) & CA 46,
1989 (1952) (Reaction of 1-nitro-2-nitrarnino-’
2-proporyimidazolidine with acetyl chloride) 3-lmino-5-phenylimino-1,2,4-triazoline (Nw-
6) M.W. Kirkwood, JACS 76,.1936 (1954)& Phenyldihydroguanazol), C6H5N: ~–~H2;
CA 49,6927 (1955) 7) A.F. McKay” et al, N: N.C:NH;
 I 35

mw 173.18, N 40.44$ZO; brownish-red powder, IMPACT, INITIATION OF EXPLOSION BY

rep-explodes mildly at 138°. May be prepd Introduction
from 3-imino-5-phenylirnino-l ,2,4-triazolidine It is common knowledge that a blow (im-
Refi Beil 26, [120] pact) can initiate explosion in certain substances
usually referred to as explosives. Aside from
superficial statements, such as the one above, the
Iminosuccinylazidic Acid (Iminosuccin-Azidsaure subject of impact initiation (also called impact
in Ger), ,CHCON3 sensitivity) of explosives has been shrouded in
HN, myth, confusion & misinformation. Until re-
CHC02H; mw 156.10, N 35.89%, cently, more time & money has been invested,
OB–5 1.3%; yellow ppt (from aq HC1). Prepd with less return on the investment, in studying
by dropwise addition of coned aq NaN02 impact sensitivity than any other aspects of ex-
to iminosuccinylhydrazidic acid dissolved in plosion sensitivity. This was most aptly stated
cold HC1. Explodes violently on heating in the following quotation (Ref 4)
Refs: 1) Beil, not found 2) Th. Curtius & “It is now becoming more widely recog-
W. Dorr, JPrChem 125, 439 (1930)& CA 24, nized that most of the standard impact
3214 (1930) and friction methods of measuring the
‘sensitivity’ of an explosion have little
physical significance. lkis is fair enough:
2-lmino-1,3,4-thiadiazoline and Derivatives. hitting a solid with a hammer or rubbing
See Aminothiadiazole and Derivatives in Vol it with a piece of sandpaper is perhaps
1, p A262–263 an experiment more proper to a carpen-
ter than to a physicist”
F. P. Bowden, F.R.S.
2-lminothiazoline Amino-
and Derivatives. See Even the concept of impact sensitivity as a
thiazole and Derivatives in Vol 1, pp A263–265 specific property of an explosive is questioned
and the additionrd entry below: in a recent publication (Ref 17), at least for
the response of confined explosive samples to
impact
Nitrosiminothiazoline. H$-S–~=NNO Nevertheless, examination of the response
HC —NH ; mw of explosives to more or less controlled impacts
129.14, N 32.54%; orange-red amorphous pow- did provide qualitative information about the
safety of handling these explosives. There is no
der; explodes ca 140° & decomp on storage in
question that Lead Azide is much more impact
moist atm; insol in water; sol in alc or eth.
sensitive than TNT, and that TNT is much
Prepd by reacting aminothiazole with NaN02
safer to handle than Lead Azide. It is the quan-
in HN03
titative meaning of the “much more” that creates
Refi Beil 27, 155
confusion and indeed it may have no quantitative
meaning at all. Presumably some of the immense
effort devoted in past years to impact testing
5-1mino-1,2,3,4-thiotriazoline. See 5-Amino-
1,2,3,4-thiotriazole in Vol 1, p A 164-R is excusable because it was based on the fond
hope (unfortunately unrealized) of finding the
ideal explosive–one that is powerful but
“insensitive”
5-lmino-2-thion-1,3,4-thiodiazolidine. See 5-
Amirio, 2-mercapto-l ,3,4-thiodiazole in Vol We have thus far avoided distinguishing be-
1, p A224-L tween impact sensitivity, projectile (or bullet)
sensitivity and shock sensitivity which also in-
volve impact loading of the test explosive. Shock
sensitivity, as the name implies, is the response
IMP. Initial Maximum Pressure (in rockets) is
the value of the pressure when it reaches a of an explosive to an externally generated shock.
steady state. See Fig under IASP in this Vol Measurements of shock sensitivity are very
Refi F. Bellinger et rd, IEC 38, 166-67 (1946) reproducible, although many existing measure-
 I 36

ment techniques only measure the shock sensi- the bottom end of the striker is shaped to
tivity of a material in the particular environment tit snugly into the open end of the cup. In
of the test, ie the measured “sensitivity” is not some tests a brass sleeve is placed under the
an absolute quantity. The characteristic time striker & over the test sample contained in i
scale of a shock sensitivity test is of the order a cup
of lflsec and peak stresses in the test sample Different laboratories use different criteria
are of the order a few kilobars to several tens for determining whether a drop-test resulted in
of kilobars. Characteristic response times in a an explosion (“go”) or failure (“no-go”). In
falling weight impact test are at least two many test facilities any visual observation of
orders of magnitude greater than in the shock smoke, flash or flame, or any crackle, pop or
sensitivity test, while peak stresses, in condensed bang detected by the operator is taken to
media, are at least two orders of magnitude less. signify a “go” result. Sometimes sound-meters
Typical test results are anything but reproducible. are used to detect the audible signals of a
Bullet sensitivity tests have times & stresses that drop test. In still more elaborate tests, the
lie between shock & impact test values. Generally, volume of gas, produced by a “go” result, is
reproducibility ii rather poor so that in this measured. In general, for “sensitive” explosives
respect bullet sensitivity resembles impact sensi- like PETN, distinguishing between “go” &
tivity more closely than it does shock sensitivity. “no-go” is quite easy. For “insensitive” ex-
For a discussion of bullet sensitivity, see “Bullet plosives like TNT, this distinction becomes
Tests” in Vol 2, pp B332-340 much more difficult, and it is for these
In what follows we will describe some impact “insensitive” materials that operator judgment
machines and impact tests, ie the apparatus and becomes unreliable and instrumental judgment
methods for “measuring” impact sensitivity. We devices become a necessity
will then present and discuss impact sensitivity Most test procedures are designed to obtain
data’ for common explosives obtained with the so-called 50% height, ie the height of drop
these machines by different laboratories. Then for which 1/2 the trials are “go” and 1/2 the
we will briefly consider how impact sensitivity trials are “no-go. ” The so-called “Bruceton” or
tests have contributed to the development of “up and down” or “stair-case” test is an efficient
the theory of initiation of explosives. Finally, method of obtaining 50!Z0heights. In this method,
we will examine impact testing from a theoreti- if the first trial is a “go” the next trial (using a
cal point of view fresh explosive sample) is made at a pre-deter-
mined drop height that is lower than the height
Impact Machines and Impact Tests. One
of the first trial. Drop heights are lowered in
frequently hears the remark that there are as
pre-determined steps (using a fresh sample for
many types of impact machines as there are
each trial) until a “no-go” is observed. Now the
explosives test laboratories. Thk is somewhat
drop height is increased to that of the last
misleading. In reality, all laboratories use essen-’
trial before the “no-go.” If this trial is a “go”
tially similar equipment but test procedures,
the drop. is again decreased in steps until a
and test data analyses differ. Basically an
“no-go” is observed. If it is “no-go” then the
‘impact machine is an apparatus that drops ‘a
drop height is increased,.in steps until a “go”
steel weight from a pre-determined height
is observed. This scheme, of increasing the
onto a plunger or striker resting on top of
drop height after a “no-go” & decreasing it
the test sample which is placed on a steel
after a “go, “ is continued until 20 or 25 drops
anvil
are made. Statistical methods of choosing the
Procedural differences among laboratories
drop height steps and analyzing the test data
. consist mainly in different methods of con-
have been carefully worked out by Dixon &
fining the explosive sample subjected to impact.
Mood (Ref 1). A concise description of test
In some laboratories the explosive is simply
procedure and analysis of results is found in
spread as a thin layer’ between striker & anvil.
Ref 5
In other laboratories fine sandpaper is placed
The Bruceton test (as expected) gives a
under :he explosive layer. Sometimes the
good value of the meari drop height, ie 50%
explosive is confined in a small steel cup and
 137 ,

height, but o the std deviation of this mean,

derived by statistical methods, often disagrees
with observations, ie observed “go’s” and
“no-go’s” frequently lie outside a 213limit
rl’’-’’s’riker
nl 0 h
around the 50% height. Martin & Saunders
used computer simulation of the Bruceton
test to assessits statistical validity (Ref 8).
Their computer runs could produce the
equivalent of 200,000 drop tests and thus
provided a good check of the large sample
theory on which the theory of the Bruceton
test is based (although in practice Bruceton
v%- Chamber Door.

sample size is far from “large”). Martin &

Saunders conclude that a Bruceton test of
25 samples yields a good estimate of the
50% height ‘but a poor estimate of its std
deviation. To get a good estimate of the
latter the minimum test sample size should
be 100 samples. They also conclude that
test height increments, ie the increase or
decrease in drop height after a “no-go” &
after a “go” should be equal to about 2cI.
In practice this means that one needs some
estimate of o before making the test in Fig 1. Anvil Striker Arrangement, ERL Machine
order to select the best height increments
The Bruceton method is also frequently
used in other destructive’ tests, eg in func-
tioning tests of detonators, gap tests for
shock sensitivity, or in tests where the test
alters a sample so that it is no longer in its
original state
Brief mention of impact machines is made
under “Physical Tests” in Vol 1, p XVII. Be-
cause there are many literature references to
the following impact machines, and not be-
cause they are inherently better than any others,
we will now describe the following: Explosives
Research Laboratory (ERL), Rotter, Bureau of
Mines (BOM) & Picatinny Arsenal (PicnArsn) s
we ER L machine is used at LASL, LLL &
NOL. A detailed view of the striker-anvil region
of an ERL machine is shown in Fig 1 & an
overall view in Fig 2
older

=ngscrew
I Concrete Base
I

Fig 2. Drop Weight Impact Machine,

ERL Model, type 12 tools
 138

It is claimed that the sandpaper under “the tained by dividing the measured 50% height by
explosive sample tends to minimize the effects the 50% height for a standard RDX sample
due to variation in surface roughness of striker and multiplying this ratio by 80 (Ref 12). It
& anvil (Ref 9). However, it was also claimed has been claimed that the volume of gas evolved
(Ref 10) that sandpaper tends to cushion im- can be related to the ease of propagation of
pact & give misleading results for very “sensi- explosion thru the test explosive. Hornby (Ref
tive” explosives like the azides. The Bruceton 13) presents data that show that increase in
method, usually involving 25 drops, is used at drop height (above the 50% height) has little
LASL, LLL & NOL. Samples are 30-40 mg effect on the amount of gas evolved by RDX
and are usually unconfined, though LASL places or by 60/40/1 RDX/TNT/wax. For pure RDX
them in a dimple in the sandpaper (Ref 11). gas evolution is always (with considerable
LASL & NOL use a 2-5kg falling weight, but variation) large (16ml). For the RDX mixture
LLL appears to be using a 5kg weight (Ref gas evolution is always small (1 -2ml). This is
18). Microphones and/or pressure transducers interpreted to mean that explosion, once
are used to aid the operator in his judgment initiated, propagates readily in pure RDX but
between “go” and “no-go” results for “insensi- not in RDX/TNT/wax. For Picric Acid gas
tive” explosives evolution increases with increasing drop height.
The Rotter apparatus as used at AWRE is According to Wilby, this shows that explosion
shown ,in Fig 3 in PA propagates more readily as impact energy
input is increased
Figure 4 shows a sketch of BOM machine

m“,’,” with samples placed in confining cups. This

(al
@

“L!
H
; -i-a
Drift
iii
I

Iiii!J
E-+l+’striker‘w
Striking Pin
Sample Cup
~Electromagnet

\
I SECTION
ANVIL ASSEMBLY B-B
,:,,
B’B
Drop
Hammer
4111’I’
I

Fig 3. Rotter Machine Impact Chamber and

Anvil-Striker Arrangement (not to scale)

A 40mg sample is placed on a brass cap

which is inverted over the anvil. The falling
weight is normally 5kg. If the volume of gas
evolved by a 0.03mg sample is more than 1ml,
then the test is considered a “go.” The Bruce-
ton method is used and results are reported Fig 4. Impact Apparatus Showing Anvil-striking
as Figure of Insensitiveness or FI which is ob- Pin Assembly
 I 39

.’

.,. --”’ ““ ,’

{_ti . .PD
. .. .. ..167354-;
.

Fig 5–1. Picatinny Arsenal Impact Test Apparatus

 I 40

“zero-in” on the minimum drop height at

!i%i-+ENTED
‘LUG’ ‘which at least one “go” is observed in 10 drops
(with fresh samples for every drop). One inch
,CAP”. below this height no explosions should be ob-
served in 10 drops. It is claimed that this
;CAVi~ “,FOR”TES~ EXP~O$l~E, “ machine is particularly suitable for impact-
,.,:,. -,
.
<,,
‘testing of “insensitive” military explosives such
=. ;DIE”{CU~”.
as TNT & Ammonium Picrate (Ref 16)
I In addition to the impact machines just
described, the search for a “perfect” impact
machine has resulted in the development of
many designs, most of which are not very dif-
ferent from each other, but are claimed to be
“improvements in the state of the art” by their
inventors. Below we list, in chronological order,
references to and very brief descriptions of some
of these machines
C.E. Bichel “Frdlapparat ziir Bestimmung der
Empfindlichkeit gegen Schlag und Stoss,” SS’ 3,
407 (1908)
W. J. Williams, “Impact Tests with the Drop-
hammer Method of Kast,” JFranklinInst 169,
Fig5–2. Parts of Picatinny Arsenal i43 (19Io)
Impact Test Apparatus Anon, “BOM .Small Impact Machine,” IEC
25, 665 (1933)
C. Hahn “An Improved Falling Weight
machine is also used with samples spread between Apparatus,” ArchPharmChemi (Copenhagen) 55,
sandblasted anvil & striker surfaces. Drop weights 259 (1948) & CA 42, 6113 (1948)
vary from 5kg to lkg but 2kg appears to be the W. J. Powell et al, “Ball and Disk Impact
weight most frequently used. The writer’s experi- Machine,” TransRoySoc A241, 287 (1948)
ence with BOM machines is that they are no N. R.S. Hollies et al, “Newly Designed Im-
better or no worse than the other types–at least pact Sensitivity Apparatus,” CanJChem 31,
for “sensitive” and “moderately sensitive” 746 (1953) & CA 48, 1683 (1954)
explosives P. Braid & R. L.angille, “A New Type of
A schematic diagram for the Picatinny Impact Machine,” CanJTech 33, 228 (1955)
Arsenal Machine is shown in Fig 5. The test & CA 49 (1955)
sample is poured into a hardened steel cup and R. C. Kopiuk describes an apparatus very
cup & sample are weighed. This weighing, to- similar to the PicnArsn machine, ASTM
gether with a previous weighing of empty cup, Bulletin No 250, 51 (1960)
gives the test sample wei~t. A brass cover is C. M. Ball, “A Colliding Ball HE Impact
then pressed over the cup and the covered cup Sensitivity Testing Machine,” 3rd ONR Symp
is positioned in a recess in the anvil. A vented on Deton (1960), vol 1, p 1
plug is placed on top & in the center of the N. A. Kholevo,” “Description of Type 1, 2
brass cover. The falling weight (2kg, lkg& llb & 3 Machines,” in Theory of Explosives (transl
weights are used) impacts the vented plug. The from Russ Teoriya Vzryvchatykh Veschestv)
test is begun with a 12-inch drop. If an explo- K. K. Andreyev et al, editors, FTD-MT 63-254,
sion is observed, drop heights are lowered in p 8 (1963)
2-inch steps until failure occurs. New sample Note: Development of these machines was
assemblies are used for each drop. If the initial actually begun in 1946.
drop results in a failure, drop heights are in-
creased in 4-inch steps until an explosion is
observed. These preliminary tests are used to
 I 41

TABLE 2 (Ref 12)

Impact Sensitivity Data. In view of the preceding
Impact Sensitivity Data Obtained with
section & the discussion to be presented in the
the Rotter Apparatus at AR DE
next section, preparing tables of impact sensitivity
(5kg falling weight& 30mg samples)
data for various explosives (even for the common
ones) is an exercise in futility. Reported results Median Figure of
from different test facilities whether they are for Explosive Insensitive-
50 heights or no explosion in 10 trials, etc and (CRS) ness
whether the impact stimulus is reported as fall Sulphurless Gunpowder 253 194
height, fall impulse or fall energy, just do not TNT 197 152
agree. When internal “standards” are used and Plastic explosive 197 152
results are reported as Figures of Insensitivity or RDX/TNT/Al/BWX, 41 .5/40/8/0.5 190 146
FI chances of qualitative agreement among test Rl?X/TNT/Wax, 60/40/1 152 117
facilities are improved but quantitative agreement RDX/TNT, 60/40 137 105
is rare. About the best one can hope for is a RDX/Wax, 9 1/9 127 98
qualitative ordering of impact sensitivity, ie Octol 94
statements like: Lead Azide is more sensitive Gunpowder 117 90
than RDX which is more sensitive than TNT Tetryl (CE) 112 86
The following Tables of Impact Sensitivity RDX; Standard 104 80
data serve to justify the above statements: RDX, Military Grade 98 75
Table 1 shows quantitative accord between HMx 73 56
NOL & LASL (they use the same type of equip- PETN 66 51
ment & test procedure), and some agreement Lead Azide* 113 20
between NOL, LASL & Picn Arsn for sensitive Lead Styphnate* 69 12
& moderately sensitive explosives such as PETN, Lead 2:4 dinitro-resorcinate* 61 11
RDX & HMX. The BOM 50% heights for * These explosives were tested with a 2kg weight,
explosives more sensitive than TNT are much and Lead 2:4 dinitro-resorcinate was used as the
larger than those of the other facilities. The standard for comparison with an FI of 11
Rotter data (Table 2) gives 50% heights that
are even larger than the BOM data. Thus
Tables 1 & 2 show that quantitative agreement
of impact data among differerit laboratories is
rare
TABLE 1 (Ref 14)
Comparison of Impact Sensitiveness Tests (Powdered Samples)
NOL* LASL* BuMines PA PA
50% Pt 50% Pt ERL (BuMines) Apparatus
50% Pt 10% Pt** 10% Pt**
cm c1 cm 0 cm cm in
Lead Azide 4 0.12 – – – 17 5
PETN 12 0.13 12 0.05 43 17 6
RDx 24 0.11 22 0.01 79 32 8
HMX 26 0.10 26 0.02 – 32 9
Tetryl 38 0.07 42 0.02 94 26 8
Comp B 60 0.13 59 0.02 – 75 14
TNT 157 0.10 154 0.03 183 98 15
Explosive D 254 0.05 190 – – — 17
* o is the std deviation of the 50% height
** This is really the hei@t at which at least one explosion WaS
observed in 10 trials. One inch below thk height there were
no explosions in 10 trials
 1“42

TABLE 3
Comparison of impact Sensitivity Tests
on the Basis of Figures of Insensitivity, FI
FIX
Explosive ARDE NOL LASL Picn Arsn LLL
(Rotter Test) (ERL Test) (ERL Test) (PA Test) (ERL Test)
Explosive D — 850 690 170 —
TNT 152 522 560 150 228
Comp A-3 98 195 -250 160 —
Comp B 117 200 214 140 128
75/25 Octol 94 — 138 170 116
75/25 Cydotol — — 132 <140 95
Tetryl 86, 126 153 80 80
HMx 56 87 95 90 94
RDX (used as Std) 80 80 80 80 80
PETN 51 40 44 50 31
Lead Azide 20 5 — 50 –
*ARDE values from Table 2; NOL, LASL & Picn Arsn values computed by
us from the data of Table 1; LLL values computed by us from the data
in Ref 18

One might suspect that use of an internal

standard might bring better agreement. Conse-
TABLE 4
quently, in Table 3, we have used ARDEs
Qualitative Ranking of the Impact Sensitivity
definition of Figure of Insensitiveness, FI, to
of Common Explosives
arrange the data of Tables 1 & 2 on a common
basis. As seen in ~Table 3, this procedure does (Based on FI data of Table 3)
not bring all the results into agreement. Dif- Ranking (a)
ferences in FI appear to be greatest for the Explosive ARDE Picn Arsn LLL LASL NOL
least sensitive & most sensitive explosives Lead Azide 1 1. (b) – – 1
Now even if we abandon all attempts at PETN 2 2 2 (c) 2 (c) 2
getting quantitative accord, and merely attempt RDX 4 3 33 3
a qualitative ranking of explosives, ie Expl, A HMx 3 5 54 4
is more sensitive than Expl B etc, we still Tetryl 5 3 (d) 3 (d) 6 5
find disagreements. As shown in Table 4 there Octol 6 9(0 6 5 –
are reversals in sensitivity rankings for RDX, Comp B 8 6 77 7
HMX & Tetryl, and Comp B, Comp A-3 & TNT Comp A-3 7 8 — 8 6
To some degree the variation in impact TNT 9 7 9 (e) 9 8
sensitivity data among different test facilities Explosive D — 9 – 10 9
can be attributed to differences in: drop (a) 1 is the most “sensitive” and 9 is the least
weights (some laboratories use 5kg weights, “sensitive” explosive
others 2kg weights etc), in test sample weights, (b) FI values mike it appear much less impact-sensitive
in sample confinement, impact surface rough- relative to PETN than FI values from other facilities
ness, methods of analyzing the data, etc.’ How- (c) Assuming that LA would have had lower FI value
ever when the effects of these variables are had it been tested
examined in any one laboratory, it is generally (d) Same FI as for RDX
found that these effects are relatively small, and (e) Assuming that Comp A-3 is more sensitive than TNT
certainly not large enough to explain the large (f) Same FI as Expl D
differences in 50% heights or even FI’s obtained
by different laboratories for the same series of
explosives
 I 43

It might appear then that impact testing bubbles trapped in or purposely introduced into
is a complete exercise in futility and should be the explosive sample; b) by intercrystalline
abandoned. This is definitely the wrong conclu- friction (for high-melting explosives); c) by fric-
sion. Impact “sensitivity” properly interpreted tion of the impacting surfaces; e) by plastic de-
has its uses. This is aptly stated by Hornig (Ref formation of a sharply-pointed impacting surface;
14): ~ by viscous heating of the impacted material
“Sensitiveness measurements should be con- as it flows past the periphery of the impacting
sidered as dimensionless, although we often do surfaces—appreciable heating in this case is
give units to them. The numbers gain their claimed to occur only for quite energetic impacts
significance only by comparison. Fortunately, The many mechanisms of generating hot spots,
we have today a considerable storehouse of ex- coupled with complex nature of the development
perience in the handling and use of a large of a hot spot into an explosion (see Ref 19) or
number of explosives and explosive compositions. the decay of a hot spot without explosion, offer
We also have laboratory measurements of their a convincing explanation for the observed vari-
sensitiveness. When a new compound or compo- ability of impact test results. Thus, in test method
sition is tested, its standing can be compared a), hot spot formation via adiabatic compression
with the known explosives and the new one may be dominant. In test method b), viscous
can be categorized as being similar to one of heating may be the main mechanism for heat
the old ones. This gives a reasonable knowledge generation. In test method c), conditions may
of the degree of hazard faced” favor rapid quenching of hot spots, and so
Theoretical Considerations. In the preceding forth. Even with a given test method several hot
sections we have been rather negative about spot generating mechanisms may be operative
impact testing of explosives. We have stressed and these can then develop into explosion by
the great variability of impact data and the lack different paths. Consequently even slight changes
of a quantitative characterization of impact in procedure or conditions may produce quite
sensitivity. Yet impact testing has triggered im- drastic changes in impact test results
portant developments in the theory of initiation Some of the quantitative consequences of
of explosives. The classic work of Bowden & hot spot theory were presented in Ref 19. A
his school on this subject is summarized in two qualitative discussion of heat flow in a com-
excellent monographs (Refs 2 & 3) and in a pressed gas bubble hot spot was also presented
more recent publication (Ref 15). However the in Ref 19. The necessity of having enough, but
hot spot theory, so successfully championed by not too much, liquid or solid spray or foam
Bowden, cannot explain all the strange and within a compressed gas bubble (in order to
apparently contradictory effects observed in have sufficient heat flow from the bubble to
impact testing of explosives. Some of these the surrounding condensed explosive) provides
weird phenomena led Kholevo (Ref 6) and another hard-to-control variable in impact
later Bobolev et al (Ref 17) to develop a testing and thus increases the variability of
rather different theory of impact initiation than test results
that of Bowden. We will now examine both of Until now we have studiously avoided de-
these theories in some detail fining what constitutes an explosion or “go”
Much of Bowden’s theory has already been result in an impact test, except mentioning that
described under Hot Spots in this Volume (we “go’s” are judged on the basis of sound, flash,
shall henceforth refer to this as Ref 19). Briefly gas volume etc. What physical events produce
what Bowden proposed was that most impact these observed manifestations? Based primarily
initiations are produced by very localized regions on the studies of Bowden (Ref 2) it is clear
of high temperature ie hot spots. He showed that in an impact test “explosion” frequently
that a falling weight impacting an explosive starts as a relatively mild deflagration which
sample can generate hot spots in the following can propagate as slowly as 10m/see, which
ways: a) by adiabaticly compressing air (or vapor turns into a much more violent deflagration,
of the test explosive if impacts are made at sub- (1 00-1000m/see), in the confined (by striker &
atmospheric pressure or at elevated temperatures) anvil) explosive. For many “insensitive” explo-
 I 44

sives this is all that occurs. For the more “sen- may be extruded by impact. Kholevo No 2 has
sitive” explosives (PETN, RDX) the fast de- no sleeve and the sample can “flow” or deform
flagration stage is followed by a true detonation. unimpeded upon impact. Kholevo No 3 is essen.
The only known exceptions to the sequence of tially the same as No 1 except that there is a
deflagration-detonation are the heavy-metal azides, very tight fit between striker/anvil & sleeve. If
For Lead & Silver Azides impact creates either the sample is spread uniformly over the entire
a full-blown detonation (no deflagration stage) striker-anvil contact area, sample deformation is
or a failure (Ref 2) totally impeded in Kholevo No 3
During impact the explosive sample is at an Unfortunately, the translation of A & B’s
elevated pressure, and the initial deflagration of book is rather uneven and it is difficult to
the sample consequently occurs at elevated capture” all of the finer details of their presenta-
pressures. As pointed out by Andreev (Ref 7), tion. Moreover their presentation is somewhat
the critical thickness for the deflagration of diffuse and lacks a good summary. Below we
secondary explosives is much greater than the will summarize the main thrust of A & B’s
usual sample thickness in an impact test. Since ideas and then select (from various portions of
the critical thickness decreases as ambient pres- A & Bs book) supporting evidence for these
sure increases, impact not only generates the ideas
heat required to initiate deflagration but also Summary: 1) Impact Initiation is a thermal
provides the necessary pressure for the defla- process that occurs heterogeneously at localized
gration. Highly localized “explosion” upon im~ regions of high temperature–hot spots
pact can be the result of too rapid a pressure 2) As usual, the impact initiation process is
drop in the impact system. Thus, deflagration divided into two stages; in the first stage part
may die out if the pressure in the system be- of the explosive is heated to a critical tem-
comes too low (approaches atmospheric). These perature and in the second stage these heated
considerations re-emphasize the difficulty or regions self-ignite
even impossibility of separating the effects of The actual impact (at fall hammer velocities
initiation and propagation in an impact-gener- of 1-5 m/see) can be considered as a pseudo-
ated explosion static process, ie the rate of loading is much
A rather different view of impact initiation slower than the sound velocity in either the
to that of Bowden et al, is presented by the apparatus or the compacted explosive sample
Russian school. The originator of this school 3) The maximum hot spot temperature is
appears to be Kholevo (Ref 6), supported by limited by the melting point of the impacted
Andreev (Ref 7), with a recent and detailed medium, but this is the melting point at the
presentation of this point of view provided by elevated pressure of the impact and not the
Afanas’ev & Bobolev (Ref 17) (from now on ordinary melting point at one atmosphere
we will refer to these writers as A & B with- 4) A necessary but not sufficient condition
out listing the Ref). Briefly stated, A & B for initiation by impact is that impact pressure
consider that the prime mechanism of hot (stress) be sufficiently high so that the melting
spot generation in solid explosives is by inelas- point of the explosive is raised above some
tic deformation of the entire impacted explo- critical temperature, Tcr. For T>Tcr the explo-
sive sample (Kholevo (Ref 6) calls this “flow”) sive, in the hot spot, will decompose adiabati-
To understand what follows we must briefly cally in times of the order 10#sec, which has
digress and describe three impact machines con- been observed experimentally. The relation be-
stantly alluded to in the Russian literature—the tween Tcr & the critical stress is then expressed
so-called Kholevo No 1, No 2 & No 3. Kholevo by:
No 1 is quite similar to Kast’s impact machine pcr = (Tcr–Tm)/~ (1)
(see section on Impact Machines). The explosive where Pcr is the max critical stress generated
sample is placed between a striker & an anvil in the explosive by the impact and Tm is the
which are contained within a sleeve. Since melting point of the explosive at one atmo-
striker & anvil fit rather loosely into the sleeve sphere. This relation is based on the assump-
there is a small air gap into which the explosive tion that
 I 45

Tin(P) = Tm + ~P (la) defines a critical thickness her. This critical

where O,is a constant which, according to Ref thickness is a specific property of the explosive
4a, has the approximate value of 0.02°C/ if the impact is made on unconfined explosive
atmosphere for all explosives. For most of the samples (ie in Kholevo No 2 type impact
common high explosives 400~cr~000C and machines) with a striker of fixed diameter
the corresponding Pcr is then S1 Okbar. Further- According to Eqs 2 & 2a, one should present
more, the hot spot radius for these explosives experimental data in the form of plots of ~ vs
is of the order of 10-4 cm. It must be empha- h/D or h (if D is a fixed sample diameter).
sized that Eq 1 says nothing about how the This will be done in a following section
hot spot is created. AU it says is that impact 6) We will now present a summary of A & B’s
must generate a stress in the explosive at description of the processes that generate hot
least equal to Pcr or Plmpact > Per. This crit- spots in impacted layers of explosive. The pro-
icality condition could be satisfied by slow cessesare complex but fortunately rather dras-
hydrostatic compression of the sample under tic simplifications lead to conclusions that are
circumstances where explosion is known not in accord with experimental results’. In con-
to occur sidering non-isothermal shear on plastic bodies,
5) If, as stated above, Pcr = 10kbar, then A & B conclude that this shear will result in a
the question arises how stresses of this magni- discontinuity in the straining rate and conse-
tude can be generated by impact in explosive quently in heat generation by the transformation
compacts whose compressive strengths are about of elastic energy stored in the sample into de-
100 fold less than Per. For unconfined explosive formation work at the shear plane. These pro-
compacts (in Kholevo No 2) this can only occur cessesare always localized and continue spon-
with “thin” explosive compacts, ie with explo- taneously until all the stored elastic energy
sive layers whose h/X<l where h & D are (and the kinetic energy of relative motion,
explosive thickness & diameter. The relation along the shear plane, of the upper & lower
between, ISu, the ultimate compressive strength portions of the sample) of the sample is used
of the explosive compact & the average stress, up. If there is sufficient energy for portions
Fu, at which the compact fails via brittle frac- of the sample (along the shear plane) to melt
ture (in compression) is: the process continues as deformation work of
~u = OU(l t D/3fih) (2) the viscous layer. When the rapidly-deforming
liquid phase is created, heat transfer in it
The stress varies over the sample (compact) occurs via convection and is more rapid than
surface such that the peak stress is (2 to 2.5)~ heat transfer in the solid which is by con-
at the center and 0u/3 at the periphery (where duction. Thus the liquid phase tends to stay
~ is the average stress on the sample). Since at temperatures that are near the melting
Pcr>>ou for most explosives, and the criticality point (at that pressure) because of rapid heat
condition is P>Pcr, effective hot spots cannot losses particularly to any solid material dis-
form near the sample periphery. Effective hot
persed within the liquid. Some of this solid
spots are also not generated at the center of
material will melt and absorb energy thereby
the sample because inelastic deformation of the
(heat of fusion). ‘Ilk modgl is obviously in
sample is a minimum near its center. As will
accord with Eq 1 which states that the critical
be shown, A & B claim that non-uniform in- temperature is the temperature of melting at
elastic deformation of the entire sample gener- Pcr
ates hot spots A & B also present arguments that indicate
Because of the variation in stress over the that inhomogeneities in the solid, unless they
‘sample, A & B relate all stress effects to ~ the are as large as 0.1 mm, do not affect the heat-
average stress. Now if we assume that there ing mechanism. They also argue that Kholevo’s
exists an average critical stress ~cr, above which original viscoplastic model (Ref 6) is unrealistic
explosions occur, and that it lies on the ~u vs and that their model of a brittle body is closer
h (or h/D if D varies) plot of Eq 2, then to reality
~cr = CJU(l + D/3@hcr) (2a) 7) Thus far we have presented A & Bs ideas
 I 46

on the initiation of solid explosives by impact. 3 does not agree with experiment, ie for these
In the real world initiation and propagation are explosives the observed Pcr > (3-4.8)GU. Thus
very difficult to separate. Consequently any another model must be developed which takes
experimental measurement of “impact sensitivity” into account the appreciable increase in Uu
will depend on the processes that control initiation that is possible in thin samples
and propagation under the particular conditions We quote A &B:
of the measurement, A & B point out that the “Suppose a rigid flat surface supports an
deformation and fracture of the solid explosive, explosive layer, which is subject to impact by
which creates the hot spots required for initia- a rigid cylindrical body (of diameter D) with
tion, may also aid transition to detonation be- flat base. Fig 6a illustrates impact on a layer
cause the deflagration started by the hot spots of high density, and Fig 6b impact on a layer
propagates into regions of greater surface area of low density, for example bulk density. In
(fractured regions) where it will accelerate. Un- the latter case, the explosive should be strongly
less some quenching mechmisms are also compacted in the impact zone before a signifi-
present, the accelerating deflagration will eventu- cant pressure rise begins. * The deformation
ally become a stable detonation
Based on an analysis of the penetration of
a thick, rigid plastic body by a rigid cylinder
(whose radius is smaller than the radius of the
body), A & B arrive at

‘Cr c 3 to 4.8
—\ (3)
Ou
and empirically Fig 6a. Layer density close to maximum
Pcr ~ 2P~r (4)
Since the force F on a sample is rr/4PD2, the
minimum force for initiation is:
Fm = n/4PcrD~ = (3-4.8 )rT/4iSuD~ (5)
.--l%--
i L+th ,
chp’o’ivc~
where the minimum sample diameter, Dm, 7777//// / /+//7777+?///,/ ‘/1A
must satisfy the conditions required for propa- II I
1 i
gating detonation in the particular thick explo-
sive sample. The obvious condition is that Fig 6b. Layer of low density (pressing of the
material takes place at the beginning
Dm = dcr (6),
of the impact)
where the dcr is the critical detonation diameter,
ie the diameter below which detonation will not *Note: Typically crystal density/bulk density
propagate no matter how it is initiated. More- ‘2 and a typical striker velocity, u. is -5
over a further limitation is that Dm must exceed m/see. The minimum time for a loosely packed
some limiting dimension al which is required explosive to be compressed on impact to near
for the generation of hot spots capable of pro- crystal density is then ‘h/2u~. For h=hc~0.2
ducing self-propagating chemical reaction. For mm this amounts to 2 x 10-5 sec or consider-
secondary explosives, one expects dcr>al, but ably longer than the initiation time of less than
this may not be true for primary explosives, the 10-ssec claimed by A & B for compacted
eg dcr= 10-2 mm for Lead Azide; in which explosives. A & B do not comment on this. If,
case as A & B suggest, no appreciable heating occurs
Dm=al (6a) until the sample is compressed to near crystal
The above considerations were for thick density, the “long” compression time should
samples, and are inapplicable to the usual con- not affect their subsequent conclusions, but in
ditions of an impact test, except for impacts practice one should observe longer times from
on a single crystal of a primary explosive. For impact to ignition for loosely packed explosives
most secondary explosives the condition of Eq than for densely packed explosives
 I 47

conditions in the impact zone are similar to ure the layer thickness under the striker be-
the conditions in instrument No 2 (the lateral comes less than Icr; with each failure material
pressure of the explosive mass surrounding the is ejected from the compression zone and some
striker can be disregarded, since the explosive of the explosive surrounding the striker is
ultimate strength even in the cast state is very scattered); for D>Dm, detonation of the whole
low). When the critical explosion initiation explosive layer may be initiated if
conditions are satisfied, ignition takes place in
the impact zone. Spreading out from the ig-
nition spot, the explosive transformation should Thus, for impact on a thin layer detonation” can
become detonative in order to advance beyond be initiated over some range of the impact para-
the compression zone. It is known that deto- meters F and D; respectively equal to or greater
nation can only propagate through a charge than Fmin and Dmin, if the layer thickness h
of diameter not less than dcr, the critical deto- is equal to or greater than lcr’
nation diameter (for, a charge of cylindrical Analogous to the requirement of dcr > al
form). In our case,the charge through which for thick samples, we now have dcr > hl. For
detonation should pass is a layer of thickness hl > dcr/2 (encountered only for primary explo-
h; detonation is only possible when the thick- sives, if at all) lcr in Eq 7 should be replaced
ness h is not less than some critical value lcr, by hl. Also, to a good approximation, for
where Icr is expected to be proportional to dcr/2 > hl (the usual case for secondary explo-
dcr, ie for detonation to propagate beyond sives) we replace lcr by dcr/2 in Eq 7, which
the impact zone it is necessary that D lcr=kdcr then becomes
(k being a proportionality factor, apparently Dm = 2.6{~cr-Ou(TO)} dcr(T0,~ , PO)/Ou(TO) (8)
close to 1/2). We draw attention to the fact
that lcr in the compression zone (a two-sided where the terms in ( ) indicate functional depen-
shell) is smaller than in the noncompressed dence, eg dcr is a function of initial temperature,
layer. Thus, the propagation of detonation is explosive particle size, and initial density of
limited by the noncompressed explosive, in the the explosive sample etc
first place by the emergence ,from the com- Let us now examine how these initial con-
pression zone into the noncompressed explosive” ditions affect Dm and consequently the force
NOW from Eq 2, ~u > ~cr & h> ICr we ob- required for initiation, remembering that Fm
tain for thin explosive layers increases as the square of Dm; thus a fairly
small’ increase in Dm can lead to a substantial
Fm = n/4D& ~cr (6)
increase in Fm and consequently a decrease in
and impact sensitivity
Dm = 3@ lcr(Pcr–-~u)/ CJU (7) For pure primary & secondary explosives
If the diameter D of the, striker is less than Dm (except for border-line HE such as Ammoriium
or the force is less than Fm then detonation of Nitrate or Ammonium Perchlorate) dcr decreases
the whole charge is impossible (provided, of as PO increases until PO approaches very close
course, that the velocity of the striker is much single crystal density when dcr may increase
less than the velocity of sound) and explosion drastically. fius if we limit ourselves to
may occur only in the impact zone. Consider P. ~ 0.9PcVst, increases in P. (according to
the variations which may be encountered in the Eq 8) should result in a greater sensitivity to
case of impact on a thin layer: impact. This is quite the opposite of what is
1) When h < lcr, detonation of the whole found for shock initiation and will be examined
layer is impossible; explosion in the impact more closely later on. At a fixed density, dcr
zone is possible if increases as K. increases (see A & B, p 90). This
F>~D2~cr increase is fairly pronounced at small p (<0.2
2) When h > Icr, then for D < Dm detonation mm) but levels off & becomes almost asymp-
of the whole layer is impossible; explosion’ may totic at large # (X.4mm, except for cast
occur only in the impact zone after one or TNT or TNT with 1% paraffin oil). Thus an
several attempts if F > ~ Dz ~cr (after each fail. increase in p, as expected, leads to a decrease
 I 4?5

in impact sensifl”vity. The effect of TO is more The Kholevo No 1 machine (with smrdl g) has
complicated. As expected, dcr decreases as TO the advantage that any localized ignition (be-
increases, but so does Ou. Since dcr & Ou cause.of confinement) spontaneously leads to
occur in the numerator and denominator of ~ explosion. Thus characterizing the impact
8, and also as a negative term in the numer- sensitivity of a laterally-confined explosive re-
ator, it is not possible to determine the effect quires only the determination of conditions
of TO without specific information on the necessary for initiation. But this determination
values of dcr & Ou at a particular TO for a depends on both the properties of the explo-
particular explosive. Furthermore, and this is sive and the conditions of deformation (magni-
not considered by A&B, a TO appreciably tude of g). Thus no specific explosive sensitivi~
above room temperature means that less energy can be defined for laterally (more or less) con-
needs to be expended for hot spots to reach fined impacts. By way of contrast, in uncon-
Tcr than for the same system initially at room fined impacts (Kholevo No 2) the concept of
temperature explosive sensitivity has meaning, but now must
Because of all these compensating factors, determine now only the conditions for initiation
the effect of ‘fO on impact sensitivity is ex- but also those for propagation
pected to be fairly small, but there may be 9) The wide scatter and probabilistic nature
regions of TO where the effect could be of impact measurements are attributed by A & B
appreciable not to any statistically controlled initiation or
The chemical reactivity of the impacted propagation processes but primarily to fluctu-
explosive is manifested primarily thru Pcr which ations in au for the explosive samples
controls Tcr (see Eq 1): the more “reactive” 10) We have attempted to present A & Bs
the explosive the lower the Tcr. Of course dcr views on impact initiation of solid explosives.
also depends to some degree on chemical In spite of the concerted effort of these
“reactivity.” Increased reactivity affects Pcr & authors to develop a quantitative or at least
dcr in the same direction, ie towards increasing semi-quantitative picture for impact sensitivity,
the impact sensitivity A & B realize that they have not achieved
8) All the above considerations were pri- that goal. We quote:
marily for well-compacted solid explosive wafers “Consider briefly the relative character of
impacted in a laterally unconfined state (Kholevo sensitivity evaluation, namely, that it is possible
No 2 machine). How do these considerations only to speak of a higher or lower sensitivity
change if impacts are made in a Kholevo No 1 of one explosive as compared with another. It
machine which provides some lateral confinement would be meaningless, for example, to say that
of the explosive sample? The degiee of lateral the sensitivi~ of some explosive is so many
confinement depends on g the thickness of the times higher than that of another explosive. No
air gap between striker/anvil and the surrounding single sensitivityy has this property: in this sense
sleeve. Obviously if g is large Kholevo No 1 it is analogous with such a property of explo-
impact results should be indistinguishable from sives as, for example, detonation capacity. It
1
Kholevo No 2 results. According to A &B, it is most convenient to compare explosives with
is very difficult to initiate explosives in the respect to sensitivity, against those explosives
Kholevo No 3 machine in which g ~ o. The about whose sensitivity fairly firm empirical
expression, analogous to Eq 2, proposed by ideas exist, eg the explosives of a reference
A & B for Kholevo No 1 impacts is series”
This writer heartily subscribes to these
~u = (su(l + h/g2~+ D/h3~) (9)
conclusions
According to A & B, the critical stresses for Expen”mental Evidence: We will now discuss
the No 1 & No 2 machines are essentially equiv- the evidence presented by A & B in support
alent, therefore, comparing Eqs 2a & 9 (where of their views. of impact initiation described
the h’s are replaced by her’s) the critical above. After a brief description of their main
sample thickness is greater in Kholevo No 1 experimental techniques we will attempt to
than the critical thickness in Kholevo No 2. present experimental data that support each
 I 49

of the ten topics of the previous section. material from the compression zone. Explo-
Since these overlap to some extent the experi- sions are also characterized by sharp pressure
mental data wilJ also overlap occasionally drops. For primary explosives A & B present
The best evidence in support of A & Bs convincing evidence that explosion occurs be-
views comes from experiments performed in fore fracture and in times of the order of
the apparatus shown in Fig 7. This apparatus 10~sec. For secondary explosives the evidence
is not as clear-cut. Incidentally, because of
the “slow” (relative to sound velocity) rate
of loading the impact process is essentially
a static process, ie stresses in the striker &
sample are equalized and there is no effect
of impedance mismatch found in shock
loading
Fig 7. Design of apparatus and connection of 1) No new evidence is presented in support
the pickup to the oscillograph of the thermal nature of impact initiation. How-
1-rollers; 2-sleeve; 3-bedplate; 4-trans- ever A & B give a detailed analysis, based on
ducer; S-charge results qbtained with the apparatus just described,
of the energy distribution in the Kholevo No 2
yields stress-time records which are analyzed machine. Thus,
to give the average stress-time, ~ vs t, striker WO= W~”+W#+ Ws+ Wex
velocity-time, u vs t, sample displacement
time, Ah vs t, and displacement vs average where WO is the kinetic energy of impact, W~ &
stress curves, Ah vs ~, shown in Fig 8. The W#j are the work of plastic & elastic deformation
of the striker & anvil, Ws are the irreversible
seismic energy losses, & Wex is the elastic and
j~jo~t plastic work in deforming the explosive charge.
In a typical case (for which explosion is ob-
served) if all of Wex goes into uniform heating
~j:~l ~ of the explosive the temperature rise in the
{Al, !~ explosive will amount to only 30°
~~~ 2) There is no direct experimental justifica-
..-. -L_- ‘ m. tion for the assumption that the initiation pro-
k I Ah:,(t) ~ cess is separable into a heating stage (to Tcr)
q --------- ,
I—_P& l
& a self-ignition stage (at Tcr). Justification
Fig 8. Interpretation of oscilloscope traces of comes from the self-consistency of the over-all
pressure pulses picture of impact sensitivity developed by A & B
3) & 4) Here again evidence is circumstantial.
curves on the left are for a Kholevo NO 2 The existence of ~cr (ideally no explosions be-
apparatus without an explosive sample, and low Pcr & no failures above ~cr) is required by
the ones on the right are with an explosive the model which is summarized by Eqs 1 & 1a.
sample. Time resolution is 5 to 10usec & the Experimental verification of the existence of
uncertainty in stress is about 10%. These curves ~cr will be presented below. It must be empha-
show that ~ (without explosive sample) is in- sized, however, that the model of Eqs 1 & 1a
dependent of hammer weight or drop weight is not the only one capable of explaining the
and is determined solely by the kinetic energy existence of Pcr
of the hammer. The Ah vs ~ curve uniquely 5) We will now present data in support of
determines the loading conditions of the par- the existence of ~cr and Eq 2. Since most of
ticular instrument for which it was obtained. these data are shown as functions of h, the
The sharp drop-offs of both the ~–t and original thickness of the explosive samples, we
Ahex-t records, for impacts with an explo- must first examine the validity of using h
sive sample, correspond to fracture of the rather than the thickness of an impacted sample
sample and ejection of some of ’the fractured Pre-pressed explosive wafers (at around 90%
 I 50

of crystal density) are shown to behave almost & for single crystals.. Particle size affects the
elastically for deformations of less than 10% spread in ~ (but not the average) in the sense
and then fracture. If one assumes thdt explo- that spread is decreased as particle size decreases.
sion” occurs before this first fracture (at least Furthermore, A & B state that pre-pressing the
for hcr > h; see below & item 7 of this section) explosives at 200atm or 20,000atm has no
then thickness of the impacted sample just be- effect on ~. The writer estimates that PETN
fore explosion, is very close to that of the & RDX at 200atm have a bulk density, PO, of
original sample about 80% of crystal density. Thus, according
f. /0:’kr,fc# to A & B, ~ does not depend on pO in the
range 80% < pO,<10070 of crystal density

~10‘f kgf.m’
12
N
10-

t-
~cr--
6-

h.mrm 4-
Fig 9. Average pressures upon fracture (Pult–
solid curves) and upon explosion (Pex– 2-
dashed curves) vs charge thickness, of 1-
HMX (00), RDX (F’ Y ), Tetryl (~) [ , 1, 1 I 1 1 1 I I
and TNT (u~) 0..? , a4 M aa U h,mm
Fig 11. Spread of the measured pressures upon
10
P./o;Jkgicnlz fracture (Pult–circles) and upon explo-
sion (Pex–crosses) for RDX
4’
\
\ Figure 11 shows the typical variation in experi- 1
,6+, )
\ mental data and indicates the accuracy with which
4 %
+ ~cr can be determined. Incidentally Eq 2 fits the I
data of Figs 9, 10 & 11 to within experimental
z
error
E Two other observations are of interest: ~
o 0.2 0+ 06 R8 10
b.mm does not depend on hammer drop height (or
Fig 10. Average pressures l’ult and Pex vs drop velocity)
charge thickness for PETN (o.) and The empirical relation,
Trinitrophenol (M) ~u = 4.2 Tm (OU in kg/cm2 & Tm in “C) (10)
Points marked t’ refer” to Diria appears to be well-obeyed by explosives for which
data are available
Figures 9 & 10 show A & B’s results in the The critical stresses and critical thickness, ob-
form of ~ vs h plots for a number of different tained from Figs 9, 10 & 11 are summarized in
explosives at around 90% crystal density’: They Table 5
claim that for PETN, RDX & HMX, ~ is un- ~
affected (within a 10% experimental uncertainty)
if particle size distribution is’ varied from 1-10p
in one series of experiments to 31 5-400p in a
second series. They also claim that ~ is the same
(within experimental error) for pressed wafers ,.
 I 51

TABLE 5: Critical Stresses& Thicknesses for h < her. For h > her, the condition ~> Pcr
in Instrument No ? for Various ExplI ;ives is not satisfied and at first glance explosion
Explosive Pcrl 0-3 kg/cm2 l~rmm should not occur. That explosions do occur
for h > hcr i} shown in Fig 12. The explanation
TNT -11 Q.08
Trinitrophenol ‘-9.5 -0.11
Tetryl -8.4 Q.12
“[--T--~J
Ok, :/ii >-+--1
Ii!
,-
RDX 7.0 0.25 u6j 1{
1/ A
?
HMX 6.4 0.43
PETN 4.8 0.27
I I Q I . 1 I I
n~1234s6 7
6) To show that shear, due to a discontinu- ~~.kg.m

ous rate of straining, is at a maximum at the Fig 12. Explosion frequency vs impact energy
upper and lower (contact) planes of an explo- for Tetryl (0) and RDX (L) for charges
sive sample, impacted in Kholevo No 2, and 0.4mm thick and for HMX (o) charges
zero at its mid-plane, A & B performed the 0.5mm thick
/
following experiment. Two sets of 1mm thick
HMX samples were prepared: set 1 contained offered for this contradiction is that fracture
a thin layer of Lead Azide at its mid-plane, of the sample occurs before explosion for
set 2 had a thin layer of Lead Azide on the h > her. If the impact energy is sufficiently
upper, lower or both sample surfaces. Set 1 high sequential fractures (see Fig 8) can pro-
samples behaved just like pure HMX in that duce a “new” sample thickness hn such that
only fractures and no explosions were observed hn < her. NOW if Pn > Pcr explosion can occur.
(h> her, see Fig 13). All set 2 samples exploded This sequential process tends to increase the
They also used set 2-type PETN, RDX, variability of the dependence of fractures on
Tetryi & TNT to show that ~cr for Lead ~ and consequently on impact energy. Thus
Azide is 2.6 t 0.2 kbar and that ~cr (at least for f vs impact energy curves should show more
Lead Azide) is independent of h or h/D spread than those for h < her. Presumably at
7) The experimental results discussed below f+ 1, ie large values of impact energy (and
deal with certain aspects of initiation and pro- consequently ~) there are more fractures and
pagation of impact explosions but some of the frequency curve gets more spread out
discussion overlaps topics 5 & 6 (flattened) than in the lower range of frequen-
The usual charge thickness (“standard” cies. The non-dependence of f on impact en-
charge) for HE in Kholevo No 2 is ‘0.4mm ergy, observed for Tetryl & TNT, is explained
(-50mg of HE). At’ this charge thickness by A & B as follows: “Suppose hl is not much
anamolous behavior is encountered with some smaller than hcr (hI it will be recalled is the
of the “less sensitive” explosives. Figure 12 limiting sample thickness for which hot-spots
shows explosion frequency as a function of can lead to self-ignition), then the charge
impact energy for three explosives (HMX, RDX thickness, decreasing during fractures & ejec-
& Tetryl) all at “standard” (or nearly standard) tions, may turn out to be below hl in which
charge, thickness. Note that HMX at h-her case no explosion should occur. However large
gives the expected “S’ shaped frequency curve. the impact energy, the explosion frequency no
For RDX h>hcr and the frequency curve is longer depends on impact energy but is deter-
flattened for f> 1. For Tetryl h > her, re- mined by the frequency with which the
sults are erratic, and f is almost independent charge thickness, decreasing in jumps, enters
of impact energy. Explosion frequency, f, never the interval hcr to h[”
exceeds ‘0.2 for an almost 4-fold increase in An interesting consequence of the above
impact energy considerations is the prediction that f-impact
On the basis of experimental evidence and energy curves should be greatly “flattened”
theoretical considerations, A & B conclude that in impact machines having small diameter
the frequency curve (f vs impact energy) should strikers. This prediction is based on the ex-
be narrowest for h = hcr and still be narrow pectation that ~cr does not depend on h or
 I 52

h/D. Thus the curves of Figs 9, 10 & 11 could TABLE 6. Charge Thickness hcr (mm) for Tran-
just as well have h/D instead of h for the sition from Fracture to Explosion (in
abscissa. Consequently one can just as easily Instrument No 2)
speak of (h/D)cr as her. Now if D is reduced
Explosive From pressure From the
hcr must also decrease to keep (h/D)cr con-
measurements frequency peak
stant. With a reduced hcr and “standard”
thickness, samples the anamolous frequency HMX 0.43 0.42–0.43
effect, and indeed failures at all impact ener- RDx 0.25 0.25
gies, should be observed more frequently than Tetryl -0.12 -0.10–0.13
at larger D (ie larger her). This expectation is PETN 0.27 0.27
in accord with experience. All the anamolous TNT ‘0.08 -0.10 ,
effects are more pronounced in the so-called
Weller impact machine (D = 1.5mm) than in Andreev and Terebelina (Ref 7) performed a 4
Kholevo No 2 (D = 10mm). It should be noted, large number of impact experiments, in Kholevo
however, that primary explosives, for which hcr No 2 type machine, in which they varied sample
is large, are initiated at rather low impact en- weight and sample location, and observed the
ergies in the Weller machine. This is so because explosion frequency at a fixed impact energy. u
hcr is still quite large, in the Weller machine, Sample location, for a freed sample weight, was
and its small D makes it possible to attain ~cr either in the central region between striker and
at low impact energies (P = 4F/rrD2 ) anvil (D=5 mm) or spread uniformly between
Useful information is also obtained by plot- anvil and striker (D= 19 mm). Obviously the

.
ting f vs h at different impact energies–Fig 13. centrally located samples were thicker than the
r uniformly-spread samples. For “sensitive” ex-
10 plosives, primaries, PETN, RDX, HMX, etc

!/J’ji-
0
0
a they found high explosion frequencies for
48 centrally-located samples and almost no explo-
~ sion for spread samples (pxcept Mercury Ful-
1 minate or Lead Picrate for which sample lo-
cation had no real effect). A & B’s interpre-
tation of these results is that for the “sensitive”
explosives h/D = (h/D)cr for the central charges I
and (h/D) < (h/D)cr for the spread charges. In
the latter case either the impact energy is too
q -2.5 kg/m; A-1.O kg/m; o-O.8 kg/m low so that explosion frequency drops to zero
Fig 13. Explosion frequency vs charge thick- at small h (see Fig 13), or else h < hl in which
ness in the case of HMX for various case there would be no explosion at any impact
impact energies energy. Conversely for “insensitive” explosives (h/D)
> (h/D)cr for central charges and (h/D)~(h/D)cr
for spread charges. The effect of variation in
sample weight can be interpreted similarly.
From these plots, one can obtain her. Table 6 A & B give no quantitative comparison between
shows that hcr based on ~ measurement are in Andreev & Terebelina’s data and (h/D)cr ob-
excellent agreement with those based ‘on fre- tained by A & B. We have done this under the
quency measurements assumption that all of the Andreev & Terebe-
Iina’s charges are at a density of 1 g/cc.
‘Qualitatively the expected trends do show up
but quantitative agreement is frequently poor
According to Eq 8 and the subsequent dis-
cussion (in topic 7 of the previous section)
impact sensitivity should: a) increase with in-
creasing sample density, b) increase ,with de-
 153 -

c{easing sample size, c) probably be independent gency is obtained as follows:

of initial temperature. The experimental findings From thermal explosion theory (eg see
of A & B (see topic 5 of this section) are not in article on Hot Spots in this Vol)
accord with suppositions a) & b) since impact CRT2 E/RT
se’nsitivit y was found to be essentially indepen- Tad = we (11)
dent of sample density & particle size. No
direct evidence of the effect of initial tempera- and from curve I of the diagram
t~re is presented. However, according to Eqs Tad = –(~ex–~) dt’/d~ (12)
2a & 9, hcr should decrease as TO increases
From Eqs (1a) & (12) the tangency condition
(because Ou decreases iS To ticreases). A & B’s
becomes,
data for HMX confirm this expectation
~Wereturn briefly to an important consider-
ation touched on at the begiming of this sec-
tion and in topic 4 of the previous section,
namely the time delay between impact and and via Eqs (11) & (12) leads to
explosion. The idealized diagram (Fig 19 of ——
@ex-p)/p = RT2/E(T-Tm) (13)
A ~ B) shown below will be helpful in the
following analysis and
I P17
1, Tad = ~dRT2 /E(T–Tm) (14)
I II The only effect of altering initial conditions
1’ to T= Toatt=O instead of T= Tmatt=O
I )
II (as assumed above) is to change the equality
f #f / 1’ sign in Eqs (13) & (14) to less-than-or-equal
ra~
F
10 1/,)1f; 10 7 el (<) signs; proof of this is given by A &B. Now
;t -O/ 1 ff?o for most secondary explosives for 400<T<700°
,/)
~,1 / C, the expected range of Tcr, the term
.~’_i_- -~” RT2 /E(T–Tm)Q3. 1 and consequently
I
Pex–~ < O.lPex
In this diagram time coordinates have been
changed by the transformation t’ = ~d–t where and Tad < o.l~d
t is real time and t’ = ~d or t = O is the time Typically Td S= 10-4 sec and consequently the
at the beginning of impact. Thus impact occurs time delay between impact and explosion (Tad)
at ;t = O and with the above transformation ex- is ~ 10-ssec or less
plosion occurs at t’ = 0,; also at t’ = O, 8) We have already alluded to the applicabil-
Z ~ ~ex. If, for simplicity, we assume that the ity of A & Bs impact model to the Weller im-
impacted sample is at Tm at t = O, then (in pact machine. Below we examine the
accordance with, Eq la) its T–t histow w~l applicability of their ideas to other impact
be’ given by ,curve I in the diagram. For each machines that also create rapid shear in the
T there is ‘a corresponding adiabatic explosion explosive samples. Let us consider the following
time T ad. Three typical T– Tad plots (curves tabulation (Table 11 of A & B) where all the
11,~111& IV) are shown in the diagram. Curve P’s refer to compression stresses in the explosive
H does not intersect curve I, therefore there
car! be no’ explosion at t! = O. Curve 111inter- Here ~cr is the same as that of Table 1; ~fric
se~ts curve I twice, therefore explosion should is from the data of Kozlov & Mamaev for ex-
haye occurred before it actually did, which is periments carried out under rapid shear; ~fnchl
contrary to the assumption of explosion at (data of Muratov) was obtained uqder conditions
t’ ~ O. Curve IV, which has a point of tangency similar to ~fric experiments except that the ex-
wi~h curve I, is thus the only possible curve plosive was confined by a tin ring; PI-P are
th~t satisfies the requirements of the problem results of experiments with Kholevo No 1 in
un~r consideration. This condition of tan- which the striker was rotated 10° to produce

.1
 154

TABLE 11. Critical stresses (in thousands of kg/cm2 ) obtained in different instruments

Pfric ~ll.p Pfric FII.P ~fric M ~1.p FI.p

Explosive PC* (50%) (50%) (loo%) (loo%) (loo%) (30%) (100%)

TNT %11 7.2 6.8 11 9.6 10.8 9.6 –

Trinitrophenol ‘-v 9.5 5.7 — 7.4’ — — — —
Tetryl ‘W 8.4 4.7 — 6.1 – 6.8 – –
RDX 7.0 4.2 5.2 5.7 7.2 6.8 6.5 9.6
PETN 4.8 3.1 2.8 5.4 4.8 5.3 5.3 8.7
Lead Azide 2.6 1.6 — 3.1 — 1.8 — —

“shear” (data of Bochkov & Kupriyanov); ~11.~ is greater than hcr in Kholevo No 2 (see Eq 8)
is the same as PI-P ‘but with Kholevo No 2; r is fully confirmed by experiment according to
bracketed numbers are explosion frequencies A&B
The trends of the various ~ values obtained 9) No experimental evidence is given by ,A &
with six different impact systems are in obvious B in support of their contention that Ou varies
qualitative accord. Closer examination of the appreciably for supposedly equivalent samples.
data reveals that ~fric & ~l-P for f = 50% are However, this contention seems logical for the
always lower than ~cr. This is to be expected highly non-isotropic nature of an explosive
since ~cr is essentially for f = 1007. (see Fig sample consisting, as it does, of a variety of
11). Consequently it is not surprising that ~cr different sizes and shapes of explosive grains
agrees well with ~fric. ~fricM & ~ll.p for 10) In topic 7 of the preceding section we
f = 100%. According to A &B, Mamaev (~fricM) summarized A & Bs development of the con-
showed that the lowest compression pressure cepts of minimum impact force and minimum
(for PETN) was obtained when the sample was impact diameter (Eqs 6, 7 & 8), and in topic
placed near the center (not the periphery) of 10 we indicated that quantitative agreement
his apparatus. This is in accord with A & Bs between theory and available experimental data
argument (derived from the study of plastic is poor. Now we present this comparison. For
metals) that peak stress P occurs at center of some strange reason, probably due to the un:
a sample and considerably exceeds the average availability of the appropriate data, A & B
stress ~ (see topic 4 of the preceding section). choose to compute Dm & Fm from data for
For “confined system” of ~l-p, the stress is dcr for po - 1 g/cc charges of roughly 0.1 mm
uniform and has the value of P rather than particle size, whereas their best measurements
~. It should be noted that ~l.p, which is a peak. in Kholevo No 2 are for pO - 1.5 g/cc samples.
stress, is roughly twice ~cr which is an average Table 6 presents their computations and also
stress. This is in accord with Eq 4 summarizes their measurements with the Kholevo
The expectation that hcr in Kholevo No 1 No 2 machine with a sample diameter D < 10mm

TABLE 7. Impact Characteristics of Some Common Explosives

kg
Explosive Oult ;mz PcrlO- 3kglcmz (h/D)crl 0-2 dcrmm Dmincm Fminkg
.— ——
TNT 340 -11 ‘0.8 12 -75 -5.3-107
Trinitrophenol 520 9.5 -1.1 7 -32 8.9-104
Tetryl 520 -8.4 -1.2 5 19 -2.4-10s
RDX 820 7.0 2.5 2.5 5.0 1.3-105
I-fMx 1250 6.4 4.3 4 4.6 1.1-106
PETN 600 4.8 2.7 2 3.7 4.8-104
Lead Azide 1550 2.6 28 — — —
 1
155

It is obvious that Dm > D’ where D < 10mm creases in Tm can be achieved by forming
is the diameter at which explosions were observed eutectic mixtures of two or more explosive com-
for all the explosives shown in the Table. Now ponents. This is done in practice, eg in cyclotols,
for TNT, at just below crystal density, A & B octols, tetratols etc. From Eq (8), it follows that
quote an experimentally found dcr - 2mm. Using a reduction in Ou (which we eliminated in favor
dcr * 2mm will reduce Dm six-fold and Fm 36- of Tm for the purpose of the above discussion)
fold over those shown in the tabulation, but will result in ,a decreased impact sensitivity–at
even this reduced Dm is still much larger than least an increase in Dm. A reduction in CJu can
D. If this 6-fold reduction of dcr as p. increases be achieved by using appropriate additives such
is also applicable to the “sensitive” explosives as surface-active agents, low viscosity materials
(RDX, HMX, PETN etc) then Dm ~ D for these etc. It seems that more development effort
explosives and, as required by A & B’s theory, should be directed towards this than has been
explosion is possible outside the impact zone expended heretofore.
(which is of dimension D). ,For the “insensitive Written by J. ROTH
explosives (TNT, etc) in Table 6, Dm > D and Refs: 1) W. J. Dixon & J, Mood, JAmerStat
(according to A &B) explosion can occur only Assn 43, 109 (1948) 2) F.P. Bowden & A.D.
Within the impact zone. Since the impact zone Yoffe “Initiation and Growth of Explosion in
is a property of the impact machine, ie the Liquids and Solids” Cambridge Press (1952)
impact zone varies with striker diameter, we 3) F.P. Bowden & A.D. Yoffe “Fast Reactions
have a contradiction to A & B’s assertion that in Solids” Acad Press, NY (1958) 4) F.P.
“impact sensitivity,” determined with Kholevo Bowden, ProcRoySoc 246, 147 (1958) 4a)
No 2, is solely the property of the explosive V.K. Bobolev & L,G. Bolkhovitinov, lzvAkad
& not a combined property of the explosive Nauk, SSSR No 4, 754 (1960) 5) M.G. Natrella
and conditions of impact. A & B make no at- “Experimental Statistics,” NBS Handbk 91,
temp to resolve thk contradiction. What they (1963), pp 10-22 to 10-24 6) Andreev &
suggest, as already discussed, is that little quan- Belyaev, article by N.A. Kholevo, (1963), pp 5-
titative significance be ascribed to Dm and/or 26 7) Ibid, pp 47-151 8) Proc Internat Conf
Fm, but that these quantities be used to devel- on Sensitivity & Hazards of Explosives (London)
op qualitative series of impact sensitivities, eg (1963), Session 6 Note: These proceedings have
Lead Azide is more sensitive than PETN which no page numbers, only Session numbers 9) J.E.
is more sensitive than RDX etc Ablard, Ibid, Discussion of Session 6, p 1 1O)
A very important facet of the general sub- E. James, Ibid, Discussion of Session 5, p 11
ject of impact sensitivity is the artificial lower- 11) A. Popolato, Ibid, Session 6 12) J. Wilby
ing-desensitization- of the impact sensitivity of & H.N. Mortlock, Ibid, Session 5 13) G. Hornby
certain explosives. If we accept Eq 8 as being & W. Merrick, Ibid, Session 5 14) D.C. Hornig,
at least qualitatively correct & take Dm as a Ibid, Opening remarks 15) F.P. Bowden, 9th
measure of impact sensitivityy,, then from Eqs SympCombstn (1963), pp 499-515, 16)’ PATR
(1), (8) & (10) and the usual situation of 3278 (1970), pp 2-4 17) G.T. Afanasev & V.K.
~cr > au, Bobolev “Initiation of Solid Explosives by
Dm ~ K(Tcr:Tm)dcr/Tm (15) Impact ,“ translated by I. Shechtman (1971), TT
70-5074, NASA TTF-623 18) B.M. Dobratz
where K is a constant. To “desensitize” an ex-
plosive, ie increase Dm, one can increase Tcr (edit) “Properties of Chemical Explosives &
Explosive Simulants~’ LLL, UCRL 51319 (1972),
& dcr (ie decrease its reactivity and capacity
to detonate) or decrease Tm. For a given” explo- p, 9-2 19) This Vol, article on “Hot Spots”
sive little can be done about increasing Tcr. In-
crease in particle size should increase dcr and
should result in decreased impact sensitivity Impact Velocity. The actuaf velocity attained by
(however see previous discussion in topic 7’ about a bomb or other projectile on reaching the
the observed lack of a particle size effect for target. This must not be confused with the so-
PETN, RDX, & HMX at high compaction). De- called terminal velocity, which is the theoretical
 I 56

velocity on impact for a given size and shape of and analogously (by substituting for crl & 02)
projectile. This theoretical velocity cannot be u2/u, = 2/(1 + p2c~/plcl) (5)
attained in practice because of air resistance
The diagram or Eqs (4) & (5) show that for
p2c2>p1c1, U2 ,<ul & rS2>01 and conversely.
Moreover by setting P2Cz = O (medium 11 is a
Impedance, Acoustic and Shock is the product vacuum; for air p2 c2 -0 in comparison to
of density and sound velocity, namely pc. Ana- p, c1 for continuous condensed media) the par-
logously shock impedanci is poU where U is ticle velocity is 2UI . This is the so-called free-
the shock. velocity in a medium whose density surface velocity, ufs, of medium I shocked to
(ahead of the shock)ispO. Both acoustic& the state OILS~. Conversely, when U2 = O,
shock impedances are used to estimate the 0 = or = 2ol (see diagram & Eq (3)). T~s
interface stress, O, and interface particle velocity, means that the interface stress on a n“gid wall
u, for planar shocks moving from one medium (consequently U2 = O), in contact with a con-
into another medium. A simple method of densed medium shocked to the state crl, UI, is
doing this, based on the so-called acoustic ap- 2U 1. That ufs Q 2UI is also obtained from the
proximation, is illustrated below exact solution (analytical or graphical) of the
From conservation of mass & momentum conservation equations for shocks in condensed
(See Vol 4, pp D 604-5) media (Refs 1, 2 & 3). The exact solutions,
0= pouu (1) . however, show that or >2 al, but usually not
much greater. In fact, for a rigid wall
Now if we assume that U = constant = c (the
acoustic approximation) ur/o1 s 2.4
As examples of the degree of accuracy of
pou q poc (2) Eqs (3) & (4), let us compute the stress &
and for a given medium o is directly proportional particle velocity for detonating Comp B in con-
to u. This is shown in the following diagram (for tact with Mg, and Comp B in contact with
actual O–U curves see Fig 3, 4 & 5 of article on steel. In each case we will replace p 1c1 by POD
Hugoniots in this Vol) which represents for Comp B but still use the appropriate pz Cz
I II for the metals. For Mg: acoustic approx
G/o1 = 2(1 + 1.71 X 8/1.74 X 4.7) = 0.75;
u2/ul = 1.25 “exact” CT2/01 (Ref 2)
= 0.99; u2/u, = 1.03
For steel: acoustic approx CJ~Crl= 2(1 + 1.71 x
8/7.8 x 6)= 1.55; uz/ul = 0.45 “exact”
02/01 (Ref 2) = 1.61; u2/ul = 0.50
Note that for the metals UZ> C2 and con-
sequently Pz Uz> p2 Cz, therefore the acoustic
approximation calculation should usually give
a lower limit value of rJ2/0 ~ & an upper limit
value for uz/ul
u~ u, 2U1 R“efs: 1) Baum et al “Physics of an Explosion:’
a shock in medium ‘I entering medium II. The Fizmatgiz, Moscow (1959) (transl 1963) Chapt
heavy black line is a geometric reflection of line IX 2) G.E. Duval, ProcMetalSocConf 9,
I thru the point al , UI. These quantities, 01 & “Response of Metals to High-Velocity @forma-
UI, are respectively the stress & particle velocity tion,” Estes Park, Colorado (1960), pp 173-79
at the interface of medium I. It is obvious from 3) O.E. Jones, Proc 12th Annual Symp on
“the diagram that Behavior & Utilization of Explosives, Albuquer-
que, New Mexico (1972), pp 128-137
tan cx = O1/UI = U2/(zrJ1-r-r2) (3)
By substituting for UI & from Eqs (2) & (3) and
simplifying
cr2/crl = ‘2/(1 + Pl%/P2c2) (4) Imperial Chemical Industries. See ICI in this Vol
 I 57

Imperial Schultz Powder. It consists of Nltro- it will move, and under certain conditions
lignin 80.1, Ba nitrate 10.2, vaseline 7.9 & what damage it sustains (see article on impul-
volatile matter 1.8Y0. Its props are reported as sive loading of structures in this Vol). Impulses
follows: can be generated by a detonating explosive, a
Calories per g 742 burning propellant, a flying projectile or
Permanent gas, cc/g 763 indeed anything that creates a pressure pulse
Water vapor, cclg 152 The impulse delivered by a detonating ex-
Total vol of gas at STP 915 plosive “at some distance (i air) from the
Relative temp 106 explosive charge is briefly discussed in Vol 2,
This is a shot-gun powder used at one time p 181-L. A more detailed discussion of
in England explosively-generated blast pressures & impulses,
Refs: 1) Marshall 1 (197), p 327 2) Barnett both in air and under water, will be given in
(1919), p 86 3) Thorpe 4 (1940), p 530 a future volume under “Scaling Laws for Blast.”
Below we will discuss explosively-generated im-
Imperiali Explosive. It consists of N~ N03 pulses delivered to structures or media in con-
65-85% & W-Si-Al alloy 15-35% tact with the explosive charge or separated from
Rejl R. Imperiali, USP 1054777 (1913) &CA it by a relatively thin layer of attenuating
7, 1419 (1919) material
Theoretical Considerations
Implosion. The reverse of explosion–when the To gain some insight into these phenomena,
walls of a confining vessel collapse inwards, in- without getting too involved in mathematical
stead of bursting outwards. For instance, when complexities, let .us first examine some limiting
a thin-walled glass container is partially fdled cases of impulse delivered to: a) a rigid wall &
with boiling water, sealed and then cooled, the b) air (for HE detonations there is very little
vessel may collapse with a lou’d noise. This is difference in the final results in the explosive
due to the fact that water vapor condenses on impulse delivered to air or to a vacuum)
cooling, creating a partial vacuum inside the a) The rigid wall problem has been treated
vessel. This causes the atmosphere, which is at in detail by Baum et al (Ref 2), on the basis
a higher pressure, to push the walls of the of a polytropic equation of state for the
container towards the inside until they are detonation products and a polytropic coefficient
broken r=3. They fmd that
Ordinary electric Iiit bulbs are imploded I = 8/27caD (1)
(and not exploded) when the walls are
where D is the detonation velocity and Ca is the
weakened by an accidental crack or from a
explosive weight per unit area of explosive. In a
blow
following section we shall obtain a similar result
Precisely controlled detonations are used to
by quite a different method
create an implosion of fissionable material to
b) Baum et al also consider this case but ordy
achieve ‘cn”tical mass in the explosion of an
indirectly & in a somewhat complex treatment
atomic bomb (See Vol 1, pp A499-504)
(Ref 3). As an illustrative example, we will now
present our adaption of Baum’s treatment:
Impulse. The impulse I, associated with a A semi-infinite explosive slab of thickness h, ,
p;essure pulse of duration t and pressure P is bounded on both free faces by vacuum (or air),
~ Pdt which is the area under the P–t curve is initiated instantaneously at one free face. We
of the pulse. For triangular pressure pulses of wish to compute the impulse delivered at the
peak amplitude Pm, I = Pint/2, and for an other free face. From the polytropic equation of
exponentially decaying pressure pulses state assumption it follows that:
I=Pm/B(l –e”Bt) where B is the decay constant. C = Cj@/~j) (2)
In the cgs system I has the dimensions of
dyne sec/cm2
and P = Pj@/Pj)r = Pj(C/Cj)r (3)
The impulse delivered to a structure deter- where the subscripts j indicate CJ quantities, ie
mines whether the structure moves, how far quantities at detonation equilibrium. if we place
 I 58

the origin of our coordinate system at the plane For many purposes, rather than using th~ total
of initiation, ie x = o at that plane & x = h at impulse I, it is more convenient to use an impulse
the other explosive face, then the usual solutions per unit area per unit explosive weight, ie
of the Riemann invariants (Ref 1) coupled with II ~ I/ca, or 10 ~ POI/ca = POII (where PO is the
the above assumption about the equation of density of the unexploded HE) which we shall
state of the detonation products, give, call the impulse constant. The term II has the
dimensions of velocity and is closely related to
x=(u+~)t (4) specific impulse which is commonly used as a
where u & c are local particle & sound velocities measure of effectiveness of propellant systems.
at time t 10 has the dimensions of dyne sec/cm3 in the
From symmetry considerations u = o at cgs system. Thus 11 & 10 are readily obtained
x = h/2. Then from Eq (4), from Eqs (l), (8) & (9) by dividing by Ca to
c = h/2t (5) get II and then multiplying II by pO to get 10
So far we have only considered limiting cases
For polytropic detonation products with I’ = 3,
and “head-on” detonations. How is the impulse
cj = 3/4D (6) generated by a given explosive system modified
Substituting the values of c & cj from Eqs (5) if the detonation is tangential (“running” deto.
& (6) into Eq (3) we obtain, nation) rather than head-on to the medium in
(7) contact with the explosive? Also what changes
P = (8/27 )Pj(h/D)3 t-3
are to be expected if the medium is neither a
In our problem, I = ~Pdt, and from Eq (7), with rigid wall nor a vacuum? A qualitative answer to
t = h/D, Pj = P~D2 & Ca= POh, we, obtain, the second question is obvious from the fore-
4 going discussion; for a “non-rigid” wall the im-
pulse delivered will lie somewhere between that
I = 1/27 caD (8)
delivered to a rigid wall and to a vacuum. How-
or 1/8 of the impulse delivered to, a rigid wall ever a generally-applicable quantitative answer
(see Eq (1)). This is also the result obtained by to this question is not available. As will be
Baum (Ref 3) shown later, theoretical calculations can be made
The results of Baum et al (Ref 4) can also be for specific HE/medium systems but these can-
interpreted to mean that if the above HE slab not be generalized to all HE/medium systems
were initiated instantaneously at its midplane, An alternate method of computing I, or
I = 2/27caD (9) better 10, is based on the Gurney formula (See
or twice the impulse of Eq (8). From symmetry, VO1 6, p Cl 95-L)
this case is equivalent to an HE slab of thick- For a running detonation, ie detonation
initiated at one end of a HE slab, the velocity
ness h/2 (thus ca/2), confined by a rigid wall
at its plane of initiation v it imparts to a plate of mass m, where the
To determine how the numerical factors in other face of the explosive slab is bounded by
Eqs (1), (8) & (9) vary with 17 (the other terms another plate of mass m’, is given by:
are unchanged by variation in r as long as the 1/2
equation of state is still of the polytropic form) 3
we “have re-computed Eq (1) in its generalized v= @ 1+3m/c– l+2m/c+(l+3m’/c) l+2m/c 2 (lo)
form, l+2rn’/c ( l+2m’/c )]
——l— [
1 = /20D(r + 1)” ‘“/rl’(r-l) (9a)
for several ~s where ~ is the Gurney constant for a running
The tabulation below detonation of the particular explosive used (Ref
5). Now the momentum imparted to plate m,
r 3 2.5 2 3/2 1
whose area is A, is mv, and rev/A = I or
Factor 0.296 0.445 0.750 1.720 m
pmhmv = I where pm & hm are plate density &
shows that the numerical factors increase as r thickness. Since 10 = pOI/c, Eq (10) can be
decreases modified to give,
 I 59

1/2 running detonation is only slightly less than

10= pO~ m/c
[1 (11) that delivered by a head-on detonation. Equa-
tion (12) rdso suggests why it is permissible to
neglect the differences between air and vacuum.
where the bracketed term is the same as in For vacuum m’ /c = O,. Even if :m’/c for air is
Eq (10) and both m/c and m’lc are on a per as high as 0.1 (we certainly expect it to be
unit area basis. For the conditions m/c >>1 & less for HE in contact with air) the error is
m/c’ > 0, Eq (11) becomes, only about 5Y0. A more sophisticated and con-
., vincing argument leading to the same conclusion
is given in Ref 10
IO= pO< 2E’ W(1 + .2m’/c) (12) Before comparing the above theoretical re-
2 (1 + 3m’/c)l’2 sults with experiment, let us return briefly to
the question of “non-rigidity” of the medium
in contact with an exploding HE slab. Erkman
This reduces to, . (Ref 6) using a numerical procedure based on
the method of characteristics obtained values
(13) of 10 for various media in contact with EL506D
L sheet explosive containing about 70% PETN &
if m’/c <<1, eg, for a system in which one face 30% binder whose pO = 1.4g/cc & D = 7100
of the HE “slab is in contact with air m/see
The writer has shown (Ref 9) that for m/c>> 1 Erkman’s results (shown in Table 1 of the
& m’/c <<1, next section) indicate that 10 decreases as
medium density decreases. Erkman did not caqy
~ . O;:;D (14) out his calculations for the rigid wall case to
sufficiently large values of t (ie, hk arbitrary
for a “head-on” detonation and, calculation cut-off does not account for all the
impulse in the “tail” of the P–t curve). Con-
~ ~ 0.95 X 0.578D (15) sequently, his values of 1.=2.8 x 105 dyne
r–1 sec/cm3 for the rigid wall is expected to be
for a tangential detonation. Thus Eq (13) be- somewhat low
comes, for r = 3, From Eqs (13) & (15), using I’=2.6 (appro-
10 = 0.250pOD for “head-on” detona- priate for PETN), we compute 1.=3.0 x 105
tion and 10 = 0.238p0 D for tangential detona- dyne sec/cm3 for EL506. In view of the above,
tion. These are to be compared with the numer- this is in excellent accord with Erkman’s result.
ical factor of 0.296 = 8/27 obtained by Baum’s If we assume that the factor of 0.95 between
method discussed above (Eq 1) head-on and tangential detonations (Eqs (14)
The ratios of numerical factors obtained by & (15)) is also applicable to Baum’s method of
Baum’s method divided by those obtained by calculating 10 for a running detonation, then
the Gurney method are: from Eqs (1) & (9a), with f’=2.6, 1.=3.8 x 105
dyne sec/cm3 which is some Z5Y0 greater than
r 4 3 2.5 2 1.5
1.20 the 10 computed by the Gurney method
Ratio 0.98 1.29 1.50 1.72
Comparison of Experiment and Theory
Thus in the expected HE range of 2.5< r <3, Defourneaux & Jacques (Ref 7) present data
for a given pO & D, the impulse constant, 1.,’ for 65/35 Cyclotol & Octol that can be used to
computed by Baum’s method will be 20-30% check the theoreticrd considerations of the
greater than that computed by the Gurney previous section. They used flash radiography to
method. As will be shown later, 10 by Gurney’s measure deflections, q , of a steel plate in con-
method is in better accord with measurements tact with a detonating slab of HE. Their measure-
than 10 by Baum’s method ments correspond to what we have called tan-
Equation (15) combined with Eqs (12) or gential or running detonation. They found that
(13) shows that the impulse delivered by a l/q is a linear function ,of m/c namely, l/q =
 I 60

1 I i
A + B m/c, where A & B are dimensionless
Plate velocity is given by v = 2D sin 9/2,
> STEEL
and for the small q of their measurements
v~Dpsothat Il=~=~Dp ))
Combining this result with the linear depen-
dence of 1/yI on m/c, it follows that at large
m/c, I LINEN
PHENOLIC
II = D/B (16)
Defourneaux & Jacques used Im to designate
II at large m/c
Combining Eq (16) with Eq (13), in which
~ was eliminated via Eq (15), we et
~ i B
the ratio R, R = (IO)exP/(IO)theor = 0.47
f)
Below we tabulate R as a function of , using 4
B = 3.95 for both cyclotol & octol (from Ref
7):
r R
3 0.94
2.9 0.99
2.8 1.04
2.7 1.10
2.6 1.18
2.5 1.25
I I I
Clearly, agreement between theory & experiment 0.2 O.* 0.6 0.s
FOAM- TO- TARGET WEIGHT RATIO
is quite satisfactory in the expected range of
2.7< r <3 (Ref 9) for these explosives CONSTANTS FOR Ek506D AS FUNCTIONS OF THE
RATIO OF FOAM NEOPRENE TO TARGET WEIGHTS
The impulse imparted to various metal, plas-
(1 tap/roil = 10’/2.54 = 395 dyne see/cm’;
tic and even foam plates by running detonations numbers in brackets are IIW number of
of EL506D sheet explosive were measured at measurements for the parlicufar data point;
In/c>> 1)
SRI (Refs 5 & 8) using a variety of measuring

TABLE 1: Comparison of Experimental & Theoretical Impulse Constants

Density
Medium of Medium (iO)obs x 10-s (lo)~heor X 10-s
(g/cc) dyne seclcm3 dyne sec/cm3
Rigid wall — 2.8 (a); 3.0 (b)
Steel 7.8 2.9 —
Aluminum 2.56 2.5 —
Magnesium 1.74 2.45 2.3
Micarta 1.36 — 2.0
Neoprene 1.25 2.0
Neoprene foam 0.63 — 1.8
,, ,9 0.40 2.4 (?) —
Polyurethane foam 0.025 2.1 ,(?) —
“vacuum” 0 — 0.39 (c)
Steel 7.8 (d) 4.9 4.8 (e)
(a) Somewhat low–see discussion in previous section
(b) From Eqs (13) & (15) for r = 2.6
(c) From Eq (8) for f’ = 2.6
(d) Had an 8-roil-thick Pb foil on the “free” HE face
(e) From Eqs (12) & (15) with m’/c ,= 1.3
 I 61

techniques. In all cases m/c >>1 & in all, but to get varying values of m’/c (see Eq (12)). The
one experiment, the HE face not in contact measured results in Table 2 show that 10 in-
with the test plate was in contact with air. The creases as m’/c increases. The Gurney treatment
impulse constants, l., based on these measure- (Eqs (12) & (15)) predicts this increase although
ments are compared, in Table 1, with theoreti- the calculated l.’s are in general some 50%
cal l.’s, primarily those computed by Erkman greater than the observed l.’s. A possible expla-
(Ref 5) nation ‘for the larger-than-observed computed l.’s
It is seen that agreement between experiment may be based on the expectation that the com-
and theory is quite satisfactory except for low puted -y’s may be too small. At the high CJ
density foams where experimental results may temperatures & low CJ pressures the detona-
be imcertain tion products may be more dissociated and/or
The writer has measured detonation velocities ionized than we computed. More dissociation
and impulses delivered for four different deto- or more free electrons (ionization) will make T
nating gas mixtures. His results (quoted in Ref approach 5/3, the -y for monoatomic gases
5) are used for the comparison of experimental The l.’s computed by Baum’s method (Eq
and theoretical l.’s shown in Table 2. Each of (1) corrected for ‘y (for gas detonations r = T =
the “slabs” of detonating gas, of necessity, had c /~) are in reasonable agreement with 1.’s
a thin plastic sheet on its “free face.” Both slab oEserved for the larger m’/c’s. This is fortuitous
since in deriving Eq (1) it was assumed that
I thickness and plastic sheet thickness, were varied

I TABLE 2: Comparison of Measured and Theoretical 10 for Gas Detonations

(In all cases m/c >> 1)
Theoretic@ I x 10-s
1+2 m’lc (dyne secTcm3 ) Obs 10 X 104
Gas m’/c (l+3m’/c)l’2 Gurney (a) Baum (b) Erkman (c) (dyne sec/cm3)
Cz Hz + Oz (d) 0.396 1.21 635 940 355 530
0.47 1.25 660 940 355 450
0.72 1.405 740 940 355 520 (e)
0.96 1.495 785 940 355 762 (e)
2.38 2.01 1055 940 355 727 (e)
2.53 2.20 1160 940 355 910
2H2t02+5He (f,) 0.99 1.50 180 210 128 149 (e)
1.65 1.76 210 210 128 170
3.30 2.30 275 210 128 175
6.60 3.10 370 210 128 205 (e)
9.64 3.70 445 210 128 365 (e)
2H2+02+10He (g) 1.17 1.57 131 140 103 115 (e)
1.97 1.88 157 140 103 120
3.94 2.48 207 140 103 131 (e)
7.87 3.38 281 140 103 155 (e)
2H2+02+15He (h)2.19 1.96 145 115 <1oo llO(e)
(a) Eqs (12)&(15) with the appropriate r, PO & D
(b) Eq (1) with the appropriate I’, PO & D using 0.95 to convert from a “head-on” to a
“running detonation”; m’/c assumed to be zero
(c) For air in contact with “free-face” of detonating slab of gas
(d)pO = 1.18 g/1, D= 2900 m/see &-y= 1.31
(e) Single measurement
(0 PO = 0.284 g/L D = 3440 m/see&~= 1.39
(8) PO = 0.238 g/1, D = 3400 m/see&y= 1.47
(h) PO = 0.214 g/1, D= 3450 m/see& -y= 1.53
 [,

i 62

m’/c = O, therefore computations based on Eq target more rapidly than it acquired it from the
(1) should agree with measured results for small HE. This produces a considerably higher pres-
m’/c and not for large m’/c. Erkman’s compu- sure in the target than would be obtained if the
tations are not directly comparable with experi- target were in direct contact with the HE
ment since he assumed that the “free face” was Pulse Duration
in contact with air where in reality it was in For detonation products that obey a poly-
contact with a thin sheet of plastic. Erkman’s tropic equation of state (probably also true for
l.’s presumably are lower limit values since the other equations of state), pulse duration is
plastic sheet provides more “confinement” than t = nh/D, where 1< n < ~. Thus, for a tri-
air angular pressure pulse
Effect of Attenuators
By interposing an attenuator material of the
appropriate shock impedance (See this Vol p 156) From Eqs (13) & (14), with’ m/c>> 1&
between the HE and the metal plate to be m’lc <<1.
propelled, one can appreciably reduce the peak
pressure at the attenuator/plate interface over
~. . fl
2
()r–l
0.578

that obtainable at the HE/plate interface in the Solving for n we get

absence of the attenuator. This, however, does
not necessarily mean that the impulse delivered n ~ (r+l)/(r–1) = 2 for r=3
to the plate is reduced when an attenuator is Baum’s calculations (Ref 2) for a “head-on”
used. Usually, an attenuator lengthens pulse detonation against a rigid wall give n ~ 1.5, ie,
duration so that the reduction in peak ampli- the impulse obtained from Baum’s Fig 142
tude is compensated by an increase in pulse ~ 1.5 Pmh/D
duration (I = Pint/2 for a triangular pressure, Essentially the same value of n is obtained
and in general I is proportional to Pt). Thus, by comparing the calculated impulse of Aziz et
for thin attenuators, a simple-minded approach al (quoted in Ref 5) with a triangular pulse to
using Eq (13) (ie, m/c >>1 and assuming that give same area as the area under their P–t
matt << mpl) leads to the conclusion that the curve. Thus it appears that the n based on
impulse delivered by a given explosive system Gurney is a little higher than the n’s of more
is about the same with or without the thin , sophisticated theoretical estimates
attenuator. This means that the reduction in For a running EL506D detonation against
peak pressure (at least for triangular or rec- a rigid wall, Erkman’s calculations (Ref 5) lead
tangular pressure pulses) is almost exactly to n ~ 2.5. Gurney-type calculations for this system
compensated by an increase in pulse duration. give n ~ 0.95(3.6/1 .6) = 2.1 in reasonable accord
In practice, as shown in the accompanying with Erkman. For gas detonations, agreement
Figure, attenuators do reduce the impulse (Ref 8) between Erkman & Gurney is also satisfactory
as shown below (except for the oxy-acytelene
delivered. )Vhat the above simple-minded picture
mixture):
does not consider is that the attenuator “traps”
gas 7 n(Gurney) n(Erkman)
some of the momentum delivered by the explo-
sive. Stated differently, a thin attenuator does
C2HZ + Oz 1.31 7.0 4.6
~Hz +02 +5He 1.39 5.8 5.4
not transfer to the massive plate all the momen-
~H2 +02 + 10He 1.47 5.0 4.9
tum, delivered to it by the explosive, even after
making allowance for the mass of the attenuator. The disagreement between Gurney & Erkman n’s
This does not mean that conservation of momen- may be another manifestation of too low a
tum is violated. It simply means that the atten- computed ~ for the oxy-acetylene mixture (see
uator retains (traps) more momentum than would above)
be expected on the basis of its weight relative Conclusions
to the weight of the plate. Conversely, Altshuler Let us re-examine the general formula (@ 9a)
et al (JETP 34, 614 (1958)) have shown that a for impulse, 10, delivered by a unit thickness of
thin metal plate, propelled across a void by an an explosive charge to a massive (m/c>> 1) in-
HE charge, delivers its momentum to a massive compressible plate
 I 63

For an explosive slab, one of whose faces 60-124 (1970) pp 25-59 9) J. Roth, SRI Lab
contacts a massive plate, and the other is in Tech Rept 001.71 (1971) pp 5, 22 & C-1 10)
contact with air, Ibid p E-1
10 ‘poD(f’t l)r-l/rr(r-l)
This equation shows that 10 will increase as POD Impulse of a Primer. When a primer is fired, the
increases, eg 10 will be much larger for HE than force of detonation or length of “spit” is called
for gas detonations because pHE >> p as. The impulse. It is measured by the maximum dis-
impulse constant will also increase as F decreases, placement of a mercury column resulting from
this means that for two HE’s of comparable the firing of the primer in an apparatus shown
POD, the one with the lower r’ will deliver the in Fig 15, p 50 of T.C. Ohart, “Elements of
larger impulse. Comparison of Eqs (8) & (9) Ammunition,” J. Wiley, NY (1946)
shows, that location of initiation can appreciably
change the impulse delivered by a given explo- Impulse, Specific. Specific impulse defines the
sive at a given m/c. Thus a system initiated at pounds of thrust produced in a rocket thrust
its free face delivers only 1/2 the impulse of chamber, rocket engine, or similar unit at the
the same system initiated at its midplane. On expenditure of one pound of propellant per
the other hand, comparison of Eqs (14)&(15), second; the ratio of thrust to the proplnt mass
confirmed by experimental evidence, shows that flow. It is one of the most used performance
t~re is rather little difference in the impulse parameters in rocket technology. Because per-
delivered by “head-on” or “running” detonations. formance and weight are of prime importance,
Experimental data, given in Table 2, show that it is highly desirable to design for a high
confining the “free face” of a gas detonation specific impulse. This makes possible a reduction
(t~,keep the gasinplace), even by thin layers in size of proplnt tanks and a saving in the total
of plastic, increases 10 over that expected from wt of fuel & oxidizer carried aloft in these tanks
a free face in contact with air. Examination of The most common equation for determining
Eq (12) reveals that the effect of m’/c becomes specific impulse is:
F
significant for m’/c >0.2. Such values of m’/c Isp = where
G
are encountered in practice even with relatively
thick “slabs” of detonating gas “confined” by Isp = specific impulse in lb/(lb/see)
thin layers of plastic on the “free face” of the F = thrust in pounds and
slab W = wt flow rate of proplnt in lb/see
Attenuators may be used to reduce both Specific impulse must vary with changes in alti-
peak pressure & impulse. They act as momen- tudes because both thrust & weight change with
tum “traps” altitude and gravitational forces
Computational procedures are presented for Rocket power plants use the heat liberated
making estimates of pulse duration in terms of by the reaction of chemical propellants, liquid
the quantity h/D. The factor, n, by which h/D or solid, as the source of energy. Specific im-
is multiplied to get pulse duration is approxi- pulse is more in Iiq proplnt applications; it is
mately (r + I)/(r– 1) difficult to accurately measure the propellant
Written by J. ROTH flow rate of solid-propellant-rocket thrust pro-
ducing units. The average specific impulse is
Refs: 1) R. Courant & K.O. Friedrichs, “Super- occasionally calculated for solid-propellant units
sonic Flow and Shock Waves” 1, 87, Inter- on the basis of thrust, duration, and proplnt wt,
science Publishers (1948) 2) F.A. Baum et al but there are other parameters that are more
“Physics of an Explosion” Fizmatgiz, Moscow convenient. Modern rocket power plants are
(1959), transl 1963, p 502 3) Ibid pp 525-28 capable of obtaining specific impulse values be-
4) Ibid pp 528-30 5) G. R. Abrahamson, SRI tween 240-250 lb/(lb/see) I
Int Rept 009-62 (1962), p 83 6) Ibid pp 48- Refs: 1) G.A.W. Boehn, Fortune, Dec 1957, pp
55 7) M. Defourneaux & L. Jacques, Proc 5th 166 & 170 2) Rocket Encycl (1959), 452-53
Deton Symp (1970) pp 457-466 8) H.E. Lind-
berg & J. D. Colton, SRI Tech Rept AFWL-TR-
 I64

IMR Propellant. Improved Military Rifle (IMR) Incendiary “Blue Pencil,” This ingenious sabotage
Propellant is a US single-base extruded proplnt device, resembling a blue pencil in appearance,
for small arms ammunition. Its compn is NC was invented by the Germans during WWI and
(13.1 5%N) 97.4, tin 2.0 & diphenylamine 0.6%. used to cause fires on ships of the Allies. It
Tin is present to act as an antiflashing agent. consisted of a celluloid tube containing a long
Dinitrotoluene (6.75%) is added as a coating to glass bulb filled with concentrated sulfuric acid.
moisture-proof the grains, also causes the first The lower part of the bulb was connected, by
phase of the burning process to take place at means of a very fine capillary, to a reservoir
a ,relatively slow rate, and has some antiflashing provided with a siphon below which was placed
action. A glaze of graphite is added to facilitate a charge of potassium chlorate
the uniform action of automatic loading machines In operation, a saboteur breaks the upper tip
and to avoid the development of large static of the bulb containing sulfuric acid and inserts
charges in blending & loading the pencil into flammable material, such as
IMR Propellant and its many modifications in cotton, sugar, explosives etc, preferably aboard
compn are manufd in the same manner as FNH a ship. After the tip is broken, air enters the
(flashless,, non-hydroscopic) & NH (non-hygro- bulb, allowing the acid to trickle down through
scopic) proplnts, except for the application of a the capillary into the reservoir, located below.
coating of DNT and glazing with graphite. The As soon as a quantity of the acid accumulates,
coating is applied by rotating the grains in a it discharges through a siphon arrangement into
sweetie ‘barrel heated above the mp of the coat- the receptacle containing the potassium chlorate
ing agent. The glaze of graphite is applied to and causes a very violent reaction accompanied
the coated grains by tumbling in a rotating by flash and flame
drum (Ref 2) Rej A.B. Ray, IEC, 13, 721 (1921)
Lindner (Ref 1.) has reported the following
characteristics of a typical IMR Propellant: Incendiary Bombs & Incendiary Agents. See
Nominal Composition under Incendiary Warfare
Cellulose Nitrate (13.1 5%N) 100.0
Dinitrotoluene (added) 8.0 Incendiary Bomb Fires and Their Extinction.
Potassium sulfate (added) 1.0 As the modern incendiary bombs, containing
Diphenylarnine (added) 0.70 magnesium or thermite, are hard to extinguish
Volatdes (residual) 2.50 by water, several mixtures have been proposed
Physical Characteristics for use in lieu of water. However, none of
Density, g[cc 1.62 these mixtures has proved very effective
Thermochemical Characteristics (calcd) The US Office of Civilian Defense (OCD)
Flame Temperature, “K during WWl I stated that, in fighting incendiary
Isochoric 2835 bomb fires, the spread of the fire is more of
Isobaric 2285 a hazard than the bomb itself. If the bomb falls
Force, ft lb/lb 331000 on a spot where it cannot start fires, the best
Unoxidized Carbon, % 3 procedure is to allow it to burn out. If it falls
Combustibles, % 59 where it can start a fire, the fire-fighter should
Heat of Explosion, cal/g 868 approach it as soon as possible, regardless of
Gas Volume, mole/g 0.042 risk, attempting to remain behind some pro-
Ratio of Specific Heats of tective cover, such as a wall, in order to avoid
Reaction Products 1.24 injury in case the bomb explodes. From behind
Covolume, cu inches/lb 28.9 cover, a strong stream of water should be
IMR Propellants are used in caliber .30,& caliber directed at the surrounding area and not at the
.50 rifle aminunition bomb, which should be allowed to burn out.
Refs: 1) V. Lindner, “Propellants,” in K & O 8 If no cover is available, the fire-fighter should
(1965), pp 698-700 .2) Anon, “Military Explo- operate from a crouching or prone position,
sives,” Dept of the Army Tech Manual TM9- to minimize the danger in case of an explosion
1300-214 (1967), pp 10-6 to 10-7 In extinguishing f~es caused by phosphorous,
 I 65

it must be remembered that, as soon as the enemy personnel, animals, etc. In “modern”
water dries out, phosphorous will start to burn warfare, incendiaries are unfortunately also used
again. In order to prevent reignition the ‘ for “strategical” purposes against civilians and
extinguished phosphorous, while still wet, should cities which have no military installations. In-
be scraped off; placed in buckets and dumped cendiary warfare has assumed ever-increasing
where there are no flammable materials. As importance in recent wars
phosphorous is very poisonous and causes ex- Enormous numbers of incendiaries were
tremely painful burns, all bodily contact with dropped by American aviation during WWI I
it must be avoided and, as the war came to an end, incendiaries
The OCD recommended the use of sand or exceeded explosives in the bombing of Japan. ‘
any of the “bomb-extinguishing” powders, be- The total amount of incendiaries dropped by
cause water can do more damage than good US aviation was 123,000 tons on Japan and
If water is available only in small quantities, 120,000 tons on Europe. Records of the late
it is better not to use it at all because insuf- conflict prove conclusively that incendiaries,
ficient amounts of water would cause bombs per unit weight, achieved greater damage to
containing thermite or magnesium to burn more industrial and other structures than did high
intensely by supplying additional oxygen and explosives
the released hydrogen could add explosive fuel Stettbacher (Ref 7, p 129) gives the fol-
to the fire lowing figures on some of the heavy aerial
Refi Anon, JChemEducation, 20, 59-60 (1943) bombardments of Germany and Japan during
WI I
Incendiary Compositions and Compounds. See Number of Bombs Dropped
under Incendiary Warfare High Explosive Incendiary
Kbln (Cologne), 6/28/1943 70,000 100,000
Incendiary Devices. See under Incendiary Berlin, 3/8/1944 10,000 200,000
Warfare Tokyo, 3/15/1945 6,000 325,000
German Hq, 5/25/1945 2,000 600,000
Incendiary Grenades. See under Incendiary
Warfare According to Stettbacher, the loss of life in
Germany was not as heavy as the loss in build-
Incendiary Liquids and Gels. See under Incendi-
ings: 500,000 dead, or one per 4.9 tons of
ary Warfare and under Flame Thrower Liquids bombs dropped, against 3.6 million buildings
partially or completely destroyed. The heaviest
Incendiary Missiles. See under Incendiary War- loss of life in a ,single raid was in Dresden–
fare 100,000 people or 20% of the population
It is the conviction of military authorities
Incendiary Mixtures. See under Incendiary such as Major General A. H. Waite (Ref 9) that
Warfare incendiary attacks broke the Japanese will to
resist before the advent of the atomic bomb
Incendiary Projectiles. See under Incendiary ‘Histon”cal
Warfare Incendiary warfare is one of the most ancient
methods of conducting war and was used as
Incendiary Shells. See under Incendiary early as biblical times
Warfare The history of evolution on incendiary war-
fare may be divided into three periods:
INCENDIARY WARFARE 1) before the invention of gunpowder and
(Incendiary Agents, Incendiary Compounds firearms
and Mixtures, Incendiary Devices, Incendiary 2) after the invention of firearms but before
Missiles, etc) the introduction of aircraft for war
Incendiary warfare accomplishes the purpose purposes
of causing fires in ene,my territory and burning 3) after introduction of aircraft, particularly
the airplane .
 I 66

First Period, Before the Introduction of the Gun bellows, air was forced across the cauldron and
In this period of incendiary warfare, incen- this projected flames against the wooden strut-
diaries were thrown first by hand and later by ture. This device may be considered a proto-
special machines, called catapults and ballistae. type of modern flame throwers
Bows and arrows were also used for throwing “~is crude machine was replaced by the
incendiary missiles. The earliest account of in- “blowpipe,” used by Roman armies. Incendiary
cendiary warfare may be found in the Bible, balls, made of resin and sulfur, were forced
where mention is made of burning oil and ig- through a tube and were ignited at the muzzle
nited fireballs, consisting of resin and straw, that as they were ejected from the tube
were thrown by both defenders and attackers A similar device was known later (about the
of fortified towns. The Bible also mentions 13th century) as “flying fire” (ignis volatilis).
(Judges 15, 3-5) that Samson used foxes with It consisted of a mixture of saltpeter 50, resin
firebrands attached to their tails to burn corn- 25 and sulfur 25% & was shot from a reed or
fields of the Philistine pipe
Beside the Bible, the first reliable record of As soon as catapult machines were adapted
incendiary mixtures was given by the Greek to siege warfare, larger and more effective in-
tactician Aeneas, who, at about 350 BC, com- cendiary missiles were developed. The first
piled the. first European treatise on the art of incendiary missiles consisted of large stones
war. He listed sulfur, pitch, pinewood, incense coated with flammable materials, such as pitch,
and tow as principal incendiary ingredients tar, sulfur, etc
Seven centuries later (AD 350), Vegetius, a Remans used the so-called ‘Yirepot, ” whjch
Roman military authority, added resin, bitumen was a kind of iron fire bomb (as large as 2 ft
and petroleum oils to this list which indicates a in diameter) filled with pitch, sulfur, bitumen,
significant advance in incendiary technique etc and either perforated or latticed so as to
All of these mixtures, however, were of low permit emission of flames from burning charges.
efficiency because they burned quickly and could One such bomb may be seen on exhibition in
easily be extinguished with water the Tower of London
According to Fisher (Ref 9), one of the “Fire Arrow” was one of the earliest incen-
earliest incendiary munition was the “fire club. ” diary weapons. It was a regular arrow with a
It was a wooden club with sharp iron prongs charge of combustible material such as oakum,
attached to each end, the center being wrapped resin, sulfur, bitumen etc attached to it. This
with incendiary materials such as tarred rope. was ignited just before shooting. In order not to
The tar was lighted and the club hurled’ against extinguish the flame during flight, the arrow had
a wooden structure, where the pointed prongs to be shot slowly and this limited its range
held the fire-bearing club in place against the A much more effective mixture was the one
wall or roof of the building until the fire spread. invented in 668 AD by Kallinikos and called
This device was described in 350 BC by Aeneas “Greek Fire” (see below) or “Sea Fire. ” The
and was supposed to have been used before his exact formula of the original composition is not
time known because the Greeks kept it a secret.
Incendiary hand grenades were clay or glass However, it seems that it contained, besides
vessels with a narrow throat. They contained a the combustible materials such as naphtha, pitch
flammable mixture, which was ignited just and sulfur, some oxidizer, which could have
before the vessel was thrown against enemy been saltpeter. This mixture was liquid that
installations. The vessel broke, bringing the was discharged against the enemy either from
flaming mixture in contact with objects to be pots, tubes or siphons, installed in the bows of
ignited ships. The, moment the liquid came in contact
A device used as early as the 5th century with the water it was ignited. This device was
BC consisted of a hollowed tree and a cauldron so effective that it caused several defeats of the
with burning coal, pitch and sulfur which were Arabic fleets in the 7th and 8th centuries, of
mounted on wheels and brought close the the the Russian fleet in 941 and 1043 and saved
enemy’s wooden fortification. ”By means of a Constantinople several times from invaders. Greek
 I 67

Fire may be considered to be another proto- order not to ignite the propelling charge prema-
type of the modern flamethrower introduced by turely, a wad of wet turf or earth was placed on
the Germans in WW1. Later, the name “Greek top of the Black Powder so that the ball could
Fire” was erroneously given to combustibles, rest on it until the deflagration of the propellant
which were ignited and then thrown by ballistae, or drove it from the cannon
other machines, and were used on land. These
With the introduction of iron balls (shot), the
compositions were semi-solid masses consisting
same procedure was followed. Hot iron shots were
of combustibles such as sulfur, pitch, naphtha,
particularly effective against naval sailing vessels.
etc and oxidizers, such as saltpeter. They were
Sometimes, even bullets from small arms were
also known as “Wildfire,” and were used ex-
preheated and used as incendiaries
tensively by the Moslems during the Crusades
A variation of the preheated iron shot was
and by the Moors during the conquest of Spain,
the hollow projectile charged with incendiary
eg, in the siege of Niebla in 1257
mixtures, intended to bring the shell to a red
Incendiary compounds were known in China
hot temperature after impact. This device was
in ancient times but the ones containing salt-
not as effective, however, as solid iron balls, or
peter seem to have appeared about the 13th
the previously described missiles hurled by
century, when they were used successfully against
catapults
the Mongols
With the introduction (about the end of the
According to the book of Marcus Graecus,
15th century) of hollow type projectiles charged
entitled “Fire, ” which appeared about 1300 AD,
“with Black Powder, these “sh”ells” also became,
the following composition was known in the
to a certain extent, incendiary missiles. This was
13th century in Europe: saltpeter 6p (66.7%),
due to the fact that, when such a shell burst,
charcoal 2p (22.2%) and sulfur 1p (11.1%). It
the flame produced by the explosion of the
was used in two’ munitions, a “thunder bomb”
Black Powder could ignite any closely-located
and an incendiary rocket, called the “ji’ying
inflammable object
tunics. ” The latter consisted of a narrow
AS Black Powder bums comparatively quickly,
cylinder filled with the above Black Powder”
this shell could not be a satisfactory incendiary
mixture which served as both propellant and
missile, unless part of the Black Powder could
incendiary for this prototype rocket
be replaced by slow burning compounds such as
The idea of propelling incendiaries by means
pitch, rosin, sulfur, bitumen, etc, and this was
of a composition containing saltpeter, charcoal
tried
and sulfur is presumed to have been discovered
However, much better results were obtained
by the Chinese. ,~e introduction of substances,
with improved “surface-burning” projectiles such
resembling the present Black Powder as, rocket
as the following:
propellants and incendiaries, was a great im-
a) “Incendia-~ Ball’’–prepared by dipping a
provement in incendiary warfare and for a while
small iron ball in molten sulfur, wrapping
these weapons were of prime importance
it in oakum, redipping in sulfur and
Second Period, After Introduction of the Gun finally rolling it in tine Black powder. The
With the invention of cannon (14th century) ball was wrapped in wire and. its diameter
that used Black Powder as a propellant it was had to correspond to the caliber of the
possible to hurl missiles much greater distances cannon
than by ballistae or catapults, thus causing b) Incendiary Elongated R-ojectile-prepared .-
greater damage to the enemy without resorting by kneading a warm incendiary mix over a
to incendiary compositions. And so, with the crossed iron frame, in a manner similar to
introduction of cannon, incendiaries became of the above
secondary importance. However, attempts were c) “carcass “-invented in 1672 and used until
made as early as the 14th century to shoot in- nearly the end of the 19th century, con-
cendiaries from cannons sisted of a thick, elongated, narrow sack
The firs’t incendiary “shot” was a stone ball, containing pitch, oakum and Black Powder
preheated on a fire or by quicklime, and propell- and enclosed in an open framework of
ed from a cannon by a charge of gunpowder. In iron straps. The composition burned with-
 I 68

out scattering and its’ flame ignited sur- with a piece of metallic potassium or calcium
rounding materials phosphide, Ca3Pz and a small closed glass con-
Other devices, such as “pitch rings” ‘~d” “in. tainer with water. The impact of such a bomb
cendiary hoops” (Ref 9, p 113) also belong to broke the glass container and the water ignited
the surface burning class of munitions either the K or Ca3Pz which in turn ignited
Military incendiary rockets, used in Europe in the main incendiary mixture
the 13th and 14th centuries, were forgotton un- Mixture of fleck-similar to the previous one,
til the British Col W. Congreve introduced an but using metallic sodium as the prirping
improved model at the beginning of the 19th substance
century. The idea to resurrect rockets as in- Fenian Fire (Liquid Fire)–consisted of a
cendiary weapons came to Congreve when he solution of yellow phosphorous in carbon di-
saw how successfully Indian troops used rockets sulfide. On evaporation of the CS2, the phos-
against British troops at the end of the 18th phorous self-ignited in the air and ignited near-
century by flammable objects
Congreve’s rocket, which was primarily an Darapski Projectiles were charged with petro-
incendiary weapon, could compete successfully leum, which was ignited by means of a mixture
in accuracy with the cannon of that period and containing 3 parts of phosphorous dissolved in
was used until the introduction of rifled barrels 1.3 parts of CS2
and breach loading, which improved the accuracy NiklFs Mixture (Feu lorrain- Lorrain Fire)
of artillery and increased its range to such an consisted of a mixture of chloro-sulfuric acid
extent that the Congreve rockets became obso- (C12S02) together with phosphorous dissolved in
lete (about 1860) CS2. This mixture was ignited by introducing
Hale’s rocket superseded that of Congreve. It a small amount of ammonia
was provided with a screw-like tail in an en-. Gugot Mixture–same as above, but replacing
deavor to give it a truer flight the chloro-sulfuric acid with the bromo-sulfuric
With the exception of the Congreve and Hale Sophronius Mixture consisted of 3 parts of
rockets, very little progress was made in the 19th concentrated Hz S04 and 2 parts of KMn04
century in incendiary warfare and it might even In addition to these mixtures, it was proposed
be said that it was again forgotten. Incendiaries to use phosphorous trichloride, which catches fire
were not used during the Crimean or the Amer- on contact with either ammonia or ammonium
ican Civil Wars, but were reintroduced by the hydrosulfide, NH4 HS
Germans during the France-Prussian War of Third Period, Incendiary Devices Used After the
1870-1871. The Germans, using incendiary pro- Introduction of Aircraft in Warfare
jectiles, burned several French cities, and forced Although aircraft was introduced as an
their capitulation auxiliary warfare weapon by various countries
After that war, the Germans decided to as early” as 1910, their actual combat use did
improve the compositions and weapons used in not begin’ until WWl. By this time, incendiary
incendiary warfare and especially to construct an materials were used in the following devices:
incendiary projectile suitable for shooting from a) small arms ammunition b) shells c) trench
rifled, high-muzzle-velocity guns, invented in the. mortar projectiles d) grenades and other hand
1860’s. After many trials, they succeeded in weapons e) aircraft bombs f) flame projectors
developing several types of incendiary shells, (described separately) and g) rockets
some of which were used later in WWl. Other An excellent description of all of these weap-
countries followed the German example and ons is given by Ray (Ref 4)
also developed incendiary shells Only a brief resum{ is given below
The following additional incendiary mixtures Small arms ammunition. Incendiary small
and devices were invented in Europe in the arms ammunition, while carrying only a very
19th century: small amount of material, has proved to be of
Mixture of Niepce consisting of powdered the greatest value in effectively attacking highly
coal impregnated with carbon disulfide, gasoline flammable targets, such as aircraft, which
or petroleum, was loaded into a bomb together might be fdled with hydrogen or carry tanks
 169

of gasoline fuel. Most incendiary ammunition is metal jacket is torn open and the incendiary
of regular caliber and fits standard machine guns. composition burns for 10 to 40 milliseconds.
There are two classes of bullets which may have Incendiary ftiers weigh from about 20 grains,
incendiary effect–real incendiqv bullets, which for cal .30, to 75 grains for cal .50 bullets.
usually function only on impact and tracer in- One of the’ most effective bullets is the cal
cendiary bullets, which begin to function .50 M23, a 500 grain bullet which is fired at
either at the instant of expulsion from the gun 3400 ft/sec
or shortly thereafter. Although the primary use b) Armor-piercing Incendiary Ammunition
of tracer bullets is to aid in directing aim, some (API), has the lead point fdler replaced by an
of them may have considerable incendiary action, incendiary composition. It is also used primarily
provided the target is struck before the bullet against aircraft. The API bullet is similar to
ceases to “trace. ” Bullets used in WWl by the (I), except that the incendiary is ahead of the
US Army carried the following incendiary steel core. The cal .50 API bullet contains 15
materials: grains of the incendiary mixture consisting of
a/ White phosphorous; b/ Ba02 & Mg; c/ barium nitrate and aluminum-magnesium powder.
Ba(N03 )2, Mg, charred linseed oil, with an This mixture ignites on impact
ignition composition consisting of red fad and It is estimated that in WWl I 50% of the
Mg planes lost to anti-aircraft fire and approx 75%
One of the German perforating tracer-incen- list to enemy aircraft were brought down by
diary bullets carried incendiary material con- incendiary ammunition
sisting of Sr(N03 )2 75, Mg 13, A 3, Fe 6, c) Armor-piercing Incendiary Tracer (API-T),
resinous material 3T0, in the rear section. On similar to API but having a tracer mixture in
top of this was pressed an igniting composition the rear of the bullet. Caliber .30 ammunition
containing KMnOQ 55 to 58, iron tiling 45 to is expected to trace for about 1200 yards and
42% and this was ignited by the flame produced caliber .50 about 1800 yards. A longer trace has
by the propellant been developed for .50 ammunition (2500 yards).
Another German incendiary armor-piercing A dim trace (dim for the first 200 yards to pre-
bullet contained igniter and incendiary com- vent dazzling the gunner) has also been developed
positions in the front section. The advantage of for .50 ammunition. The incendiary composition
this type of bullet was that the burning com- for calibers .30 and .50, which ignites on impact,
position in front of and around the armor- consists of barium nitrate and aluminum-mag-
piercing shell of steel was more likely to ignite nesium powder, the tracer composition consists
gasoline from a perforated tank than if the of strontium peroxide and nitrate, magnesium
composition were in a separate container, which and other ingredients. The tracer is ignited by
might break away from the bullet on impact. means of a barium peroxide and magnesium
The priming or igniting composition which powder mixture, which is pressed on top of the
ignited on impact consisted of Mg, KC103 and tracer’ mixture at 70,000 psi. The pressing is
Sb2S3, while the incendiary composition con- done by a step punch in order to create a
tained Mg, Al, Ba(C103)2, sulfur and a little NC large surface to present to the hot propellant
During WWl 1, the following incendiary and gas which ignites the barium peroxide-Mg
tracer small arms ammunition were used by the mixture
US Armed Forces: For .50 caliber bullets with a trace of 2500
a) Incendiary Ammunition (I) was used yards, a slower buriiing tracer composition con-
primarily against aircraft as a means of setting taining Sr(N03 )2, KC104 and Mg is usually used
fire to enemy planes. The straight incendiary In the so-called “night-tracer cartridges, ” which
bullet has an incendiary charge in the nose and neither blind the gunner nor reveal his position
in a steel sleeve ahead of the lead slug. The to the enemy, a dim igniter (essentially Sr02,
incendiary mixture consists of barium nitrate and Ca resinate and Mg) burns for the first 200 yards
magnesium-aluminum powders. The bullet func- for the .30 and .50 caliber bullets. A tracer
tions on impact, the mixture being ignited by bullet for .45 caliber submachine gun traces
the heat and sparks of impact. The gilding for 160 yards
 <

I 70

d) Tracer Bullet (T), similar to ordinary ball that time such shells played an important role
bullets, but having the rear half of the lead core During WWl, shells were produced ranging
replaced by igniter and tracer compositions, from 37mm to 17.5cm. The smaller sizes were
which are essentially the same as in the API-T used for attacking aircraft from the ground
bullets. There are tracer bullets for .30 and .50 while the larger calibers were used against all
caliber rifles sorts of ground targets. There were tracer shells
A special .50 caliber bullet, called “Jf21 head- which had appreciable incendiary action over a
lite tracer” was developed to satisfy the air force considerable portion of their trajectory. There
requirement for a bullet to simulate a ball of were also incendiary shells which did not func-
fire. The object was, for psychological effects, tion as incendiary devices until at the moment
to make the enemy think that he is under fire of explosion when the incendiary material was
from much larger caliber weapons than small ignited and scattered
arms. For this, the standard M 1 tracer bullet The consensus regarding incendiary shells was
is modified by replacing the usual igniter and that the small caliber tracer-incendiary shell was
tracer composition with strontium peroxide quite effective against aircraft, but that the
alone. Although in this case, the tracer distance larger type, designed for use against ground tar-
is reduced from the usual 1800 yds to about gets, was not as successful
600 yds, the visibility is about three times that A common type of tracer-incendiary shell,
of the usual tracer bullet carrying red lead and magnesium, was produced
Among foreign ammunition, the Japanese in the US in 75mrn and 3“ sizes. It was used
caliber .50 “explosive-incendiary” bullet is of principally for shooting down balloons. This
interest. It was provided with a point-detonating shell was of very simple construction–just a
fuze and a charge of high explosive, with the cylinder with a threaded neck, in which a fuse
incendiary fdler placed behind the explosive was inserted, and six vents below the threaded
charge. After the projectile penetrated the target, part. The fuse charge ignited the primer which
the explosive filler was detonated, the jacket or in turn ignited the incendiary mixture and the
shell shattered and the incendiary composition incandescent products of combustion were
ignited. The composition of the incendiary mix- emitted through the six holes in the head. The
ture was Ba(N03 )2 38, NaN03 20, Mg powder smoke from this combustion left a definite
36, Al powder 6% (Ref 9, p 58) trace of the projectile, and the hot gases evolved
e) Incendiary Shells. for 6 to 25 sec possessed efficient incendiary
The first satisfactory incendiary shells suitable action
for firing from modern high-muzzle-velocity, A more complicated tracer-incendiary shell
breach-loading, rifled cannon were developed by was used by the British and Germans. In this
the Germans before WWI shell. (usually 75mm), the flash from the time
It should be noted, however, that in modern fuse was transmitted through a tube (located in
warfare, the incendiary-loaded artillery shell has the center of the cylinder and extending from
become of secondary importance. This is because the top, near the fuse, almost to the bottom of
good targets for incendiaries are nowadays the shell) to the primer. The primer ignited the
seldom found within range of artillery. If such incendiary composition, containing Mg, Ba(N03 )2
targets are found, they usually can be destroyed and binder with or without Sr(N03 )Z, and blew
more readily by incendiary aircraft bombs than out the base of the shell. This resulted in
by artillery. Thus, the effective use of the in- emission of flame from the base of the shell,
cendiary shell is narrowed to certain specialized lasting about 15 seconds
targets and to situations in which the air force There also existed several models of shells
cannot be easily utilized designed solely for incendiary effects. Most of
For these reasons, many types of incendiary them contained thermite with inflammable or-
shells that were standard during WWi have since ganic materials. Others contained phosphorous,
been discarded. Nevertheless, it is interesting, sodium, etc
from a historical point of view, to give a short The British designed a 77mm shell which
description of shells used during WWl because at ‘carried thermite (Al + Fe203 ) as an incendiary
 171

material and ophorite (Mg + KC104 ) as an phosphorous (Ref 9, p 53). These shells were
igniting and expelling charge. This type of shell mostly used in trench mortars
acted not onJy as an incendiary, but also as The Japanese Army incendiary shells were
shrapnel producer, because it scattered hot metal used in 75mm guns and 90mm mortars. The in-
and slag produced by the thermite reaction cendiary material consisted of rubber pellets
For larger sizes, eg, 15.3cm, a shell was de- impregnated with a solution of 88% phosphorous
signed which contained units of thermite or and 1270 carbon disulfide. A burster charge of
other incendiary materials held in perforated . picric acid scattered the incendiary pellets,
cases. These irnits were ignited from a central which ignited on exposure to air and burned
tube and expelled from the front of the shell for about five minutes. These shells were only
by the explosion of the powder charge located effective against readily ignitable materials
in the base (Ref 9, p 53)
The Germans developed a 15cm shell, for use Antiaircraft Incendiary Shells. The ant iaircraft
against ground targets, which contained 12 or incendiary shells used during WWl were very
more celluloid cylinders surrounded by yellow successful against hydrogen-fdled airships but
phosphorous imbedded in paraffin’. A central did little damage to airplanes. The problem of
tube of Black Powder was used as a bursting successfully attacking airplanes by incendiary
charge shells from the ground has not been solved up
The largest incendiary shell used during WWl to the present time, although the Germans and
was the German 17.5cm “ikfinen wer~er,” de- Japanese developed some “ground antiaircraft
scribed in detail in Ref 4, p 716 shells, for example, the following:
A 7 .7cm shell developed by the Germans for German 20mrn Incendiary Shell-carried an
use against aircraft scattered steeI slugs and incendiary composition containing phosphorous,
flaming incendiary units .on bursting, called thermite and other compounds. This charge was
“j7aming onions” by allied aviators pressed into the lower part of the shell by means
Towards the end of WWl, the US Army de- of a stepped ram. A charge of HE placed on top
veloped a base-opening shell, which on func- of the incendiary charge was detonated by means
tioning, ignited and expelled a consolidated large of a booster initiated by a fuse. This shell, as
mass of incendiary material well as the 20mm Japanese shell, described be-
During WWll, the US Army retained only low, proved to be more successful in air-to-air
the white phosphorous shell, which was not than ground-to-air firing
officially listed as incendiary ammunition. Yellow German 88mm and 128mm Antiaircraft Shell.
phosphorous also served as a smoke and anti- Used during WWl 1. The incendiary pellets were
personnel agent with only incidental incendiary designated as FK44 and FA252. The FK pellet
value-it easily ignites light combustible material. supposedly weighed about 27g and was approx
As an example of. such shells, Fisher (Ref 9, p 15mm in diam and 30mm in length. The pellet
53) describes the 81 mm smooth-bore mortar was said to consist of a detonator, a’ striker and
shell. This shell weighs 11.5 lbs, has a range of a diaphragm. Three holes allowed gasoline: to
slightly under 2000 yds and carries 4 lbs of enter the pellet and to create a hydrostatic head
solid yellow phosphorous. On impact, the nose as the’ pellet entered the fuel tank of the target.
fuse detonates the burster charge of Tetryl The hydrostatic head detonated an explosive
(placed in a thin-walled tubing, extending into fdler of pressed PETN/wax/Al. The pellet was
a cavity in the phosphorous), which breaks the intended to blow a hole in the fuel tank large
shell and simultaneously ignites and scatters the enough to prevent” resealing ,and to ignite the
burning phosphorous gasoline. The 88mm carried 72 pellets and the
A 4.2” chemical mortar shell was also 125mm, 124 (Ref 16)
used for incendiary purpows. It contained a Other German Incendia~ Shells. German
burster charge of Tetryl, placed in thin-walled munitions also included incendiary core frag-
tubing extending into a cavity in the ‘phos- mentation shells. These incorporated a central.
phorous. The Tetryl broke the shell and ‘ flash tube which ignited the incendiary falling of
simultaneously ignited and scattered the burning each fragment prior to detonation. The shell
 I 72

functioned in a manner similar to the Italian The Stoke’s bombs were loaded for best re-
shell described below. The materials used for sults with about 7.5 lbs of thermite as the in-
the core are as follows: cendiary compound, and ophorite as the explosive
., igniter. The ignition was started by a time fuse
Dag- The 8“ Liven’s incendiary drum was a metal-
1ngredient, % BI ‘ Dag-Small Powdered B19S B19K
lic container, 20” long and 7 5/8” in diameter,
Ba(N03)2 49.0 – ‘– – –
resembling an ellipsoid in shape. It was closed
Ba02 —. 70.0 69.2 8.4 3.5
at one end and open at the other. It contained
Fe203 ‘ — — — 62.5 65.8
balls of cotton or jute impregnated with “solid
Al, flaked — 25.0 25.0 20.8 21.9
-oil” (thickened oil), prepared by treating a mix-
Al, powder — 5.0 5.0 – ‘ –
ture of fuel oils (bp 170-225°) with sodium
Mg/Al alloy 50.0 – 0.8 8.3 8.8
stearate. The lighter part of the oil mixture
Necresil 1.0 – – – –
was readily ignited by the flash from the ex-
NC*
plosive charge, which was. loaded in a central
*NC added as a granulating’’rnaterial in the form of tube, and this ignited the heavier oils. One end
collodion (Ref 16) of the drum was fitted with an impact fuse
which caused the drums to explode on landing,
Italian Incendiay Shell. Italian antiaircraft and to scatter burning material over an area 50
incendiary pellet projectiles, in WWl 1, consisted yds in diameter
of a 76 or 90-caliber shell loaded with a num- Some Liven’s drums contained cotton waste
ber of incendia~-filled cylindrical pellets. The impregnated with a mixture prepared as follows:
pellets were ignited by a flash from a central TNT was dissolved in’ benzene and fuel oil and
flash tube. A delay mixture activated a secondary gas tar oil and a solution of yellow phosphorous
explosive in the base which broke the shell into in CS2 were added. The mixture was insensitive
flak. Composition of the incendiary tilling is not to shock, had a very low coefficient of expan-
given in Ref 16 sion (0.0 174 per “C between -1OOand 55°) and
Japanese 20rnm Incendiary Shell–carried a a low vapor pressure
small incendiary charge of Ba(N03 )2 50, Mg 40 These drums were projected from a mortar-
and Al 10% like, smooth-bore barrel, called the Liven’s
Japanese Incendiary Shells of Larger Clrlibers Projector. It had an 8“ bore and was 37.5”
were loaded with yellow phosphorous and pro- long. A propellant charge ignited by an electric
duced large spectacular aerial bursts, but their primer was used to obtain a maximum range
value was probably more psychological than de- of 1450 ‘yards
structive to aircraft (Ref 9, p 55) Grenades and other small devices. Small
Japanese 120mm Incendiary l%ojectile con- portable incendiary devices, such as hand gre-
tained 48 steel pellets embedded in a canister nades, are very valuable because they can
fdled with white phosphorous. Each pellet had easily set fire to flammable targets. These
an annular cavity to increase the amount of grenades can also be used for throwing into dug-
phosphorous that could be retained by each outs and for destroying material abandoned in
pellet. The shell was exploded by means of a retreat, such as damaged planes
bursting charge of HE, fired by a point-deto- The following grenades ,were used during
nating fuse WI’:
7kench Mortar I?ojectiles. During WWl, the Phosphorous grenade consisted of a sheet
following trench mortar projectiles were develop- metal can filled with yellow phosphorous and
ed: 3“ and 4“ Stokes bombs and 8’; Liven’s provided with an explosive device. Although the
drums. They were used mostly to destroy grass, primary aim of such grenades was smoke-
shrubbery or camouflage which could act as a production they were also incendiary weapons
screen for enemy movements, to clean out Z7rermite grenade consisted of a cylindrical
woods, to demoralize the enemy during gas pro- sheet iron container filled with thermite (about
jector attacks and to indicate the range in night 600g) slightly moistened with sodium silicate. In
attacks the center of the thermite was a cavity in which
 “ 173

was inserted an igniter bag of Al + Ba202. The thermite grenade consists of a steel
Strands of a quick match connected the igniter canister 2 1/2” in diameter and 4 3/4” high
bag to a piece of Bickford fuse provided with vents in the upper part and con-
Zhermite-gelled oil grenade was developed with taining about 20 oz of thermite. In the top
the idea of combining the adv~ntages of thermite there is a “bouchon-type” fuse with a lever held
and gelled oil. The former dew$ops temperatures in unarmed position by a safety pin. A plastic
high enough to melt metals, while the latter cup with igniter (starter) composition is attached
produces a long duration flam~. The grenade to the lower part of the fuse. When the safety
consisted of a heavy cardboard container whose pin is removed, release of pressure against the
lower half had a celluloid cent airier filled with igniter fuse lever permits the tiring pin to strike
gelled oil, while the upper half contained a primer (after a delay of about 2 seconds),
thermite with a celluloid binde ~ (4% by weight which results in ignition of the starter com-
of celluloid dissolved in a small, amount of position followed by that of the thermite. Com-
acetone). The grenade was fire! ~y withdrawing bustion continues for about 30 seconds and
the safety pin and releasing thel ‘ bouchon” develops sufficient heat to burn difficultly ig-
firing handles. The spit of the fuse ignited the nitable materials and to melt metals (even
booster, which set off the ignitfx (Al + Ba2 02) steel). Such grenades may be used for the
and then the thermite. The res~ltmg molten destruction of guns, airplane equipment, etc
iron and slug penetrated and ignited the cellu- about to be abandoned
loid container with the gelled ~fl By attaching an exterior Prirnacord detonator,
During WWi, the Germans d~eloped several the grenade may be exploded during burning of
portable incendiary devices con~lstrng of a the thermite, thus scattering particles of molten
metallic or pasteboard tube fiileld with mixtures iron a distance of about 75 feet
of oxidizer and combustibles (eg, KN03 62.5, A US Army, WWII, incendiary grenade, AN-
sulfur 27.0, carbon 10.5Yo) and Ifitted with a M-14, contained a thermite composition desig-
friction-igniting device. Some of these devices nated as “Therrn8” having the following
were of larger size, containing as much as ingredients: Thermite* 70-81%, Ba(N03 )2
1670g of the above mixture. In practice this 14.85-15.15, Al flake 1.01-0.99, Al grained 2.77-
device served either as an incen ~ary or smoke 2.83, sulfur 0.89-0.91, castor oil 0.303-0.297
producer, depending on circums~ances (Ref 15)
The French developed an inc~ndiary can, for *Therrnite has the following composition (parts
throwing into trenches or dugo~ts, containing by wt): Al (granular) 1.0, Iron oxide, magnetic
about 3 liters of petroleum oil ~nd weighing (Fe, 0.) 2.75
about 7 lbs. It was provided with a friction
igniting and exploding device A phosphorous grenade is constructed in the
Although uses for incendiary grenades are same manner as the thermite grenade, but func-
limited, they were still used dur~g WWl 1. The tions as a bursting rather than a burning munition.
present incendiary grenades are pf two types: On exploding, solid pieces of phosphorous are
1) standard types, regularly produced and scattered up to a distance of 75 ft and burn for
supplied, and 2) improvised frangible grenades. about 30 seconds. This grenade may be used
Standard grenades, although normally thrown for setting fire to easily ignitable material, such
as gasoline, etc . .
by hand to a distance of 75 to 100 feet, can
also be fired from rifles or gren~de launchers The Japanese, during WWll, used two kinds
up to 750 ft. When projected fr~m rifles, using of grenades, those filled with yellow phos-
a special cartridge, the incendiary grenade is a phorous and those containing rubber pellets
valuable weapon “for attacking tahks and other impregnated with phosphorous-carbon disulfide
vehicles solution (Ref 9, p 56)
Frangible grenades. According to Fisher (Ref
Standard grenades. Accordi ng to Fisher
(Ref 9, p 55-6), there are two kinds of standard 9, p 56) and Ohart (Ref 10, p 359), the fran-
gible grenade is an ordinary small glass bottle
grenades used at the present tim~ by the US
filled with gasoline (preferably thickened) or
Armed Forces, a/ thermite type !md b/ phos-
other combustible liquid and tightly closed.
phorous type
 I 74

Some type of impact igniter is attached b y A later type of German bomb weighed 10
means of a tape to the upper part of the out- or 20 lbs and could be dropped either from
side of the bottle. The bottle breaks when airplanes or airships. It consisted of a sheet-
thrown against a tank or other hard-surfaced metal torpedo-shaped container filled with an
object and the igniter sets fire to the liquid. If incendiary composition consisting of a pasty
well ~imed against a tank, the liquid may mixture of gasoline, and paraffin with or
penetrate inside the tank and burn the personnel without K perchlorate. The igniter was a
The so-crdled~olotov cocktail, used for the mixture of Al and Fe filings with Ba(N03 )2,
first time during the last Spanish Civil Warj placed in a central tube and a charge of
also belongs to the frangible type of grenades Black Powder was used to disrupt the casing
Aircraft Bombs. It was recognized as early and scatter the incendiary material. The bombs
as 1910 that bombing from airplanes was of were wrapped on the outside with tow rope
the greatest military importance. It was also and then were shellacked
recognized that incendiary bombs possessed The German example was followed by the
great potential destructive power. The first French and British and later by the Americans
successful incendiary bombs were developed by A 20 lb bomb developed by the French was
the Germans during WWI and dropped for the called “Chenard” and was considered to be
first time (19 15) from airships over London. successful. It contained a mixture of rosin and
The Allies soon followed their example. During celluloid as the principal incendiary material.
WWll, the US Air Force used such bombs very The bomb ignited while falling and reached the
effectively, more so than the Germans, to burn target in flamei
out most of the large German and Japanese The British developed several intensive type
cities bombs, such as the one filled with gasoline and
The bombs developed and used from 1915 up ignited on impact by a V&y cartridge but none
to WWI I may be divided into the following was as successful as the small unit bombs
types: developed by them later
1/ Mrge bombs, known as intensive type, The US developed a 50 lb bomb which con-
which practically burn up where they are sisted of a sheet zinc body in the shape of a
dropped prolonged ellipsoid, filled partly with thermite
2/ Large bombs, known as scatter type, which (bound with Na silicate) and partly with gelled
on functioning, scatter a number of in- oil. The bomb. was provided with an impact
cendiary units over a wide area fuse connected to an igniter. When the bomb
3/ Small unit bombs, called darts in the USA, functioned on landing, the therrnite was ignited
which can literally be rained down upon a and burned through the casing. The enormous
target amount of heat liberated liquified and ignited
Most of these bombs are described in detail the gelled oil to spread the conflagration
by Ray (Ref 4, pp 718-720) and only a short 2/ Scatter type bombs. A 20 lb impact-
summary is given below functioning bomb developed by the French,
1/ Intensive type bombs comprise a large contained as incendiary material cotton impreg-
variety of models and carry practically all types nated with a flammable liquid mixed with K
of incendiary materials. The most satisfactory chlorate and paraffin. As a combination
bombs developed during WWI consisted of igniting and explosive material, a sulfur-bound
thermite and large amounts of highly inflam- thermite (Thermaaloy) was used. Thermaaloy
mable materials. The first bombs dropped in can act as a mild explosive as well as a great
1915 by German Zeppelins were of the inten- heat producer, when ignited under confinement.
sive type. These bombs weighed 20 lbs and Thus on’ ignition of the thermite the bomb
contained gasoline, thermite and an ignition exploded, scattering burning theimite and the
mixture:, ,They were wrapped with tow rope impregnated cotton. However this bomb was not
impregnated with tar and Ba(N03 )2. A percus- considered a great success
sion fuse served to cause the first ignition. A ’40 lb air-burst bomb developed by the
These bombs were dropped from airships only British was filled with yellow phosphorous and
 I 75

was used against observation balloons and during WWI but, in modified form, they found
ground targets wide use in WI I
A 50 lb “scatter-type”, bomb developed by
Bombs used during WWII
the US is identical with the intensive type as
A most important contribution to incendiary
far as outside dimensions are concerned. In-
warfare was made by the Germans, who con-
cendiary material to be scattered consists of
ceived the idea of using the magnesium alloy,
either cotton-waste balls impregnated with
called “Electron” (see below) for the construction
inflammable materials, such as turpentine or
of bombs. Although this bomb was invented
CS2, or gelled oil held in small celluloid con-
as early as 1917, it was not used in WWl, but
tainers. When the bomb lands, ignition and
was first employed in the military operations of
ejection of the units are effected by an explo-
sion of Black Powder in the nose WWl1, beginning in 1939 (See Elektron Bomb in
This type of bomb was never used because Vol 2, pp B234 to B237). It caused considerable
by the time it was fully developed the small damage to London and other British cities during
unit bombs, or “darts,” were considered more the early part of WWl I but later in the war when
effective the Allies, especially the US, developed their own
3/ Small unit bombs. The British originated incendiary bombs of better quality and in larger
the idea of dropping a large number of small quantities than those of Germany, it was the
unit bombs instead of one large scatter type Germans and their Japanese allies who suffered
bomb and consequently developed the 6.5 oz most. The Italians were spared incendiary warfare
bomb The US Chemical Warfare Service produced
In its action the little bomb resembles that four types of incendiary bombs during WWl 1.
of a mortar and projectile. It consists of a One type, the magnesium bomb, was copied
cartridge very much like a shotgun shell which after European designs, while the other three
is functioned on impact by a strike point in types were developed, after Pearl Harbor, en-
the base of the body of the assembly. The tirely by American scientists
flash from the cartridge ignites an incendiary The M50A2 4 lb Incendiary Bomb was
charge of “flaming thermite” consisting of similar to British and German models. It was
11 pts of thermite and 6 pts of Ba(N03)2. hexagonal in shape and had a body of cast-
The little bombs were loaded into containers magnesium alloy (1 .25 lbs), an iron nose plug
hung underneath an airplane in such a manner and a sheet-metal tail. It was 21.3” long and
that containers could be released individually. 1.69” across the flats. It was fdled with 265
Each container carried 144 or 272 bombs and grams of “Therm 64-C,” which has the follow-
the total number of bombs carried by a single ing composition; Al. (granular) 16.0, Al (flake)
plane was 16,000 9.0, Fe~Oq (iron scale) 44.0, Ba(N03 )Z 29, sul-
Following the British idea, the US Army fur 2.0%. This filling is ignited by a “first fire”
developed two types of small bombs and called composition (igniting mix). It burns fiercely
them “darts.” for one minute (without consuming outside
The first type, primarily intended for use oxygen) at 2985°C and melts and ignites the
against crops and forests, burned with a large magnesium alloy of the casing. Some of the
flame but did not have great penetrating power. magnesium vaporizes and the Mg vapor mixed
It was in the shape of an elongated shotgun with air burns with a very hot flame (2000”C).
shell and contained an incendiary mixture corr- The magnesium continues to burn for a maxi-
sisting of Ba(C103)2 54, rosin 16, Al 14 and mum time of 10 minutes and due to the fact
asphaltum varnish 16?10.The primer was a mix- that it requires little outside oxygen (0.9p per
ture of reduced iron and KMnOo lp of Mg) it can burn even in closed buildings.
The second type, intended for use against Fires produced by such bombs are difficult
buildings, contained a thermite-gelled oil mixture but not impossible to extinguish. The disad-
as an incendiary. This bomb had sufficient vantage of such bombs lies in the fact that
penetrating power to pierce a roof the fire is mostly confined to a very limited
The unit bombs were not produced in quantity area. These bombs are generally released in
clusters
 I 76

In order to spread fires over a larger area, the Tetryl fractures the entire nose of the
an explosive element is sometimes added to bomb, producing more than 400 fragments.
the bomb so that when it explodes, after being This bomb acts not only as an incendiary, but
partly burned, it scatters burning pieces over an also is effective against personnel (Ref 15, parts
area having a radius of as much as 50 ft. This 111& V)
greatly hampers fire- fighting because it is never In the M69-WP bomb, 0.4g of the gel con-
known just when the bomb will explode and tained in the nose of a regular M-69 bomb
cause injuries to fire-fighting personnel. In the was replaced with a plastic cap containing white
US M50XA3 bomb, 36 grams of tet~l is used phosphorous. When the “gelgas” is ejected from
as the explosive charge and a delay fuse and the casing, the force of explosion breaks the
detonator is included in the ensemble (Ref 10, cap and scatters the WP about the area. The
p 235 & Ref 15; parts III & V) smoke produced by WP obscures objects, makes
The M-69 (6 lbs) incendiary bomb is a breathing difficult and hampers fire-fighting
hexagonal case of sheet steel 19.5” long and All the types of bombs described above were
2.9”’ across the flats. Its central portion con- p?cked together in closed containers (containing
tains a charge of 2.2 lbs of “gelgas” or “Napalm” from 25 to 100 bombs) which fell like a single
held in. a cheese cloth sack and an ejector- bomb from a plane and broke open a few
igniter charge @aced near the fuse) of 0.4 oz thousand feet above the target, releasing the
of Black Powder and magnesium. This was later individual bombs in a tight pattern. The hexa-
replaced by a Tetryl booster surrounded by gonal shape of these bombs allowed packing
phosphorous, serving as igniter for the gelgas them in larger quantities per unit space (Ref
or Napalm. Attached to the outside of the bomb 15, part 111)
are four lengths of green-colored cotton gauze, Bombs Released Individually weigh 70 Ibs
40” long and 3” wide. These break free as the and up, for example, the M47A2 and the M76
bomb starts to fall and act to stabilize the US bombs. These were designed for precision
fall and to provide drag, so that the descent bombing. A particular advantage of such bombs
slows down to 225-250 ft per second. This is their ability to penetrate heavily-roofed
prevents the bomb from smashing to pieces structures that would resist the impact of light
when it lands, yet the bomb has sufficient force (cluster) bombs When dropped from high al-
to pierce tile, slate, wood or galvanized iron titudes, these bombs have impact velocities of
roofs. After the bomb lands, the impact acti- about 1000 feet per min and may pass through
vates a delay fuse which, after 3 to 5 seconds reinforced concrete up to 15“ thick
delay, ignites the “igniter-ejector” charge. This The M-47 incendiary bomb weighed approx
ejects the sack with burning gelgas or Napalm 70 lbs and consisted of a sheet-steel cylinder with
from the tail of the casing to a distance of 75 a rounded nose and tail. It was 45” long and
to 200 feet. The gel scatters around as “gobs” 8-1/8” in diameter and was filled with jellied
of fire, which cling to surrounding objects and gasoline. Originally, a Black Powder central
continue to burn for the next 8-10 minutes. burster was used, but it was not as satisfactory
The bomb may be fused either for delayed as the later, model with a TNT-Tetryl burster,
action so as to permit penetration into struc- which was surrounded by white phosphorous
tures before functioning, or for immediate action used as the igniter for the gasoline gel. This
so as to scatter flaming material over roofs or bomb was initiated by a nose fuse
other surfaces The M76 bomb, also died “goop bomb” or
In the 6 lb M69X bomb, 0.4g of the jellied “Blockburner,” was the largest incendiary bomb
gasoline was replaced in the nose of the bomb used in WWI 1. It weighed 475 lbs. It consisted
by a charge of Tetryl to act as a burster charge. of a metallic cylinder with rounded nose and
The bomb is so constructed that when the tail and was loaded with 180 lbs of “pyrogel”’
main ejection-ignition charge forces the “gelgas” (see below). It was provided with standard nose
from the bomb case, a delay fuse leading to and tail fuses and a standard igniter and
the Tetryl charge is also ignited. After a delay burster. On reaching the target, the burning
of from 1 1/2 to 6 seconds, the explosion of pyrogel was scattered by the force of the
 I 77

bursting charge to a distance of 150 to 500 ft d/ German 50kg Petroleum Solvent Incendi-
and burned with an intensely hot flame. The ary Bomb was similar to (c) but contained
pyrogel mixture combines the good features of petroleum solvent 87.7, polystyrene 11.7 and
both jellied gasoline which scatters and phosphorous 0.5% as the incendiary mixture
penetrates into hard-to-reach corners of struc- e/ Japanese 1kg Irrcendia~ Bomb consisted
tures, and of magnesium which concentrates a of a casing, 10” long and 3“ in diameter, fdled
white-hot flame on the target (Ref 15, parts with red phosphorous and containing a burster ‘
Iv & v) (exploder) tube fdled with Picric Acid. The bomb
For other standard incendiary bombs (1946) was exploded on landing by the PA. This
see Ref 15, part V and table of contents of i~ited and scattered the phosphorous. Frag-
part L For incendiary compositions, both ments of the bomb were thrown as far as 150 ft
experimental and standard, see part 11 fl Japanese 50kg Rubber-Pellets Bomb con-
Jettisonable Airplane Fuel Tank Bombs. sisted of a casing, 40.5” long and 4.5” in diam-
Another type of US incendiary bomb was the eter, fdled with many rubber pellets or balls
coverted auxiliary airplane fuel tank of 75 to impregnated with yellow phosphorous in carbon
300 gallon capacity. They were filled with disulfide and containing a burster tube with
jellied gasoline and provided with a fuse and high explosive, such as PA. On landing, the
an igniter. Such bombs spread fire over a large bomb was exploded by the burster and pellets
area and were very effective against Japanese were scattered to a distance of up to 150 ft.
targets (Ref 10, p 239 & Ref 15, part IV) As soon as the CS2 evaporated, the phosphorous
In addition to the “electron” bomb pre- ignited the rubber and this continued to burn
viously described, the following foreign incendi- for 5-7 minutes
ary bombs used in WWl I might be mentioned: g/ Japanese 60kg Thermite Bomb consisted
a/ German Incendiary-Explosive Bomb was a of a casing, 40” long and 8“ in diameter, con-
magnesium incendiary bomb which was lengthen- taining three “electron” inserts filled with
ed in the nose to provide space for a high thermite and a burster charge of high explosive.
explosive charge. The total weight of the bomb On landing, the burster charge scattered the
was 5 lb and the total length, including the burning inserts as separate thermite units, thus
tail, was 2 1“. On landing, the, incendiary part increasing the radius of damage
of the bomb ignited but the explosive part re- hl Japanese 60kg’ Gelled-Oil Incendiary Bomb
mained intact and exploded up to 7 minutes consisted of a casing, 42” long and 9.5” in
later. In some bombs, the explosive part be- diameter, filled with gelled oil, such as kerosene
came detached on landing and rolled away and paraffin wax. Inside the falling there was a
from the incendiary section tube fdled with thermite which had a quick
bl German 50kg Incendia~-Explosive Bomb match running through its center. On impact,
consisted of a casing, 30” long and 8“ in diam- the oil was ejected and was ignited by the
eter, which contained, besides the incendiary thermite
charge, a 12 lb charge of TNT lodged in the i/ Japanese 560 lb Bomb consisted of a
nose. On impact, the bomb ejected 60 small cylindrical, metallic casing loaded with pieces of
metal containers with thermite-type filling and 1-inch iron tubing, each 2-3/4” long. It was
6 larger tumbler-shaped fire pots containing a filled with a special thermite mixture. On
magnesium-type falling. This was ‘followed al- landing, the burster charge fractured the casing,
most immediately by explosion of the TNT ignited the thermite and scattered the pieces
charge of tubing to a distance of about 150 ft
C[ German 50kg Phosphorous Incendiary j/ Flame Thro wer– described separately in
Bomb consisted of a casing similar to the pre- Vol 6 of Encycl
vious bomb, ffled with a mixture of yellow kl Miscellaneous Incendiary Ammunition.
phosphorous 86.5, benzene 13.1 and polystyrene Among these may be mentioned “incendiary
0.4%. The bomb was split open on impact by cans and boxes” used during WWI as a means
the bursting charge and the incendiary was of defense against gas attacks. The heat gen-
scattered in the form of a sticky self-igniting erated by these devices produced air currents
liquid
 178

which dispersed and deflected the gases tiles to conditions of modern warfare is still
Various incendiary devices were designed for somewhat uncertain despite the increasing im-
sabotage purposes, among them the ingenious portance of the rocket itself. At extreme
device called “incendiary blue pencil,” previously ranges, the rocket cannot compete with the
described bomber in attacking incendiary targets because
Special devices were attached to gasoline tanks of the diffuse pattern of rocket impacts
of airplanes by means of which the airplane Refs: 1) Daniel (1902), pp 151-4 2) Marshall, 1,
could be quickly destroyed in case it was forced (1917), pp 12-30; 2, (1917), p 568 & 3, (1932),
down in enemy territory 197 3) HB. Faber, “Military Pyrotechnics,”
1/ Rocket Incendiary Projectiles. During WWl I Govt Printing Oft, Washington, DC, Vols 1 & 2,
several rocket incendiary projectiles were devel- (1917) 4) A.B. Ray, IEC, 13, 641 & 714 (1921)
oped, among them may be cited: 4a) A. Stettbacher, Nitrocellulose, 6, 202, 220
German 32cm Rocket Projectile Incendia~ (1935); 9, 75, 100, 138 (1938); 13, 203, 224
carried a charge of 13 gals of flammable oil. (1943) 5) A.M. Prentiss, “Chemicals in War,”
It was used in anti-aircraft fire (Ref 9, p 55) McGraw-Hill, NY (1937) 5a) N.D. Cheronis,
5-inch Incendiary Rocket, used at ranges of Chemical Warfare in the Middle Ages, JChem
about 5,000 yds, was an effective weapon when Education 14, 360-5 (1937) 6) C. Wachtell,
fired from landing craft in amphibious opera- Chemical Warfare, ChemCatCo, BrookIyn (1941)
tions. The rocket ‘head was loaded with thermite 6a) Anon, JChEducation, 20, 59-60 (1943), Re-
or oil incendiary mixtures cent Developments in Incendiaries 7) A. Stett-
German R1OOBS Air-to-Air Rocket. The bacher, Protar (Switzerland) (1944), pp 158-164
rocket weighed 100kg and was 2 10mm in dia 7a) Volta Torrey, New Incendiary Bombs Packed
and 1,800mm long. It was propelled by 25kg with Gelgas & Pyrogel, PopScience (May 1945),
of conventional solid propellant which gave the pp 100-106 8) Anon, Various Chemical Mix-
missile a specific impulse of 4,200 kg/see with a tures used in Chemical’ Warfare Service, Chemical
burning time of 0.9 sec. The rocket attained a Industries 57, 79 (July 1945) 8a) L.F. Fieser et
speed of 550-600 m/see and had a range of al, “Napalm,” IEC, 38, 768-73 (1946) 9) G.J.
about 2,000 m. The warhead weighed about Fisher, “Incendiary Warfare,” McGraw-Hill Co, NY
30kg and contained 460 thermite-fdled cylinders (1946) 10) T.C. Ohart, Elements of Ammunition,
each weighing 55g. The pellets were given an J. Wiley & Sons, NY (1946) 10a) G.J.B. Fisher,
initial velocity of 500m/sec in addition to the “Incendiary Warfare,” McGraw-Hill, NY (1946)
velocity of the rocket. The rockets were 11) W.A. Noyes Jr, Ed, “Chemistry (Science in
mounted under wings of a plane (Ref 14) WWH),” Little, Brown & Co, Boston (1948) 12)
German Enzian Ground-to-Air Rocket. The A. Stettbacher, “Spreng-und Schiesstoffe~’ Rascher
rocket weighed l,800kg which inchrded the Verlag, Zurich (1948), pp 124-129 13) War
weight of four assisted take-off units weighing Department Manuals on Incendiary Compounds
80kg each. These units functioned for 5 sec & Devices
and were then jettisoned. The missi!s had a a. TM3-215, Military Chemistry & Chemical
length of 12 ft and a wing spread of 14 ft. Agents (1942), pp 149-150
The power supply had a duration of 73 sec b. TM9-1980, Bombs for Aircraft (1942)
which resulted in a vertical range of 16,000m c. TM3-325, Livens Projector Ml (1942)
and a horizontal range of 25,000m. The pay- d. TM3-330, Incendiary Bombs (1942)
load was either 300 or 500kg. These warheads e. Flame Throwers (See below)
consisted of a metal shell, 1 1/2mm thick con- 14) M. Cutler et al, “Preliminary Survey on In-
taining cylindrical pellets of mild steel, 20mm cendiary Pellet Warheads for Guided Missiles,”
in dia by 30mm long containing an incendiary Guided Missile Rept No 7 (Dee 1948), Tech
core. This rocket appeared near the end of Command, Army Chem Center, Md 14a) L.
WWl I and large-scale production was never Finkelstein & A.E. Gaul, “Incendiaries,” Vol 18,
attained before hostilities ended (Refs 14 & 15) History of Research & Development of Chemical
According to Fisher (Ref 9, p 55), the Warfare Service in World War II, The Chemical
applicability of incendiary-filled rocket projec- Corps Association, Washington, DC, Reinhold,
 I 79

NY (1948) 15) F.L Ordway & R.C. Wakefield, (1924). Incendiary shell-structural features
“International Missile & Spacecraft Guide,” A. Wolfson, 26, 4720 (1932). Incendiary
McGraw-Hill, NY (1960) 16) Anon, “Military ,compound, which may be ignited by a spark
Pyrotechnic Series, Part I, Theory & Applicationj” produced by friction, is prepd by mixing solid
AMCP 706-185 (1967), Chapter 5, Production of fuels, such as hex (CHZ )6 Nq or metaldehyde,
Heat 17) H. Ellern, “Military & Civilian Pyro- with readily, flammable substances, such as
technics,” Chem Publg Co, NY (1968), Chapter NC, P or nitrophenols. The composition may
25, Fire Starting & Fire Setting be pressed into tablets
The following references on incendiary com- A. Stettbacher, 30, 1563 (1936) and 32,
positions, devices and uses are given in Chemical 8781 (1938). Review of chemical and mechani-
Abstracts: cal incendiary devices
G. Fox & G. Quayle, 13, 1766 (1919), Ignit- T. A. Craven, 31, 1618 (1937). Incendiary
er compound for “thermite”: Na202 50, Mg projectile containing a charge prepd by coating
powder 10, sulfur 5, KN03 5, carbolic acid 30. yellow phosphorous with a solution of a
It ignites on contact with H2 O vegetable resin and a second coating of
J. Buck@ham, 13, 1931 (1919), Incendiary KC103 -Sb2 S3 composition. The charge may be
projectiles containing yellow phosphorous with wrapped in cotton gauze impregnated with
or without powdered aluminum NaN03 with or without Mg composition to
G. Vautin, 13, 2284 (1919), Binding material facilitate ignition
for thermite, etc, consisting of Na and K J. L. Nayler, 33, 1941 (1939). Description
silicates alone or mixed with borax or gelatinous ‘of various incendiary bombs, particularly those
Fe(OH)3 containing oils, Mg and P, and ways of com-
G. Webb, 13, 2284 (1919), Incendiary mix- bating the fires
tures suitable for projectiles: MgO 1.1p, Mg E. Fisher, 37, 5241 (1943). Incendiary suit-
(wax-coated) 3.7p, Ba(NO.), 7, HQO–sufficient able for filling bombs and flares is prepd by
to make the mixture set mixing thoroughly Mg dust with pulped paper
G. Webb, 13, 2284 (1919). Incendiary com- in water and then faltering to produce a uni-
position, such as MgO 3.45p, Mg (wax- or resin- formly flat sheet or ribbon. After drying, the
coated) 3.7, Ba(N03 )2 7. ‘fhis mixture was dw- sheet is cut into pieces
pressed. The alkaline earth serves as a retarder W. R. Bluedorn & R. N. Nelson, 38, 257
of combustion and, by varying the quantity of (1944). Incendiary bullet of special construction
t~: ,~ngredient, the rapidity of combustion can containing finely divided Ti as combustible
be fixed as desired within wide limits material
A. Chanard, 14, 350 & 1045 (1920). An ChemicaI Warfare Service, 38, 1295 (1944).
incendiary material prepd by incorporating a Brief history and description of modern
small amount of celluloid or NC in combustible incendiaries
substances such as resin dissolved in gasoline, C. W. van Hoogstraten, Chem Zentr 1941,
heavy oil, tar, etc H, 3272 & CA 38, 1880 (1944). Various types
W. T. Scheele, 15, 3751 (1921). An incen- of incendiary bombs as well as means of
diary mixture adopted for use in bombs and combating the fires produced by them are
shells contains hexamethylenetetramine described
((CH, ). N.) 22.5 to 33.33 and Na, 0, 77.5 to W. C. Kabrich, 39, 2649 (1945). Research
66.66 in the Technical Division of Chemical Warfare
Another mixture contains hexamethylene- Service in incendiaries, etc
tetramine (CHZ )6 Nq 25, Na2Oz 50 and paraffin W. K. Griesinger, 39, 1284 and 4742 (1945),
(or cylinder oil) 25 Canadian Pat 424914 (1945). Gelatinization of
J. H. Hammond Jr, 17, 472 (1923). Incen- hydrocarbon distillates in order to prepare
diary shell containing a thermite charge ignited solidified fuels suitable as incendiaries, is achieved
by a mixture of Ba02 and Al, fired by a by mixing a hydrocarbon distillate with 0.5-1 O%
concussion fuse by volume of an aqueous solution containing 10-
W. L. Clay & A. H. Hallowell, 17, 473 40% by weight of petroleum sulfonate and
 I 80

5-1 5% by weight of an alkali metal hydroxide. isobutylene polymer, mol wt 50,000 to 100,000).
Petroleum sulfonate was derived from acid Small amounts of metal soaps may replace part
sludge separated from partly cracked gasoline- of the polymer. Na, K, P and thermite mixtures
oil fractions which had been treated with Hz SOq may be included. The bomb contains a nose
Ford Motor Co, 40,210 (1946). Incendiary fuse, a black powder ignition charge, a thermite
material is prepd by reducing MgO to Mg vapor and nose charge and a tube of thermite extending
quenching the vapor in oil. This produces a thin through the incendiary charge
slurry consisting of finely divided metallic Mg D. P. O’Brien, USP 2451864 (1948) & CA
and oil. The slurry is allowed to settle, the oil 43, 1190 (1949). An explosive charge for in-
is decanted and the thick slurry is filtered, cendiary bombs consists of Mg 32p, Ca3P2
leaving a thick, heavy mud 2p and KC104 1P
L. F. Fieser et al, 40, 5567 (1946) and Ind D. L. Woodberry et al, USP 2452091 (1948)
EngChem, 38, 768-73 (1946). “Napalm” (Detailed & CA 43, 1190 (1949). Thermite mixtures can
description of preparation and properties). Some be improved by incorporating Ba(N03 )Z, small
other thickened fuels are described amount of an oil and addnl Al beyond that
A. Grobstein, 40, 5568 (1946). Incendiary required by the thermite; eg, Fe oxide scale
with high penetrating power is prepd by placing 61.2, granular Al 19.2, grained Al 2.8, flaked
a capsule with Li nitride (Li3 N) into an in- Al 1.0, Ba(N03)2 14.6, S 0.9 and castor oil
cendiary bomb filled with thermite or other 0.3%. Particle sizes are of importance and are
composition. On burning, the thermite produces specified in detail
sufficient heat to fuse the nitride into a mass, Wm. F. VanLoenen, USP 2530489 (1950) &
which then becomes a penetrating, hot, corrosive CA 45, 2670 (1951). It is disclosed that a
agent. Nitrides of Ce, K, Ca or La are rdso mixture of Mg, C and MgO obtained by the
suitable Hansgirg process (see below) protected by
J. Billing &,J. W. Fisher, 40, 6818 (1946). hydrocarbon oils and a metallic carbide, such
Incendiary projectiles are charged with a highly as CaC2 or a phosphide, form an incendiary
inflammable thickened fuel, prepd by dis- composition which ignites in water or similar
solving a quantity of metallic soap of a fatty oxidizing liquid
acid containing 10 or more C atoms per mole, Note: The USP 2530491; 2530492 and 2530493
in a liquid hydrocarbon, preferably of the describe various modifications of the above in-
benzene series cendiary mixture
G. J. B. Fisher, “Incendiary Warfare,” Mc- F. Hansgirg, USP 1884993 (1932) & CA 27,
Graw-Hill, NY (1946) 942 (1933). A mixture of Mg, C and MgO
H. Bond, Edit, “Fire and the Air War,” prepared by a special process
National Fire Protection Association, Boston, L. Finkelstein, USP 2553568 (1951) & CA
Mass (1946) 45, 7354 (195 1). Gelled gasoline for Falling in-
H. R. Dittmar & D. E. Strain, USP 2443378 cendiary bombs is. prepd by dissolving in
(1948) & CA 42, 6538 (1948). Incendiary gels 88.75p gasoline, 3p stearic acid, keeping the
containing a liquid hydrocarbon (such as gaso- temp at 26°. Isobutylmetacrylate 5p was next
line, benzene, etc), 3% or less Hz O, some alkali stirred into the mixture, then CaO was added
(such as NH3, NaOH, Ca(ON)2, etc), 1 to 10% and finally water 1.25p
of a salt of a hydrocarbon-sol, salt-forming, M. E. Barker, USP 2558726 (1951) & CA
acrylic resin (such as polymers of alkyl acrylates, 45, 9864 (195 1) describes an incendiary device
or alkyl acrylites contg small amts of free COOH consisting of a mass of NC in the form of a
groups), with or without salts of fatty acids (such disc, or leaf, with a hollow center filled with
as alkali metal stearates, palpitates, oleates, etc white P and sealed with a material such as
H. H. Cooke & E. J. Holzclaw, USP 2445311 gelled Na silicate. The disc is stored under water,
and 2445312 (1948) & CA 42, 7985-6 (1 948). or in atmosphere of saturated steam. Men ex-
Incendiary mixtures consisting of flammable posed to air the coating of silicate loses its
naphtha thickened to form a highly viscous water of gellation thus making it porous. Air
mass by means of isoolefin polymers (such as then penetrates through the pores and causes
 I 81

the P and then the NC to ignite. The t~ckness (1958) & CA 52, 5826 (1958). An incendiary
of silicate coating is so adjusted that a time for military purposes is described. It contains
delay of one to 3 hours is obtained after a core of Zr, Ti, and Pb which sparks intensely
start of air exposure when abraded and an enveloping Fe case. A
J. A. Southern et al, USP 2570990 (1951) compn contg 35% Zr, 30% Ti and 35% Pb
& CA 46, 1768 (1952). An easily combustible (Zr and Ti <15p, Pb –200 mesh) is mixed
mixture suitable as fuel for incendiary bombs with a xylene-4% Perbunan (synthetic rubber)
and grenades, flame throwers, etc. Consists of soln in the presence of 0.875 cc/g of powd
7-1470 volatile hydrocarbon fuel such as gasoline, metal. The particle size of the electrolytic Fe
and 93 to 86?Z0of soap-type gelling agent, powder for the case is important in order that
which is composed of Al’ oleate 50-75, Al the poro~ity be controlled
stearate 25-50, to which is added about 1YO of C. B. Linn, USP 2881066 (1959) & CA 53,
oxy-aromatic antioxidant compound 14522 (1959) claims incendiary fuels consisting
E. F. Bullene, ArmForcesChemJ 5 (4), 4 & of gels formed by the condensation of 2 moles
CA 46, 1768 (1952) gives a review of gelled of an aromatic hydrocarbon with a ketose and
liquid hydrocarbon fuels gel-formation in benzene. The condensation of
L. F. Fieser, USP 2606107 (1952) & CA d-fructose with 2 moles of toluene, in an
47, 1392 (1953). Incendiary gels prepared by autoclave with HF catalyst, is given as an
mixing light hydrocarbon fuels with thickening example
such as Al soap of a soap-forming carboxylic Raymond E. Schaad, USP 2891852 (1959)
or unsatd fatty acid or the Al salt of such & CA 53, 17513 (1959). Materials useful as
acids as the other component; eg, gasoline 90, rocket fuels, semisolid or gelled fuels for
Al coconut soap 5, Al napthenate 5% bursting and tail-ejection-type bombs, and in-
M. D. Banus & J. J. McSharry, USP cendiary fuels for flame throwers and hand
2688575 (1954) & CA 48, “1421O (1954) grenades are described. They are made by
specify that Ti powder for use in first-f~e mix- mixing 0.1 -25Y0 by wt of satd, unsatd, or aro-
tures for incendiary bombs or shells should matic nitrohydrocarbons or their mixts, such as
have a density of 0.4 to 1.7 and contain tO.425% nitro- or dinitromethane, -ethane, -propane, or
hydrogen. Method of attaining these specs are -butane with divinylated ketoses or diaryl
described deoxyketitols prepd by reaction of C3~ ketose
L. E. Medlock, BritPat 742283 (1955). sugars with Cb.x aromatic hydrocarbons. The
No CA listing found. These non-detonating, latter include Cc ~, toluene, naphthalene, anthra-
waterproof compositions consist of pulverulent cene and tlieir alkylated derivs
oxidizing and reducing agents distributed uni- J. Allovio, “USP 2988438 (1961) & CA, 55,
formly through rubber or artificial rubber. Used 25257 (196 1) claims a free-flowing, homogeneous
for such purposes as fuses, igniter cords, and incendiary mixture of granular material uniform-
incendiary charges ly dispersed in a polymeric matrix
H. Z. Cier & H. G. Schutze, USP 2794003 M. K. Shevchuk, “Zazhigatel’nyie Sredstva
(1957) & CA 52, 1602 (1958). Incendiary gels, i Zashchita ot Nikh” (Incendiary “Agents and
solid fuels, etc are prepd without external gela- Protection from Them), Voyennoye Izdatel’,
tion agents when Na, K, Ca, Ba, Hg or Al Moskva (1961 )–a book in Russian
derivs of oil-sol sulfonyl chlorides of ,satd par- P. Chereau, FrP 1318773 (1963) & CA 58,
affin or naphtenic hydrocarbons contg 6-16 C 13702 (1963), claims: rocket fuel or incendiary
atoms are formed in the hydrocarbon to be composed of a combustible metal, eg, Al, Mg, or
gelled. Most of the gels contain O.1-5.0% water, Li or a liquid fuel such as kerosine, in fine grains
alkali and 1-5% metal. The hydrocarbon, S02, or droplets encapsulated in situ by formation of
and Cl are exposed to light at 150”F for 15- a polymer skin. Thus, 0.18 of 2,4-tolylene
360 min to give the sr.dfonyl chloride; addn of diisocyanate is dissolved in 41 .8g of paraffin oil.
a basic Al soln or Al foil or powder with A portion (24.5g) of this mixt is added drop
stirring forms the gel by drop to a stirred soln contg 2g of ethylene
C. Blake & Wm. S. Graff, USP 2819163 glycol in 250g water. Discrete spherical particles

I
 I 82

are formed which are encapsulated by a skin P. Huber, BelgP 644290 (1964), claims poly-
of polyurethane. The particles are sepal by styrene and/or polyisobutylene (3-5%) can be
centrifugation used as a gelling agent for inflammable hydro-
A. D. Coates & E. O. Baicy, USP 3120459 carbons & other org liquids, such as CSZ. De-
(1964) & CA 60, 9094 (1964) claim the pending on the intended use, the compositions
following: A storage-stable powder useful as an can be made shock-resistant, adhesive, and/or
incendiary component, a solid rocket-fuel addi- productive of thick black smoke
tive, or a metal heating powder is obtained by Review article: Chemical warfare: incendiaries.
coating a powd material which contains excess L. W. Greene, Kirk-Othmer Encycl Chem Tech-
O or liberates O on heating, such as KC104 nol, 2nd Ed, 4, 895 (1964) & CA 65, 3661
@referred), N;C104, Ba(CIO. )2, KN02, NaNO,, (1966); including a survey of incendiary require:
Ba(N02 )2, or NaC102, under conditions which ments, agents & bombs; 8 refs
avoid decompn with 30-8070 (of final coated J. E. Claiborne, USP 3250652 (1966) & CA
product) of an exotherrnic metal, such as Al 65, 2057 (1966) claims: exothermic composi-
(preferred), Mg-Ti alloys, or certain Mg–Al alloys, tions useful as propellants, incendiaries & nu-
by treating the O-contg material with metal clear blast simulators, which upon addn of
vapor at 5 x 104 mm. Thus, 40-80 mesh KCIOq, small amts of Hz O produce flame & hot ex-
treated as described with Al vapor produced by panding gases, are provided by intimate mixts
heating Al ribbon or wire with Ti wire fila- of 10-100 mesh powdered metal (preferably
ments, yields a product which, when rnitiated at least half Zn), 10-250 mesh NHQN03, &
by flame or an elec impulse, reacts’ in a self- 10-250 mesh NH4 Cl as a loose massor as blocks,
sustaining manner grains, or strands bound with an anhyd heat-
F. N. Vannuccj, USP 3126259 (1964) & CA softening gum or a thermoplastic resin or lacquer.
60, 15676 (1964) claims a gelatinous incendiary Conventional diluents may be included to
material is made by mixing 1 part of a powder- reduce. reaction rate if desired. Thus, a mixt
ed material consisting of Si02 & MgO with an of 40-80 mesh Zn 30/powd NHq Cl 20/powd
equal amt of water, adding 1 part of a hydro- NHq N03 47/ & polyvinylchloride molding powder
carbon such as kerosine or gasoline, and 3% was heated to the softening point & pressed
separating. The resultant incendiary can be used into blocks which, when exposed 6 hrs to 8570
to ignite coal or other fuels or in incendiary relative humidity, spontaneously ignited, or;
shells, bombs & flame-throwing devices. The when immersed in 10% of their wt of Hz O
powdered material can be made from yielded copious amts of H, NH3, Cl, N, & N02
serpentine rock H. W. Koch & F. Popperl, NASA Access
R. J. Laran, USP 3157464 (1964) & CA No N66-31925, Rept No T-37/65 (1965) & CA
62, 2530 (1965) claims: HCIOq & TiC14 were 66, 117, 557, (1967), discuss the them cornpsn &
combined at -10° in a mole ratio of 8:1. The incendiary characteristics of napalm & Phosphor-
product was 97-8% Ti(CIOq )4. This compound Mg compounds. Test arrangements for obtaining
exists in 3 tryst form; it can be stored without temp rates in various environments are described.
decomposition if air & Hz O are excluded & Burning time is measured as a function of
temp is kept low, eg, with dry ice. Also, freshly amount (sic) & spatial extension of the flame
sublimed BeC12 & anhyd HCIOq were allowed A. Laths, USP 3314836 (1967) & CA 66,
to react for several hrs at -15°. A white powder 117565 (1967) claims a military flame producing
Be(C104)Z, was obtained in 16% yield, excess compsn containing colloidal yellow P in a
acid having been removed in vacuo. Close temp flammable medium
control (-75 to 25°) & the absence of Hz O are M. Piccone, USP 3396060 (1968) & CA 69,
essential to these reactions. The products are 78900 (1968) describes a long-burning, low d
powerful oxidants, insensitive to, shock & ther- incendiary compsn containing Ti/Al-Mg alloy/
mal decompn, useful as igniters for propellants oxidizer. The oxidizers used were Ba or Amm
& incendiaries. Ti(C104)Q explodes on contact nitrates and K-perchlorate
with Etz O & ignites on contact with HCONMez J. R. E. Pleasant et al, USP 3414443 (1968)
or HCONHZ & CA 70, 39441 (1969) claim an incendiary
 I 83

compsn, which may be self-igniting for emer- Incendiary Flash Tests for Small Arms Ammu-
gency kits & survival & distress fires. Metals nition. The purpose of these tests is to in-
or Metal hydrides are mixed with wax & a vestigate the ability of incendiary bullets to
gelling agent develop, upon impact, an incandescent flash,
S. Schiff, USP 3416899 (1968) & CA 70, sufficiently hot and sustained to ignite explosive
39432 (1969). A napalm-type material is prepd vapors, or to initiate combustion in other
by hydrogenation of a hydrocarbon soln of a readily combustible materials. These tests also
3:1 butadiene-styrene block copolymer establish the relative size, position and persis-
P. G. Yur’ev, Zll ,Vses Khim Obshchest 13 tence of the flash as compared with a standard
(6) 648 (1968) & CA 70, 69710 (1969), pre- chart. Tests are made under controlled con-
sents a general review of chemical incendiaries ditions against a target of fixed design
with particular emphasis on US Army weaponry; Detailed description of these tests is given
with 20 refs thru 1967 in Ordnance Proof Manual 7-19 (1945) (1 1 pps)
G. H. Custard, USP 3421439 (1969) & CA
70, 89345’ (1969). An incendiary projectile is Incident Wave in Blast. See VO1 2, p B182-L
claimed which consists of a 20mm hollow body & Fig in p B183 under Blast Effects Due to
equipped with an impact-responsive primer, a Reflected Shock Waves
booster charge & a main HE charge. The body
of the projectile is of Ti or Zr which on ignition Increments. See under Base Charge of a Pro-
burns at temps of 2725 -3325°C for up to 1 rnin pellant in Vol 2, p B24 f.. ~.
S. Samuel et al, USP 3441955 (1969) & CA
71, 23400 (1969). White P is mixed with Increment Appoint (Fr) or Zusatzladung (Ger).
hexamethylenetetramine to produce a smoke An additionrd quantity of propellant used when
screen mixt which is also an incendiary. Al or the charge contains some flash reducers in order
Mg may be added to the mixt to raise flame not to impair the ballistics of a weapon
temps or paper pulp, cellulose or high-melting Refi Davis (1943), 326
hydrocarbons to produce longer burning times
J. Wlnkler, USP 3460922 (1969) & CA 71, I ncT or IT. Incendiary Tracer
93351 (1969) claims a thixotropic-gelled
flammable hydrocarbon compsn, containing Indazolone, 5,7 Dinitro.
powdered metals and/or AN, for use in flame- 02N -CO
NH
throwers, rocket fuel and napalm. The hydro- NH >
carbon gel is prepd by an in situ cross-linking o
of a polyurethane N02
V. P. Wystrach et al, USP 3464869 (1969) mw 304.3, N 18.470, OB -58.0%; yellow prism
& CA 71, 103746 (1969) claim a match-ignitable, (from w), decomposes 185-215° without
tacky compsn for use” in flares, signals & in- melting; s] sol in water, benz & chlf; moderately
cendiaries. Example compsn is made by mixing sol in boiling ale. Prepd by reacting 3,5-dinitro-
Mg, AN, Napalm B with an acrylonitriline/ benzene with hydrazine hydrate. The Na-salg,
acrylic acid/Me-methacrylate copolymer. It burns Na2C7H2 Nq OS, tryst, sol in w, alc or acet,
with a bright yellow flame explodes on heating. Reaction of the dinitro
V. A. Lehikoinen, USP 3498857 (1970) & indazolone with HgC12 gives a crystalline needle-
CA 72, 113395 (1970) claims thermites and like product that is very unstable
thermates (thermites + flake Al, S, hydrocarbon Refi Beil 24, 115 & (239)
oil and/or oxidizers such as Ba(N03 )2, KMuOq,
etc) of improved ignitability due to inclusion Index of Damage. See under Damage Effects &
of 2-50% of ferrocene-type compounds. Damage Potential of Air and Ground Blast Waves
Varying the proportion of ferrocene modifies in Vol 3, pp D3-4
the burning rate of the incendiary compsn
Index of Ignition. See Index of Inflammability
under Physical Tests in Vol 1, p XVII
 I 84

India Saltpeter. Same as Potassium Nitrate mw 352.2, N 1s.g~., OB -136.870; deep-red

crystals (from NB), sol in hot NB or phenol,
Indicator Test Paper for Detecting Stability of insol in alc or .eth. Prepd by mixed acid nitra-
Double-Base Approx 60 commer-
Propellants. tion of indigo, or reaction of Diacetyl-6-nitro-
cially available dyes were investigated in experi- indoxyl (in air) with hot sulfuric acid. On heat-
mental indicator test papers. Laboratory & ing it puffs off giving off redwiolet vapors
surveillance tests indicated that 3 of these
selected for further evaluation were less sensitive Indigo, 6,6’-Dinitro. A dark-red powder, insol in
to double-base proplnt degradation products w, s] sol in ale, eth or benz, sol in hot aniline.
than N/10 Methyl Violet paper. The order of Prepd by heating 2,4-Dinitrophenyllactic acid,
sensitivity was as follows: N/l O Methyl Violet, methylketone with Na2C03. Sublimes on glass
0.1% Ethyl Violet, 0.1 % Trypan Red & 0.1% surfaces, puffs off on platinum surfaces
Benzoazurine. On exposure to four different Refi Beil 24, 429 (382) & [245]
types of partially degraded but still serviceable
double-base proplnts for a period of 1 yr, Indole-carbonic acid, 5,7-Dinitro (called 5,7
strips of each of these experimental indicator Trinitroindol carbonsaiire or Dinitrostrychol in
papers remained either unchanged or became Ger). ,HC~
only slightly faded. The N/10 Methyl “Violet (02 N), C, H, CCOOH, mw 251.3,
paper became. totally bleached within 3 months =NH Z
However, strips of the experimental indicator N 16.7%, OB -9 1.7%; pale yellow tryst (from
papers, when exposed to oxides of N fumes gen- ale), darkens 250°, mp ‘284° (with decomp);
erated in the lab and to double-base proplnt insol in most SOIVSexcept hot ale. Prepd by
fumes generated at an elevated temp, became heating 5,7-Dinitro-indol-dicarb oxylic acid in
either entirely bleached or totally faded water. Its Et ester-Trinitro derivative melts at
Refs: 1) S. Helf, PATR 1782 (Ott 1950) ,2) 202-205° and is stable (Ref 2)
P. Rochlin, PATR 2242 (Sept 1952) (Concluded Refs: 1) Beil 22, [49] 2) CA 29, 158 (1935)
that the 3 experimental test papers appeared to 2) F.C. Mathier & R. Robinson, JChemSoc 1934,
be superior to N/10 Methyl Violet paper for 1415 &CA 29, 158 (1935)
detecting instability in stored proplnts)
Indole-carbonic acid, 5,7,x-Trinitro (called 5,7
Indice Nitrometrique or Indice de I’Action Trinitroindol carbonsaike or Trinitrostrychol in
Stabilisatrice is a value introduced by M. Giua I Ger).
.& G. Guastalla and reported in AttiAccadScienze (02
/ c~O#OOH,
N)2 C6 Hz\M/
mw 296.3,
Torino 60, 73 (1925) & Chim & Ind 29, 63T
(1933) N 18.9%, OB -63 .0%; leaflets (from water), mp
It was shown by the above authors that nitro- 218-220° (with decomp); sol in hot water or
gen content of nitric esters such as NC or NC ale, S1sol in benz or eth. Prepd by nitrating
cannot be determined by the nitrometer method, 5,7-Dinitro-indole-dicarboxylic acid with fuming
if stabilizers such as centrality are present, be- nitric acid. Puffs off on heating
cause centrality absorbs some nitrogen oxides Refl Beil 22, [49]
thus giving a low result for N. The difference
between the nitrometer N content of NC in Induced Ground Waves. See Vol 3, p D4-L
absence of a stabilizer and N content of NC in under Damage Potential of Air and Ground
presence of a stabilizer may be taken as an Blast Waves
index of stabilizing action of the stabilizer; the
bigger the difference, the better the stabilizer. Induction Period. See under Delay to Ignition
This difference is called indite nitrom<trique in Vol 3, p D53-R; also under Hot Spots in
this Vol
Indigo, 5,5’-Dinitro.

o
Indurite. The first successful American smoke-
02 N –co\ ,CO N02
less proplnt invented by C. E. Munroe in about
-NH’C=C’NH o 1891 and patented in 1893 (USP 489684). It
 I 85

was prepd by washing ordinary Guncotton (CC) control or extinguishment reduces to a

with methanol, in order to remove the lower manipulation of these three essential constituents
NC’s, and then gelatinizing (colliding) it with Classification of Fires
NB (nitrobenzene). in the proportion, GC 40 Class A Fires. These are fires in ordinary
and NB 60. It was made with or without combustible materials where the quenching and
oxidizing salts, such as KN03 etc. The resulting cooling effects of quantities of water or solu-
gelatinous mass was rolled into sheets of de- tions containing large percentages of water are
sired thickness and cut into squares or strips of first importance. Ordinary combustible
which were hardened (“indurated”) by the action materials tend to produce glowing embers after
of hot water or steam. This treatment also dis- burning, and these must be quenched to pre-
tilled off most of the NB and left a hard and vent rekindling
tough colloided substance Class B Fires. These are fires in j7amrnable
When tested, it gave satisfactory results in liquids (oils, gasoline, solvents, etc.), where a
guns ranging from the one-pounder to the 6“ blanketing or smothering effect is essential to
gun. The reason why it was not adopted by put the fire out. This effect keeps oxygen
ordnance. was that at a slightly later date Lt away from the fuel, and can be obtained with
Bernadou introduced in USA pyro powder, which carbon dioxide, dry chemical (essentially sodium
was the same as Mendeleev’s “pyro-collodion” bicarbonate), foam, or a vaporizing-liquid type
powder, but with slightly higher nitrogen content of extinguishing agent. Water is. most effective
Refs: 1) C. E. Monroe, JACS, 18, 817-46 (1896) when used as a fine spray or mist
2) Davis (1943), 296 Class C Fires. These are fires in electrical
equipment, where the use of a nonconducting
Industrial (or Commercial) Explosives, also called extinguishing agent is essential. Water spray,
Civil (or Civilian) Explosives. See Agriculture carbon dioxide, dry chemical, or vaporizing
and Forestry Use of Explosives in Vol 1, p liquid is satisfactory
Al 12-R; Blasting Explosives in Vol 2, p B202.L; Metal and Gas Fires. Such fires have not yet
Commercial or Industrial Explosives in Vol 3, been classified. These require special agents and
p C434-R; and Dynamites in Vol 5, p D1 584-L techniques. For a discussion of extinguishing
agents and techniques for these classes of fire
Industrial Disaster Control is briefly discussed see p 206
in the “Dangerous Properties of Hazardous Definition of Terms
Materials” by N. Irving Sax, Reinhold, NY The meanings of fire control terms as used
(1957), pp 166-169 in this book are as follows:
Flash Point (flash p). This is the lowest
Industrial Fire Protection. from
We quote temperature at which a liquid will give off
Section 6 of “Dangerous Properties of Industrial enough flammable vapor at or near its surface
Materials,” 3rd Edit, by N. Irving Sax, Van such that in intimate mixture with air and a
Nostrand, Reinhold, NY (1968) spark or flame it ignites. The flash point of
“WHAT IS FIRE? Fire, combustion, or liquids is usually determined by the Standard
burning requires three things: (1) a fuel (any Method of Test for Flash Point with the Tag
oxidizable material), (2) oxygen (usually air), Closed Cup Tester (ASTM D56-52, available
and (3) a certain temperature (heat). Fire is from the American Society for Testing Materi-
the chemical union of oxygen with fuel, ac- als, 1916 Race St, Philadelphia, Pa). This method
companied by evolution of thermal energy, is also the standard of the American Standards
indicated by incandescence or flame. If any Association (ASA Z 11.24-1952, available from
one of these three constituents is not present the American Standards Association, 70 East
in the proper proportions or degree, no fire 45th St, New York, NY). The Interstate Com’-
will occur. If a fire exists and even one of merce Commission uses the Tag Open CUP
them is sufficiently altered, the fire will go (TOC) Tester giving results 5– 10°F higher (less
out. Therefore, in its simplest form, all fire flammable). Other methods frequently used are
 I 86

Cleveland Open Cup (COC) and Pensky-Martens regarding a material, its formula can give a clue
(PM). The closed cup flash point value is to its fire hazard. For instance, all materials
usually several degrees lower (more flammable) ‘ composed solely of carbon and hydrogen are
than the open cup, as the test in the former combustible and in some degree flammable. If
case is made on a saturated vapor-air mixture, they are liquids with a low boiling point they
whereas in the latter case the vapor has free can be assumed to be fire hazards
access to air and thus is slightly less concen- Underwriter’s Laboratories Classification (uIc).
trated. For this reason, open cup values more This is a standard classification for grading the
nearly simulate actual conditions (see below), relative fire hazard of flammable liquids against
Fire Point (fire pt). This is the lowest the following standards:
temperature at which a mixture of air and
vapor continue to burn in an open container Ether class 100
when ignited. It is usually above the flash Gasoline class 90–100
point. Where the flash point is available, only Ethyl alcohol class 60–70
it is given; if it is not, the fire point may be Kerosene class 30–40
given. It is at least as significant as the flash Paraffin oil class 10–20
point as an indication of the fire hazard of Where this value is known it is an excellent n~ea-
a material sure of the relative hazard of a flammable liquid.
Autoignition Temperature (autoign temp). Unfortunately, it is available in only a few instances
This is the temperature at which a material Susceptibility to Spontaneous Heating. Many
(solid, liquid, or gas) will self-ignite and sustain materials combine with atmospheric oxygen at
combustion in the absence of a spark or flame ordinary temperatures and liberate heat. If the heat
(ASTM Designation D286-36). This value is is evolved faster than it is dissipated due to poor
influenced by the size, shape and material of housekeeping, a fire can start, particularly in
the heated surface, the rate of heating (in the the presence of easily ignited waste, etc. [“Fac-
case of a solid), and other factors tory Mutual Modified Mackey Method,” Indus-
Vapor Density (vap d). This value expresses trial and Engineering Chemistry (March 1927)]
the ratio of the density~of a vapor to the Explosive Range or Flammability Limits.
density of air. The vapors of most flammable These values expressed in percent by volume of
liquids are heavier than air, thus they can fuel vapor in air are the ranges of concentration
readily flow into low areas, excavations and over which a particular vapor or gas mixture
similar localities. Hence, ventilating outlets in with air will burn when ignited. If a mixture
a plant should be located near ground level. within its explosive range of concentrations is
For combustible gases and vapors which are ignited, flame propagation will occur. This
lighter than air, ventilating outlets should be range will be indicated by Iel for lower explo-
near the ceiling sive limit or uel for upper explosive limit. The
Melting Point (rep). This is the temperature values given, unless other wise indicated, are
at which the solid and liquid forms of a sub- for normal conditions of temperature and
stance exist in equilibrium. This value indicates pressure.
at what temperature flammable materials that FIRE PROTECTION
are solid at room temperature may become The two main aspects of fire protection are
flammable liquids prevention and loss limitation
Boiling Point (bp). This is the temperature Prevention e
at which a continuous flow of vapor bubbles Fire, prevention is an inseparable requirement
occurs in a liquid being heated in an open con- of fire safety. Since, in order for a fire to start,
tainer. The boiling point ‘may be taken as in all three necessary constituents–fuel, oxygen,
indication of the volatility of a material. Thus, heat–must be represented, effective fire preven-
in the case of a flammable liquid, boiling point tion simply boils down to manipulation of
can be a direct measure of the hazard involved these constituents to the extent that a fire can-
in its use not start. For instance, where a flammable
Formula. ,In the event of a lack of information material such as acetone is used out in an open
 I 87

work shop, two of the three needed constituents oxygen. Also the higher the concentration of
are immediately present, ie the fuel and a supply oxygen in an atmosphere, the more rapidly will
of oxygen. Now the only thing lacking to start burning proceed. Industrially it is difficult to
a fire is heat. Thus by referring to acetone in manipulate the oxygen concentration in a work-
Section 12 it is found that the flash point is ing area, particularly since a concentration of
14°F, which means that at any temperature oxygen far enough below normal to keep fires
above 14” F, acetone can evolve enough vapor from starting would also be too low to support
to form a flammable mixture with air which human life.
will catch fhe if exposed to a spark, flame or When industry has found it necessary to work
other source of ignition. Thus, strictly from with materials so sensitive to oxygen that they
the standpoint of fire prevention in an instal- would catch fire at ordinary temperatures merely
lation using acetone, the following avenues are Upori being exposed to air, it has found it possi-
open: ble to isolate such materials from air, either in a
(1) The working (ambient) temperature must vacuum chamber or in a chamber filled with an
be kept below 14”F, or inert atmosphere, such as argon, helium, or
(2) The supply of atmospheric oxygen must nitrogen. In Section 12 the materials which re-
be cut off, or quire such isolation are so noted
(3) Sources of ignition, such as flames, glow- Heat. As a necessa~ component of fire, this
ing cigars and cigarettes, sparks, etc must be is often manipulated to render an industrial
eliminated from the area, or set-up safe from fire. The most difficult aspect
(4) The area must be ventilated so that even of controlling the heat component of a fire is the
though the acetone gives off enough vapor to easily overlooked fact that to start a fire it is
form a flammable mixture with air, the vapor often necessary to heat to a sufficient degree only
will be drawn out of the area by means of fume a ve~ small quantity of fuel and oxygen mixture.
exhaust equipment as rapidly as it is evolved, Then, since fires are by definition exothermic,
thus preventing the build-up of dangerous con- the very small fire started by a tiny heat source
centrations of vapors supplies to its surroundings more heat than it
Naturally, since conditions (1) and (2) above absorbs, thus enabling it to ignite more fuel and
are relatively difficult to attain on an industrial oxygen mixture, and so on, until very quickly
scale, conditions (3) and (4) are the ones most there is more heat available than is needed to
likely to be used propagate a large fire. The heat may be pro-
Furthermore, although total removal of any vided by various sources of ignition, such as high
one of the necessary conditions for a fire will environmental (ambient) temperatures, hot sur-
absolutely prevent its occurrence, such stringent faces, mechanical friction, sparks, or open flame
restrictions on industrial operations are seldom Fuel. The third aspect of fire prevention will
economically feasible. Industrial materials are, be discussed in detail in the following section
however, studied with a view to ascertaining
just how much leeway there is, so that a com- Sources of Ignition
promise between absolute fire prevention and The following are the chief sources of ignition
economy of operation may be reached. It is for and suggestions for reducing the hazard due to
this reason that, while we know how to prevent them:
fires, they still do start, and why loss limitation (1) Open Flames. At or near a flammable-
is such an important part of industrial fire liquid installation it is necessary to check for
protection such sources as burners, matches, lamps, welding
Below is some discussion of the three essen- torches, lighting torches, lanterns, small furnaces,
tials of fire. and the possibility of broken gas or oil lines
Oxygen. Although under certain unusual becoming flaming torches. Ample isolation may
circumstances it is possible to produce com- often be obtained by means of partitions.
bustion-like chemical reactions with materials In this respect the partition should be substantial
such as chlorine or sulfur, it is safe to say that enough to contain the fire while the sprinklers
nearly all combustion requires the presence of or other fire-fighting apparatus put it out. Fire-
 I 88

resistant construction (brick or concrete walls) (g) Motor frames, control boxes, conduits, etc
is generally recommended should all be grounded in accordance with the
It is important to confine the flammable liquid general requirements for installation of electric
while it is in use. Safety cans should be used for power as outlined in the National Electrical
transporting small quantities of flammable liq- Code
uids about a working area, as well as for storage (3) Overheating (excessive temperatures at
at a bench. Wherever possible, closed systems points requiring heat). ”Such processes should
should be used to prevent the spread of fumes, be kept out of combustible buildings and closely
etc. In the event of a fire, it is imperative to pre- supervised. The use of automatic temperature
vent spreading of the fire. Hence all tanks should controls and high temperature limit switches is
have trapped overflow drains leading to a safe recommended, although supervision is still
place. Dikes must be used to contain the over- important
flow of burning liquid; otherwise fires could (4) Hot Surfaces. The incomplete immersion
easily spread o~er large areas, trapping personnel of hot metal in quenching baths, the contact of
and causing great damage. The principle behind flammable vapors and hot combustion cham-
this form of protection is to contain the tire bers, hot dryers, ovens, boilers, ducts and steam
at all costs. Installations of flammable liquids lines all are frequent causes of flammable vapor
in upper stories should be made only in such fires. Care should be taken that material whose
a fashion that burning liquid will be prevented auto-ignition point is lower than the temperature
from flowing down stairwells, pipe openings, sometimes reached by operating equipment be
cracks in walls, etc, by means of waterproof kept at a safe distance from such equipment.
floors, dikes, overflow pipes, etc This equipment should be carefully supervised
(2) Electrical Sources (electric power supply and maintained to prevent accidental overheating,
and generating equipment, heating equipment, etc
and lighting equipment). The following precau- (5) Spontaneous Ignition. Many tires are
tions for good maintenance are suggested. A caused by spontaneous heating of materials,
complete listing cannot be given here. The pro- accelerated by external heat from processes such
visions of the National Electrical Code are the as dryers, ovens, ducts, impregnating or steam
recognized standard and these should be care- lines adjacent to piles of waste materials. Some-
fully observed in installing electrical equipment times the accumulated heat in a closed, unventi-
in hazardous locations lated warehouse will be sufficient to accelerate
(a) Use special wiring and conduit oxidation to the point of an actual fire. Wher-
(b) Use explosion-proof motors, particularly ever flammable liquids are handled, particularly
if located at ground level or in pits or low places those which are known to be liable to spon-
(c) Use only specially engineered heating taneous heating, it is important to pay particular
units, keeping in mind the autoignition tempera- attention to housekeeping and ventilation. Fires
ture of the material in use (hot water or steam are almost sure to follow neglect of these mat-
heating units are much to be preferred) ters. All equipment and buildings should be
(d) Controls for motors, thermal cut-outs, kept free of deposits and accumulations of wip-
switches, relays, transformer co”ntactors, etc ing rags, waste materials, oil mops, etc
which are liable to spark or heat up should not (6) Sparks, etc. Sparks from mechanical
be installed in flammable liquid storage areas. tools and equipment, hot ashes from smoking,
Use only explosion-proof, push-button control unprotected extension lights, boilers and fur-
switches within such an area naces, backfire from gasoline engines, are all
(e) In dangerous atmospheres and for storage, potential causes of fire. Smoking should be
only vapor-tight globes with electric lamps may prohibited in areas where flammable liquids are
be used. In well-ventilated areas, ordinary lamps stored or are used in the open. AU equipment
will do. Fixed lamp installations are to be pre- in such areas should be maintained in first
ferred to extension cords. Also, approved safety class condition. Wherever possible, spark-proof
flashlights are preferred to portable lamps or non-sparking tools and materials should be
(f) Do not install fuses or circuit breakers in haz- used
ardous locations except in explosion-proof cases
 189

(7) Static Electricity. This is due to electrical ily between oxygen and a fuel in its vapor or
impulses generated on the surface of a material other finely divided state. Solids are most easily
by friction, such as calendering, printing, and ignited when reduced to powders or vaporized
the like. Many fires are caused in the rubber and by the application of heat, but except in a few
paper industries by this means. Most of these casesthe temperatures required for the vapori-
occur during the months when humidity is rela- zation of solids are well above normal ambient
tively low, and artificial heat is used. Maintain- temperatures
ing a relative humidity of from 40–50 percent Liquids present a different case. Some liquids
in rooms where flammable liquids are used will will give off dangerous quantities of flammable
greatly reduce the chance of static sparks. Elec- vapors well below normal room temperature
trical grounding, static discharge devices, etc (the vapor pressure of a liquid is a measure of
should be mandatory, and all flammable liquid this effect); others do so at points only slightly
tanks, piping and equipment should be so inter- above room temperature, and still others at
connected and grounded that the chances for much higher temperatures. It is apparent that
static sparks are minimized. In all this type of the temperature at which a liquid evolves vapors-
equipment, belts should be eliminated and direct which can form flammable mixtures with air is a
or chain drives used wherever possible. If belt measure of its hazard potential. This is indi-
drives must be used, the belt speed should be cated by the flash point
kept below 150 ft/min, or a special belt dressing So indicative of fire hazard is the flash point
should be used which will reduce the possibility of a liquid that the Interstate Commerce Com-
of the formation of a static spark mission rates any liquid whose flash point is
(8) Friction. Many fires are caused by me- 80° F or below as a high fire hazard, the theory
chanical friction, ie from fan impellers rubbing being that 80”F represents the upper limit of
on casings, poorly lubricated fan bearings, normal or “room” temperatures; any liquid
grinding processes and machining, etc. Fans and which wiU flash at or below this “point is danger-
other equipment should be frequently inspected ous. A flash point of from 80–350” F indicates
and maintained in the best possible condition. a moderate fire hazard; above 350° F the fire haz-
Other processes known to generate a good deal ard is considered slight. The national Fire Pro-
of heat due to friction should be well separated tection Association rates as a high hazard a
from locations where flammable liquids are liquid whose flash point is less than 20° F; mod-
stored or used erate from 20–70” F, and slight from 70–200° F.
It is vitally necessary that a complete program Only liquids having a flash point less than 200”F
for the handling, transfer and use of flammable are generally called flammable by the National
liquids be set up and maintained. This program Fire Protection Association
should start when the process is initially under In this book we use the ICC classification for
construction. Where flammable liquids are liquids of flash point at 80”F or less as being
called for in the original write-up of a process, dangerous fire hazards; we use the range from
the first question is to determine whether the about 80—225° F to indicate moderate fire hazard;
flammable material can be replaced by a non- flash points in excess of about 225°F are rated as
flammable one. If the question of cost arises it slightly hazardous. It should be understood,
should be remembered that to the possibly low however, that practically all organic materials
cost of the flammable liquid should be added the will burn if exposed to sufficiently high tempera-
cost of special protection needed to use it safely tures. The ratings given above are merely as in-
as well as its effect upon the insurance rate. It dication of the risk involved in handling or
may well be that in the final analysis, the cost of storing them
a flammable material is not as favorable as it It is important to isolate a potential fire haz-
seemed at first. However, there are many flam- ard. Thus it is necessary to use closed and vented
mable materials in constant use for which there tanks to hold flammable liquids. In this way the
are no substitutes, but even they can be safely possibilities of igniting the tank of liquid are
handled if proper precautions are taken greatly reduced, as is the chance of materials at a
(9) Fuel. Combustion takes place most read- distance from such a tank becoming involved in
 I 90

fires. It is also important that flammable mate- sidered satisfactory to install a smooth ceiling
rials be housed in fire-resistant structures be- below the piping and other projections. This
cause burning liquids can generate great heat does not eliminate the hazard and may intensify
and often set fire to the buildings in which they it; unless the ceiling is extremely well designed
are burning and installed, dust will penetrate it and settle not
A vital point in flammable liquids safety only on the piping but on the upper side of the
is the prevention of the accumulation of ceiling itself. Then a shock may be sufficient to
explosive concentrations of vapors in closed fdl the entire false space with a combustible dust
off areas. Wherever either moderately or cloud which a spark may set off. If piping can-
highly flammable liquids are used or stored, not be relocated or eliminated, it would be bet-
ventilation is a very important consideration ter to leave it exposed and provide for a regular
The amount needed, whether natural or me- cleaning program
chanical (fans and blowers) depends upon the It was for reasons such as the above that a
materials and the conditions involved. No de- starch dust plant recently constructed in the
pendence should be placed upon the odor of the southwest, where weather conditions are mod-
material as a warning, because some flammable erate the year round, has been built entirely of
vapors are heavy and tend to settle and because open construction so that there is no confine-
smell is deceptive. The safe procedure is con- ment of the force of any explosion and the
tinual testing with an explosion or flammable constant flow of air through the plant provides
vapor indicator little opportunity for dust layers to build up
Besides flammable liquid fires, the results of As in the case of flammable liquid fires and
which can be somewhat mitigated by effective explosions, the control of dust explosions is
loss limitation techniques, there are two more based upon prevention of ignition and second-
types of disaster, protection from which is nearly arily limitation of damage in the event ignition
entirely dependent upon-prevention does occur
(10) Dust Explosions. Practically any com- To prevent ignition, open flames, smoking,
bustible, when in the form of dust and mixed and cutting or welding are prohibited until the
with air in the proper proportion, will burn so area is made dust free. Electrical wiring should
rapidly as to cause a severe explosion if ignited be of the type suitable for a dusty atmosphere
by heat, a spark or flame. Ignorance of this fact and static electricity, too, must be eliminated.
has led to many serious disasters. Grain, flour, Highly dangerous materials of this sort are han-
coal dust, and metal powders all constitute haz- dled most satisfactorily in enclosed systems in
ards in this regard. Explosions have been known which suitable inert gasesare introduced into the
to occur in plants handling fertilizers, wood system to replace the air normally present. This
dust, powdered milk, soap powder, paper dust, precaution is particularly applicable to the field
cocoa, spices, cork, sulfur, heard rubber dust, of powder metallurgy. The kind of inert gas
leather dust, and many other products. For the used must be chosen on the basis of its suitability
prevention of dust explosions good housekeep- for the operation in question
ing is of the utmost importance. All equipment (11 ) Salt-bath Explosions. The third type of
must be dust-tight and kept so. Explosion vents disaster in which after-the-fact protection is
should lead outdoors to a safe location, and the much less important than prevention is the
vent ducts themselves should be strong enough molten salt-bath explosion. There have been
to withstand the force of the explosion. Vacuum serious disasters involving such baths, because
cleaning is superior to sweeping. The use of personnel involved on both the management and
compressed air to blow dust off equipment and the operating level failed to appreciate the
thus create dust clouds should be forbidden potential hazards of the situation. Due to mechan-
Ledges, exposed piping, beams, etc in the ical failure or human failure, or a combination of
ceilings should be kept free from accumulation of both, molten salt baths have been allowed to ex-
dust. Where a dusty operation is to be installed plode. The hazards of molten salt baths may be
in a location where there is piping and pro- summarized as follows:
jections overhead, it is often erroneously con- (1) Violent generation of steam due to water
 I 91

introduced as “carry-over” on a piece of work operations in which prevention is the most im-
from a preliminary cleansing or quenching bath, portant phase of fire protection. In each of these
condensation on overhead service piping, leaky cases whatever action is taken after the act and
roofs and operation of automatic sprinklers, also whatever physical protection is provided can
contact with liquid foods placed on ledges only furnish some degree of mitigation of loss
near the baths for “warming-up” by workmen and it is often insufficient to prevent a large
(2) Sudden and explosive expansion of air scale disaster
occluded in blow-holes of castings and that Loss Limitation
trapped in tubes, closed piping, or hollow metal The other aspect of a realistic fire protection
work when immersed in molten baths without program is limitation of loss due to a fire which
pre-warming includes a prokision for the prompt discovery
(3) Violent and uncontrollable chemical re- and equally prompt extinguishment of the fire. It
actions between nitrate baths and carbona- is certain that everyone has at one time or
ceous materials such as oils, soot, graphite, and another wondered why a particularly destructive
cyanide carry-over from adjacent carburizing fire was allowed to happen, when supposedly a
baths great deal of effort is constantly being devoted
(4) Vigorous and explosive reaction between to the prevention of such fires
overheated nitrate baths and aluminum alloys It may be that too often the prevention aspect
(5) Explosive reaction between normally of fire protection has been the total or nearly
heated nitrate baths and carelessly introduced total effort at protection, with the result that
magnesium alloys when even a small fire starts it has a good chance
(6) ‘I’hermit-like reaction between aluminum to become a calamity. However, even the ut-
alloy articles lost in bath and the iron oxide most vigilance’would have been of no avail in
sludge blanketing and insulating the bottom of guarding against some of the fires which are on
bath container record, and once the fire has started its cause is
(7) Structural failure of bath container while immaterial. The cause of the loss is much more
in operation under conditions tending to lower important, and the facts which determine that
the normal durability; reaction between metal of are the physical conditions and those measures
bath container and nitrate due to localized which have or have not been taken to limi{ the
overheating extension of the fire
(8) Failure of temperature controls, with con- One of the means of preventing the extension
sequent overheating of nitrate bath of fire is to segregate hazardous processes and
(9) Storage and handling of bulk supply of so- storage into separate buildings. But even where
dium nitrate, and careless disposal and storage hazardous processes are not involved, the con-
of waste nitrate without regard to active proper- centration of too much value in one fire area
ties of the salt must be guarded against. This is best accom-
(10) Accidental or uninstructed setting of plished by the erection of separate buildings,
temperature control above safe operating limits adequately spaced, which in turn presents prob-
The precautions for safe operation of molten lems of maintenance and operation. Suppose a
salt baths are summarized as follows: major plant has an operation involving flam-
(a) Guard against the introduction of any mable liquids. Such processes as spray painting
extraneous matter or dipping use tremendous quantities of flam-
(b) Protect completely from overheating by mable solvent; extraction processes and the
automatic control and temperature readings manufacture of products of which flammable
taken at regular intervals solvents are major constituents are typical ex-
(c) Isolate the operation as far as practicable amples of processes which require subdivision.
(d) Instruct all personnel thoroughly and The flammable liquid operations and all its ap-
completely in regular and emergency procedures purtenances must be physically separated from
From the foregoing it can be clearly seen that the rest of the plant for maximum safety. Care
the handling of flammable liquids, flammable should be taken that the separate buildings are
dust or molten salt baths are the three chief no larger than production efficiency demands; in
 I 92

other words, only as much should be put under one side of the wall to the other. In all cases,
one roof as is necessary to be in one building. the doors provided should be of the type ap-
Where space or production requirements pre- proved for the opening in the wall. In many
clude separate buildings, the area in which cases, doors approved for use only on vertical
flammable liquids are handled must be physi- enclosures such as stairways are installed in fire
cally separated from the rest of the plant by walls and will not serve their intended purpose in
approved fire walls or, where these are not the event of fire. If openings are necessary in
practicable, by water-curtain type >prinklers fire walls for the passageof conveyors and no
Subdivision of one large risk into smaller fire type of door installation is practical, then the
areas may also be accomplished by means of fire openings should be specially protected by
walls which stop the spread of fire from one area hooded automatic sprinkler heads directly over
to another. To accomplish this, the wall must be the opening on each side of the wall. A fire wall
carried thro,ugh the roof and either go through should be thought of as a dam which any smaIl
the side walls for a distance of at least 36 inches leak can cause to fail
or turn back on both ends for a distance of sev- The spread of fire from floor to floor in a
eral feet to provide a barrier around which the building is prevented by the proper enclosure of
fire cannot travel vertical openings such as stairways, elevators,
Many otherwise sound fire walls have failed shafts, and process openings through the floor.
because holes were made in the walls to permit The question of stairways deserves particular
the passageof pipes, conduit, etc, and then comment because in so many cases, self-closing
never properly closed. Every hole in a fire wall stairway doors are found to be wedged open to
must be sealed at the time such work is being permit easy passagefrom floor to floor. Such
done. The weakest point in a fire wall is the fire examples of poor management entirely negate
door provided to permit access from one section the cost of closing the stairway off by providing
to another. At any given time a high percentage the doors in the first place
of such doors are found upon inspection to be One of the prima~ reasons for enclosing
useless as fire barriers: They must be test op stairways is to permit the passagewithout in-
erated regularly. The chief deficiencies are miss- jury of personnel from upper floors to the street
ing fusible links, damage to the doors by ma- level past the floor which is on fire. If the stair-
terials handling equipment, which damage way doors are wedged open this may be impos-
would prevent their operation, or blocking by sible. The stairways can immediately become
material left in the doorway so that the door choked with hot air, smoke and gasesfrom the
cannot close stairwell
Proper maintenance includes regular inspec- Provision of fusible Iink arrangements to close
tion, physical guarding to prevent damage, the such doors’ is not very satisfactory because fumes
painting of “keep clear” lines on the floor, and a and smoke will pass through without operating
constant program of education. Wherever prac- the link. In at least one laboratory the problem
ticable, such doors shouId be closed at night to of stairway doors being wedged open versus the
insure that they will be closed in the event of fire. desirability of having them closed in a hurry
Where the use or occupancy of the building has has been solved by providing for electric latches.
changed and fire doors are not needed any These latches hold all the doors open, but con-
longer, the openings should be bricked up to the nected to the fire alarm system is a relay which
same thickness as the original walls. Even a causes all the electric locks to release when a fire
pair of fire doors, one on each side of the open- alarm is sounded, thus closing the doors
ing, is less resistant to the passageof fire than A further loss-limiting device which is useful
the fire wall in which they are instrdled. In where flammable dusts and vapors are used is
normal operation, because of the aisle space the explosion vent. It is important to install
leading to the opening, the heat on the door explosion vents in areas where flammable liq-
should be less than elsewhere in the building. If uids or dusts are used because of the possibility
the doors are closed and contents are piled of great damage due to explosive ignition of such
against the doors, fire may be transmitted from mixtures and air. Therefore, on a practical basis,
 I 93

properly designed explosion vents are a suitable fire extinguishment of the metal. Thk is par-
safeguard, as they reduce the chances of de- ticularly” applicable to the use of sodium, potas-
struction indoors by allowing the force of the sium, lithium, zirconium, uranium, thorium,
explosion to be transmitted outdoors and magnesium. For instance, it has been
In order to fully relieve the pressures produced found that ordinary sand, even when dry, is a
by explosions in vapor and air mixtures, a vent very poor material for extinguishing metal fires;
area as large as 1 square foot for every 10 cubic it may react with the hot metal and add more
feet of room volume would be necessary. How- heat to an already intense fire. Often salt
ever, it is unlikely that more than a fraction of (sodium chloride), sodium bicarbonate, graph-
the total volume of a room will at any time be ite, magnesium carbonate, magnesium oxide, or
within the explosive range. Therefore for a small mixtures of all of these materials have been
room with a floor area of about 200 square feet, found effective; in every case the supplier of this
the venting area should be at least 1 square foot material will know how it must be handled.
for each 30 cubic feet of room volume. For Water should never be applied to burning
larger areas, this proportion may not be obtain- metals”
able, but in no case should the vent area be less
than 1 square foot for each 50 cubic feet of Industrial Hygiene (Industrial Health, Occupa-
volume tional Diseases, Occupational Hazards). Industrial
Approved explosion venting windows are hygiene is a branch of medical science dealing
available. Also, sky-lights, roof hatches, or with principles and rules for preservation and
light windows hinged at the top and carefully in- improvement of health of those working in
stalled to swing outward under even slight pres- industry
sure can be useful. Under some conditions, Due to the fact that most explosives are
doors equipped with releasing latches may be toxic, particular care should be taken in
utilized as vents handling them and the rules prescribed in books
Furthermore, where the conservation of heat on Industrial Hygiene should be observed. The
in a plant is important, and the walls of the War departments of each country also have
building are otherwise of strong construction, a special rules applying to war plants, arsenals
section of exterior wall may be built of light etc
wood, or hollow tile or some other material See also Health Hazards of Explosives and
which is relatively weak compared to the rest Propellants in this Vol
of the building so that in case of an explosion, Refs: 1) W. G. Thompson, Occupational Diseases,
these sections will give first Appleton, NY (1914) 2) Great Britain Minis-
It is important that snow or ice be kept from try of Munitions, Industrial Health and Efficiency,
collecting on explosion vents so that they can op- HMPO (London) (1918) 3) Courtois-Suffit et
erate freely in case of an explosion” Zedet, Hygiene industrielle. Lutte contre les
In discussing the extinguishing of fires, Sax intoxications clans fabrications des poudres et
makes the following remarks about metal fires: explosifs, Bailliere, Paris (1932) 4) International
“Fires caused by burning metals are very dif- Labor Office, Occupational and Social; Encyclo-
ficult to e~tinguish and cannot be handled in the pedia of Hygiene, Pathology and Social .Welfare,
ordinary manner. For instance, to spray water Geneva (1930-1934) 5) G. Lutz, Gewerbehy -
upon burning metal might cause an explosion giene, Wissenschaftliche, Verlags, Stuttgart (1933)
which would spatter flaming particles of metal to 6) R. Fabre, Exposes de toxicologic et hygiene
great distances. Usually the best way to attack industrielle, Hermann, Paris (1935) 7) L. B.
burning metal is with specially formulated dry Chenoweth & W. Machle, Industrial Hygiene; A
type fire-extinguishing agents. For instance, Handbook of Hygiene and Toxicology for Engi-
when one is planning to use a metal in a form in neers and Plant Managers, Crofts & Co (1938)
which it might readily become ignited, it is wise 8) J. B. Ficklen, Manual of Industrial Health
to discuss the situation with the manufacturer or Hazards, Service to Industry, West Hartford,
supplier of this metal and obtain from him ex- Corm (1940) 9) L. I. Dublin & R. J. Vane,
plicit instructions for the storage, handling, and Occupational Hazards, US Govt Printing Office,
 (,

I 94

Washington, DC (1942) 10) W. A. Cook, Metal I. R. sax “Dangerous properties of Industrial

Finishing 40, 19-23, 25 (1942) (Industrial hy- Materials” (3rd ‘Edit) Van- Nostrand, Reinhold,
giene at work in defense industries) 11) G. NY (1968)
Rodenacker, Die chemischen Gewerbekrankheiten
und ihre Behandlung, Barth, Leipzig (1942) Industrial Toxicology. See under Toxicity &
(Reproduced by Edwards Bros, Ann Arbor, Toxicology
Mich) 12) L. Schwartz, Trans National Safety
Congress 31, I, 173-8 (1942) (Occupational Inert Gases’ Explosive Compounds. Until quite
dermatoses in war industries) 13) I. R. Taber- recently, the noble gases(Xc, Kr, A, Ne, Ra &
shaw & M. Bowditch, New England JMed 229, He) were considered chemically inert and in-
1003-7 (1943) & 231, 706-10 (1944) (Indus- capable of reaction with other elements. While
trial hygiene as applied to the manufacture of this concept remains generally unchanged, at
chemicals for munitions (51 references)) 14) least a few noble gas compds can be prepd.
R. Hussey, lndHygFoundAmIncProc, 8th Ann Xe fluorides and oxyfluorides constitute the
Meeting 1943, 26-8 (The Army Industrial Hy- principle noble gas compds made to date. Scores
giene Laboratory) 15) E. Rosser, K. B. Leh- of explns have been experienced during prepn
mann & F. Flury, Toxicology & Hygiene of and use of Xe fluorides, of which perhaps the
Industrial Solvents, Williams & Wilkins, Balti- following were the most serious:
more (1943) 16) A. D. Brandt, Manual of 1) An expt was being conducted in which a
Industrial Hygiene, Saunders, Philadelphia (1943) soln contg 0.39g of XeF4 dissolved in 1.5ml
17) J. E. Weiss, Ed, Industrial Health, Occu- of w was being evapd under vac at room temp
pational Hazards, Inc, Cleveland, Ohio (1943) to yield a white solid thought to be Xe(OH)4
18) US Public Health Service, Industrial Hy- or Xe02 .2H20. While the silica container
giene & Medical Service in War Industries, (under vat) was being heated gently with warm
Saunders, Philadelphia (1943) 19) National (30–40°) air from a blower, a deton took place
Assoc of Manufactures of the USA, Health on which shattered the container and inflicted
the Production Front, NY (1944) 20) W. M. serious injuries (Ref 1)
Gafafer, Manual of Industrial Hygiene & Medi- 2) In Ott 1963, an expl occurred during heating
cal Service in War Industries, Saunders Co, of a 3“ OD, 1/8” wall, 6%” long cylindrical Ni
Philadelphia (1944) 20a) L. Schwartz, Occu- reactor contg Xe and F gases. The incident was
pational & Related Dermatoses, US Govt Print attributed to failure of a thermocouple-activated
Office, Washington, DC (1944) 21) E. F. ‘ regulator which permitted pressure buildup be-
Bellingham et al, US Public Health Service Bull yond the rating of the vessel (Ref 5)
No 289, 95pp (1945) (Bibliography of indus- 3) An expln during Nov 1963 was attributed to
trial hygiene) 22) National Safety Council, reactions of moisture which entered a liq N z
Industrial Safety and Health; A Bibliography cold trap following failure of a mechanical
(1945) 23) N. V. Hendricks, ChemMetEngrg pump over a weekend. It was presumed that the
53, No 1, 124-5, 128 (1946) (Control of occu- moisture reacted with XeF6 in the trap to form
pational hazards through industrial hygiene) 24) expl Xe03 (Ref 5)
A. D. I*;andt, Industrial Health Engineering, J. The case with which highly expl Xe03 may be
Wiley, NY (1947) 25) J. M. Dalla-Valle, The formed at room temp by reaction of Xe fluorides
Industrial Environment and Its Control, Pitman, with moisture has been strongly emphasized
NY (1948) 26) R. T. Johnstone, Occupational (Refs 2, 3 & 4). Xenon trioxide, Xe03, is a
Medicine and Industrial Hygiene, Mosby, St Louis wh sol comparable in deton sensitivity to nitro-
(1948) 27) F. A. Patty, Ed, Industrial Hygiene gen triiodide and in expl force to TNT
& Toxicology, Interscience, NY, 2 VOIS(1948- Refs: 1) N. Bartlett & P.R. Rae, Science 139,
1949), 2nd revised edition, (1958) 28) R, E. 506 (1963) 2) D.F. Smith, JACS 85, 816
Kirk & D. F. Othmer, Eds, Encyclopedia of (1963) 3) S.M. Williamson & C.W. Koch,
Chemical Technology, Interscience, NY, v 7 Science “139, 1046 (1963) 4) H.H. Hymen,
(195 1), pp 847-870; C. H. Hine & L. Lewis, Noble Gas Compounds, Univ of Chicago Press
industrial Hygiene & Toxicology (13 refs) 29) (1963) 5) Anon, FLACS (Florida Chem Sot)
XVIII, 23–4 (1964)
 I 95

Inert Simulants for High Explosives. In certain equipment, may follow a predetermined course
physical tests on weapons & explosives, eg the in space with ref primarily to the relative
effects of humidity and temp cycling on the positions of the missile and certain preselected
dimensional stability of the weapon, it is celestial bodies is called an inertial-celestial
desirable to simulate the explosive filler by an guidance system
inert filler. Many such inert simulants have been Ref A.S. Locke et al, “Guidance,” Van Nos-
proposed and tested (Refs 1, 2 & 3). Simulants trand, NY (1955), pp 583-95
for Comp B & TNT have been patented (Ref
4). The simulant for Comp B consists of a mixt Infallible Powder. One of the old duPont
of 30?0 of 1,2 hydroxystearic acid, 5% wood explosives
rosin & 6570 dead-burned gypsum. The simulant Ref Marshall, 1, p 330
for TNT is a 40/60 mixt of hydroxystearic acid
& dead-burned gypsum Infallible Propellant. A double-base proplnt
A series of mock explosives to simulate consisting of NC (13.25%N) 59.25, NC 40.00
PBX 9404, LX-04 & LX-10 has been developed & DPhA 0.75%, coated with graphite. Grains
in AEC laboratories 0.055 inch in diam & 0.007 inch thick when
The composition, density, thermal properties subjected to 65.5° Surveillance Test and 120°
& mechanical properties (elastic, viscoelastic & & 134.5° Heat tests were of satisfactory
failure behavior) of these mock explosives are stability
given in Ref 7 Refi W.H. Rinkenbach, “The Stability of Double-
Re~s:;l) A.J. Clear & O.E. Sheffield, “Inert Base Powders,” PATR 1359 (oct 1943), p 2
Simulants for High Explosives,” PATR 1618 & Table IV
(July 1946) 2) O.E. Sheffield, “Development of”
Inert Materials to Simulate Explosives:’ PATR Infantry Rocket Weapons. The title of a paper
1667 (Ott 1947) 3) I.L. Kintish & N.D. Baron, by Major Brill in Ordnance (Ref 1), where a
“Use of Perlite to Improve Calcined Gypsum/ brief description is given of the following
Water Inert Filler;’ PATR 2340 (Ott 1956) 4) weapons:
I.R. Kintish & J.E. Ranier, USP 3119705 (1964) 1) Rocket Launcher, 2.36 inch, known as
&CA 60,9094 (1964) 5) W.W, Bechtel, Bazooka, developed in 1942. It was 54” long
“Borax 5 Mol as an Inert Substitute for Pressed and weighed 12 lbs; could penetrate up to 4“
Explosives”, PA Tech Memo 1747 (NOV 1965) armor at close range. Used successfully during
6) M. Roth, “Development of a Dimensionally WWII (Ref 1, p 629) (See also Bazooka in Vol
Stable Inert Filler for Ammunition”, PATR 2, p B26)
3283 (may 1966) 7) B.M. Dobratz, “Pro- 2) Rocket Launcher, 3.5 inch, is the modern
perties of Chemical Explosives & Explosive successor of original 2.36 inch launcher. Used
Sirnulants”, UCRL-51319 (1972), pp 12-1 to successfully during Korean War
16-8 Note: Both launchers used non-guided missiles
until 1959, when US Govt adopted French, anti-
Inertial, Terrestrial and Celestial Guidance tank, wire-guided missiles SS1O & SS11. The
Systems for Missiles. An inertial guidance
sys- SS1O is no longer in the US Army inventory
tem is one which is independent of information, and SS11 has been adopted to helicopter arma-
other than gravitational effects, obtd from out- ment as the Ilf22, but for ground use it was re-
side the missile placed by the Entac Missile (Ref 1, p 630)
Missile guidance, wherein the predetermined 3) Entac/Engin T~&guid4 Anti-Char (Tele-
path set into the control system of a missile can guided Antitank Device). A French boxlike
be followed by a device in the missile which ‘ launcher using a solid-propelled, wire-guided
reacts to some property of the earth such as missile. The target is optically tracked by the” .
magnetic or gravitational effects, is known as infantryman. The missile is designed for use
terrestrial reference guidance against tanks, armored combat vehicles and some
A system wherein a missile, suitably instru- defensive installations. It is armed with a HE
ment ed and containing all necessary guidance shaped charge warhead. Total weight of the
 I 96

launcher and missile is 37.5 lbs (Ref 1) 628-30 (1966) 2) General Dynamics, Report,
4) Redeye. A 3-inch weapon developed in Ordn 50, No 276, 571 (1966)
US during the Vietnamese war & designed to
provide combat troops in the forward battle Infernal Machines (Hollenmachinen in German;
area the capability of destroying low-flying Engins Criminels in French; and Adskiy6
aircraft. The length of its tubular-type launcher Mashiny in Russian). Various devices used by
is 4 ft and the total wt of missile and launcher anarchists, revolutionaires and criminals against
is ca 28 lbs. In its nose the missile carries an kings, presidents, politicians and rich persons;
infrared sensing device which enables the also for sabotage. These devices consist of bombs,
guidance system of the missile to “home” on grenades and mines, and can be exploded either
the heat of the enemy’s aircraft engine.’ A small by instantaneous or time fuzes
charge ejects the missile from its launcher and, Refs: 1) Daniel (1902), “Engins Criminals”,
at a distance far enough to protect the soldier pp 268–83 2) Stettbacher (1933), 417
from the rocket blast, a fuse ignites ~he major (Anarchistenbomben) 3) A. Stettbacher,
rocket charge. Miniature computer circuitry Nitrozellulose 1938, 75, 100 & 138 and Schweiz-
within the missile directs a set of steering fins ChemZtg 1944, 27–37 (11 Figs) 4) Stett-
which enable the missile to change direction as bacher (1948), pp 130–32 (Sabotagezunder)
necessary and chase the target at supersonic (Sabotage Igniters) 5) Stettbacher, P61voras
speeds until it intercepts it (Refs 1 & 2) (1952), 164–66 (Bombas de Sabotage)
5) Light-Antitank Weapon (LAW), M72, also 6) W. Powell, “The Anarchist Cookbook”,
known as A472 Rocket Grenade, is the smallest Lyle Stuart Inc, NY (1971), Expls & Booby
antitank weapon because its total wt is only Traps, pp 132–51 7) K. Saxon, “The Poor
4.5 lbs and its length is 25 inches. It can be Man’s James Bond”, Atlan Formularies, Eureka,
carried and fired by one man using its dis- California (1972), Bombs, pp 31–70
posable packing container as a launcher. A
telescopic aluminum inner section is extended Inflammability or Flammability (latter is preferred
prior to firing; the outer section is made of in modern usage). The ease with which a mater-
fiberglass-plastic composition. A solid-fuel ial (gas, liquid or solid) will ignite, either
rocket motor furnishes propulsion and burns spontaneously (pyrophoric), from exposure to a
out before the rocket leaves the launcher. high-temperature environment (autoignition), or
When the missile emerges, several narrow to a spark or open flame. It also involves the
magnesium tins (folded against the motor case rate of spreading of a flame once it has started.
when packed in the tube) spring into position The more readily ignition occurs, the more
and stabilize the missile (Ref 1, p 630) flammable the material; less easily ignited
6) TOW (Tube-launched, Optically-tracked, materials are said to be combustible, but the
Wire-guided) Weapon has been developed to line of demarcation” is often indefinite, and de-
provide greater firepower than possible with pends on the state of subdivision of the
Entac. Although similar to other antitank material as well as on its chemical nature
missile systems, TOW uses somewhat different Closely related to inflammability is the gener-
guidance principles. The optically tracked al subject of inflammable or jlammable (preferred)
missile is automatically guided in flights by materials. These are defined as: any solid,
commtids transmitted by means of a 2-wire liquid, vapor or gas that will ignite easily and
link “between the gunner and the missile burn rapidly. Flammable solids are of several
(Ref 1, p 630) types: (1) dusts or fine powders (metals or
7) lkL4 W (Medium Assault Weapon). Two organic substances such as cellulose, flour, etc);
missiles have been under development during (2) those that ignite spontaneously at low tem-
the Vietnamese War–one by industry and the peratures (white phosphorus); (3) those in which
other by the Research and Development internal heat is built up by microbial or other
Directorate of the Army Missile Command (Ref degradation activity (fish meal, wet cellulosic
1, p 630) materials); (4) films, fibers, and fabrics of low-
Refs: 1) Major J. H. Brill, Ordn 50, No 276, ignitio”n point materials
 I 97

The National Fire Protection Association propagation when the mixture is dispersed into
divides organic liquids into three classes: (1) a dust cloud in the presence of a standard
those having a flash point (Tag closed cup) source of ignition. The more inflammable the
below 100”F (flammable, dangerous fire hazard); dust, the higher will be the percentage of inert
(2) those having a flash point at or above 100”F dust needed to prevent ignition. This classifi-
and below 140°F (flammable, moderate fire cation was adopted in the Bureau of Mines
hazard); (3) those having a flash point at or study o’f coal-mine dusts. The equipment used
above 140° F (combustible, slight fire hazard). in these tests was the Godbert-Green wait appa-
Thus the critical flash point temperature for a ratus and an open-spark inflammability apparatus
flammable liquid is 140”F (Tag Closed Cup). The former consists of an electrically heated
However, shipping regulatory authorities (ICC, vertical cylindrical tube (furnace), the top of
CG, IATA), as well as the Manufacturing Chem- which is connected to a small brass chamber
ists Association, use 80°F (Tag Open Cup) as containing the dust’ sample to be tested. A
the critical flash point temperature pneumatic system is used for blowing the dust
Flammable gases are ignited very easily; the downward thru the heated tube. In the usual
flame and heat propagation rate is so great as ignition test, the lowest tube temp at which a
to resemble an explosion, especially if the gas is flame appears at the lower mouth of the tube
confhed. The m’ost common flammable gases is taken as the ignition temp of the dust cloud.
are hydrogen, carbon monoxide, acetylene and In the relative inflammability test the temp of
other hydrocarbon gases. Oxygen, though essen- the furnace is held constant at 700°C (1292°F)
tial for the occurrence of combustion, is not and only” the amounts of Fuller’s earth is
itself either flammable or combustible; neither decreased until no ignitions are observed
are the halogen gases, sulfur dioxide or nitro- In the open-spark apparatus, a high voltage
gen. Flammable gases are extremely dangerous continuous spark having an average power of
fire hazards, and require precisely regulated 20 to 24 watts is passed through a spark gap
storage conditions between tungsten electrodes in a pyrex tube,
Note: The terms “flammable,” “nonflammable,” and the cloud of powder or dust being tested
and “combustible” are difficult to delimit. is blown thru the tube. The relative inflamma-
Since any material that will burn at any tem- bility is determined as in the furnace test by
perature is combustible by definition, it follows finding the minimum amount of Fuller’s earth
that this word covers all such materials, irre- needed in a mixture with the inflammable
spective of their ease of ignition. Thus the dust being tested to prevent ignition of the
term “flammable” actually applies to a special mixture by the spark
group of combustible materials that ignite easily Refl 1. Hartmann & J. Nagy, USB of M,
and burn rapidly. Some materials (usually gases) RI 3751 (1944)
classified in shipping and safety regulations as
nonflammable are actually noncombustible. The Inflammability of Explosives Tests (Flammability
distinction between these terms should not be Tests). See also Index of Inflammability in Vol
overlooked. For example, sodium chloride, car- 1, p XVII. These tests are designed to ascertain
bon tetrachloride and carbon dioxide are non- the behavior of explosives towards open flame.
combustible; sugar, cellulose and ammonia are The following tests are described by Reilly (Ref
nonflammable 1):
Refi CondChemDict, 8th Edit, (1971), pp 391-2 Test No 1:, Same test as Fuse Test described
under Ignition Sensitiveness
Inflammability (Relative) of Dust Clouds. See Test No 2: A smrdl sample of explosive is
also Dust Explosions in Vol 5, p D1 578-R and placed on an asbestos board and a small flame
Ignition Temperature Tests in this Vol. Relative of a Bunsen burner is directed against it for 10
Inflammability of a dust is defined as the per- seconds. It is considered noninflammable if it
centage by weight of an inert dust, such as does not ignite in this period. Control samples
Fuller’s earth, required in a mixture with the of known explosives should be included for
inflammable dust to prevent ignition and flame comparison
 I 98

Test No 3: If the explosive withstands the Influence Tests. See Detonation of Influence
Fuse Test, it is subjected to the Red Hot Iron or Sympathetic Detonation Tests Vol 1 p X
in
Test described under Ignition Sensitiveness” Tests with additional information given below:
Test No 4: Wood Fire Test: In some cases, These tests are designed to measure the
larger quantities, ie a pound or two, are burned distance (usually in air) over which detonation
in a wood fire to ascertain the degree of danger may be conveyed from one explosive (donor)
the explosive may offer in case of fire. The to another (acceptor)
observations should be made under precautions In blasting operations it is important that an
at a safe distance. (Compare with “Iron Box explosive be capable of transmitting detonation
Test,” described under Ignition Sensitiveness) across an inert gap which interrupts the conti-
Test No 5: Ignition Time Test: A small nuity of the explosive charge. The inert gap can
quantity of the explosive is fastened to the end be created in practice by air gaps, dirt or wads
of a pendulum which swings through a flame of paper getting between cartridge (sticks) of an
in such a manner that the time required to ig- explosive charge
nite the sample can be measured. (For details, It is important that transmission shall not be
see under Ignition “Time of, Test] too poor, because this involves the danger that,
Andrew & Kostin (Ref 2) describe an inflam- if for any reason different cartridges are sepa~
mability (or ignition) test for explosives in which rated from one another by too great a distance,
a “donor” explosive is used to ignite an “ac- the entire charge might not be detonated. Some
ceptor” explosive placed below the donor in a explosives transmit so poorly when frozen that
1cm diam vertical glass tube. As the density of detonation is incomplete even when there is no
the donor is decreased its igniting ability also break in the continuity of the charge. Total or
decreases partial failure to detonate is a frequent cause
Refs: 1) Reilly (1936), p 66 2) K.K. Andrew of accidents, as the explosive is apt to go off
& I.D. Kostin, CR Acad Sci (Russ) 54, 231 in subsequent handling of the material being
(1947) & CA 41>5307 (1947) blasted. Accidents also occur in subsequent
drilling of bore holes near unexploded charges
Inflammability or Flammability (preferred) According to Marshall (Ref 1), a simple
Limits. Gaseous fuels mixed with gaseous oxi- method of determining the distance of trans-
dants (usually air or oxygen) will ignite only mission, is to set out a row of small cartridges
within certain composition ranges. The max at increasing distances apart and to determine
fuel-rich composition capable of ignition is how many of them explode when the end
known as the upper ji’amiability limit and the cartridge is detonated
min fuel-poor composition is known as the The distance at which the explosion is trans-
lower flammability limit. These vary widely with mitted from donor to acceptor cartridge depends
fuels and oxidants and are discussed under the not only on the nature of the explosive itself
individual gaseous fuels or vapors, eg see acety- (its sensitivity, brisance, power, velocity of
lene gas in Vol 1, p A59-L, or acetone vapor detonation etc) but also on the following factors
in Vol 1, p A34-L. General references on this (yrovided both cartridges are from the same
subject include: material and are of equal size):
Refs: 1) H.F. Coward, “Limits of Inflammability 1) Density of the explosive
of Gases and Vapors;’ B of M Bull 279 (Re- 2) Kind of medium through which the ex-
vised 1939) 2) L. Doll< “Inflammability plosion is transmitted
Limits of Vapors from Solids,” Magasin CTO; Transmission of detonation is different for
Paris (1953) & CA 48,13222 (1954) 3) G. air gaps and dirt gaps. Transmission distances
Dixon-Lewis & G.L. Isles, Seventh Symposium are much greater in v wet soil than in dry
(Intl) on Combustion (1960) 4) B. Lewis & soil. In the open, distances (across air gaps) are
G. Von Elbe, “.Combustion, Flames & Explo- shorter than in bore holes. In the open, the
sions of Gases,” AcadPres, NY (1961) medium on which the cartridges are laid also
 I 99

influence transmission distance: shortest gaps by shock, is given by:

on porous media (loose soil) ‘& longest gaps on S; = kM
dense media (steel) where k is a different constant for each explo-
3) Gaps increase as the cartridge diameter sive, and will depend on the density and
increases physical state of the explosive; M is the weight
Test Methods of explosive
The gap test or halved cartridge test is This equation will apply, on the other hand,
described in Vol 1, pp XIV & XV. Examples only if one uses a primer of fixed L/d (length/
of the gap sensitivity (inches of air across diam), and k will be a maximum for any explo-
which detonation is transmitted from donor sive of fixed composition, density, and granu-
to acceptor) are given below for US dynamites lation for L/d - 1.0. Also this relationship may
(Ref6). Also see Vol 5, PPD1591 &D1737 be readily upset if there is a chance for the
(Table 5) explosive to hurl solid fragments, because flying
36 inches–for 60% ammonium gelatin con- particles can set off an explosive over far greater
taining NC 26.0, NC 0.4, N~ N03 32.5, NaN03 distances via hot-spot mechanisms than the blast
29.5, wood flour 2.0, starch 2.7, ivory-nut meal wave itself. In addition, k will depend upon how
3.9, sulfur 2.0, lime 1.0. Vel of Deton 4900 one expresses sensitiveness results. For example,
m/see; wt strength 67% the maximum distance for consistent detonations
26 inches–for ammonium gelatin containing (100 per cent D, O per cent F) is usually
NC 26.0, NC 0.4, N~N03 57.2, red dog 4.0, roughly about one-half the minimum distance
clear flour 3.0, ivory-nut meal 4.4, starch 3.0,’ for consistent failures (O per cent D, 100 per
sulfur 2.0, lime 1.0. Vel of Deton 4800 m/see; cent F). It is usually best to adopt the 50 per
wt strength 61 fZO cent F point as the reference point for defining
20 inches–for a dynamite containing NC k, because this point can be most accurately
9.0, NH4 N03 42.0, NaN03 26.8, ivory-nut meal established. That is, the per cent detonation
13.7, fine buckwheat hulls 5.0, sulfur 3.0, lime versus gap distance curve is in general an S-
0.5. Vel of Deton 2700 m/see shaped or probability curve
15 inches-for 20% ammonia dynamite con- Refs: 1) Marshall,2, (1917), 430; 3, p 128 2)
taining NC 8.5, NHQN03 16, NaN03 55.0, Barnett, p 212 3) C.E. Munroe & J.E. Tiffany,
sulfur 6.5, fine buckwheat hulls 6.0, ivory-nut Physical Testing of Explosives, USB of M, Bull
meal 7.0, lime 1.0. Vel of Deton 2500 m/see; 346, Washington (193 1), pp 59-60 4) A. Ptfrez
wt strength 20.2?I0 Ara, pp 112-13 5) C.E. Bichel, Testing of
10 inches–for dynamite containing NG 9.0, Explosives, London (1905), pp 49-50 6) LA.
N~ N03 75.0, NaN03 3.2, straw 12.3, lime Grageroff, Private Communication 7) Cook
0.5. Vel of Deton 2700 m/see; wt strength 67% (1958), p 196 8) AMCP 706-177, (1971), p
8 inches–for a permissible dynamite con- 123 9) Ibid, p 126
taining NG 10.0, N~ N03 9.0, salt 2.5, oat
straw 12.0, lime 0.5. Vel of Deton 2600 m/see Modified Injluence (tiopagation) Test. Gawthrop
4 inches–for a dynamite containing NG 10.5, (Ref 1) and others used a modified gap test to
N~N03 73.0, NaN03 4.0, wood pulp 9.0, determine the relative ability of a shielded donor
balsawood 3.0, lime 0.5. Vel of Deton 2200 charge to transfer detonation over an air gap to
m/see; wt strength 63% an acceptor charge. Clark (Ref 2) also used this
2?4 inches–for Pic Ars Low Velocity Dyna- method for the determination of the gap in the
mite (Ref 8) transmission of detonation from a small charge
1 inch–for Hercules Medium Velocity Dyna- (0.5 to 2g) of HE to a cartridge of 40% straight
mite (Ref 9) ,dynamite
From the above it is clear that gap sensitivity For these tests, Clark placed a small charge
depends strongly on the NG content of the of HE in a No 8 detonator shell and pressed
dynamite it under a reinforcing capsule at 3400 psi. The
Cook (Ref 7) suggests that Sc, the air gap detonator was placed centrally in a cylindrical
over which detonation will be transmitted solely oaken shield, with its long axis parallel to and
 I 100

coinciding with the long axis of the shield and Refs: 1) D.B. Gawthrop, JFrankInst, 214, No 6,
with its base flush with the end of the shield. p 647 (1932) 2) LeRoy V. Clark, IEC 25, 668
The shield containing the detonator and the (1933) 3) Ibid, p 1388
cartridge of acceptor explosive (40% dynamite),
with the cut end facing the detonator, were Infared Guidance Systems. See German section
then wrapped in three layers of heavy paper under Guidance Systems for Missiles in Vol 6
The maximum gap through which detonation
would be transferred with certainty was deter- Infrared Spectroscopy, Application to Explosives
mined in four trials & Propellants. The infrared region is that portion
Modified Gap Test results are given in the of the electromagnetic spectrum which is located
following tabulation (which shows that DDNP between “visible light and the microwave radio re-
is an efficient donor): gion. It “is conveniently divided into near infra-
red, which extends from the edge of visible light
Modified Gap Tests
(0.0008mm, 0.8~ or 8000 angstroms) to about
Detonator Base Charge Wt of Max Air Gap 0.025mm (25mB or 250,000 angstroms) and the
Base over which far infrared, which extends from the near infra-
Charge Detonation
red to about 1mm (1000~ or 10 million
(8) Of 40Y0
angstroms). The ~egion up to about 0.002mm
Straight
(2m# or 20,000 A) of the near infrared is
Dynamite
called photographic or photoelectric because
Oc~j; (cm)
DDNP 0.50 radiation in this region is readily detected
MF 0.50 150 photographically or photoelectrically
MF 1.00 300 Infrared (IR) radiation can be dispersed into
Tetryl primed with LA 0.66 400 a spectrum by means of coarse diffraction grat-
PA primed with MF 1.25 300 ings or prisms of special material, such as rock
MF-KC1O, (80:20) 2.12 90 salt, which is transparent to much longer waves
MF-KC1O, (80:20) 1.05 100 than glass, after which the rays can be detected
Lead styphnate, 1.74 50 with a device which is sensitive to small heating
Nitromannite– effects such as bolometers, thermocouples and
Mercury fulminate 1.16 90 various other radiometers
The infrared spectrum (especially the near-
Results are strongly influenced by the tube infrared) has assumed great importance in chem-
in which tests are conducted. The following ical and biological research because of the
tabulation (Ref 3) shows that tests in iron tubes highly specific absorption of chemicrd com-
result in much longer gaps than tests in paper pounds at these wavelengths. The infrared ab-
tubes: Gap, in meters sorption of a given organic compound may be
through used to characterize that particular compound.
Weight of Paper Iron The infrared spectrum of a mixture of several
Explosive Charge (g) Tube Pipe compounds among which there is no interaction,
Pentryl* 0.50 4.00 16.5 does not lie. between the spectra of the individual _
DDNP 0.50 3.50 – compounds, but consists of a direct superposition
0.50 1.50 - of the spectra of the individual compounds
MF
MF 1.00 3.00 – A general reference on IR spectroscopy is
Tetryl primed with MF 1.34 2.50 12.5 Ref 7
4.00 – Application of infrared (IR) spectroscopy to
Tetryl primed with LA 0.66
1.25 3.00 12.5 the study of explosives & propellants can be
PA primed with MF
MF/KCIO, (80:20) 2.12 0.90 3.5 divided into three general areas:
1.05 1.00 – 1) Identification and quantitative estimation
MF/KC103 (80:20)
1.74 0.50 3.5 of unreacted explosives, propellants & inert in-
Lead Styphnate
gredients in expl & proplnt compositions
Nitromannite–
12.5 ‘2) Study of the composition of combustion
Mercuric fulminate 1.16 0.90
or explosion products. With rapid scan spectro-
*Primed with O.20g of MF (reinforced)
 I 101

meters such studies can provide kinetic data Examples of studies belonging to area 2)
3) Study of the intermediates or equilibrium are: e
composition in the preparation of explosives Studies by Crawford & Rotenberg (Ref 4)
Most of the published work belongs in area who used a rapid-scan spectrometer in conjunc-
1). Particularly pertinent are the studies of tion with a strand burning apparatus to examine
Pristera et al (Refs 2& 12) on IR spectra of NC-NC “low” temperature decomposition and
explosives & the identification of the ingredients flames. During the decomposition of commer-
of a complex propellant (Ref 2). In Ref 12, cial double-base propellants, the gas products
Pristera gives the IR spectra of EDNA, MEDINA, were: NO, Nz O, C02 & CO. When these pro-
a; (1 & ~ HMX, Tetryl, BTTN, NC, DEGN, Man- pellants were burned under 100-150 psi nitro-
itol Hexanitrate, Met~iol Trinitrate, NG, PETN, gen pressure at a linear velocity of -100 cm/see,
TEGN, 1,5-Dinitronaphthalene, l,8-Dinitronaph- C02 & CO absorption bands appeared even at
thalerze, 1,3,8-Trinitronaphthalene, 2,4-D NT, TNT, 2 cm away from the burning surface. Nitric
AN, Ammonium Picrate & 1,3,6,8-Tetranitrocar- oxide was barely detectable and Nz O was com-
bazole. Further information on other explosives, pletely absent
explosive mixtures and the inert ingredients in Leclercq gives some IR spectra for residues
these mixtures is contained in Ref 1 of explosive that had been burned (Ref 8)
The following tabulation (from Leclercq in Zirkind reviews investigations of radiation
Ref 8) shows the symetric & antisymetric stretch emission of rocket exhausts since 1940 (Ref 11).
frequencies of the N-O bond in various compounds: Emission characteristics of the exhaust plume
are strongly dependent on rocket engine para-
Compound Sym freq Antisym freq
meters & the propellant system. If these &
(cm-’) (cm-’)
motor operating conditions are stipulated, machine
RN02 1500-1550 1320-1360
computations can give exhaust composition &
RNNOZ 1550-1600 ‘ 1200-1260
sometimes temperatures
RON02 1600-1660 1250-1300
Examples of studies pertaining to area 3)
Metal N03 one band only at 1350-1400 cm-l
are:
IR spectra of nitroaliphatic compounds are Simecek’s study of the preparation of the
reviewed by Slovetskii (Ref 13). This review con- lower nitrates of PETN and measurement of
tains 237 references thru 1969 their IR spectra (Ref 6)
In the absence of conjugation N3 absorption Leclercq’s study of the nitration of amyl
bands of organic azides occur in the 2100-2110 alcohol and cellulose by following the amount
cm-l region (Ref 9). Conjugation or presence of of OH remaining after nitration by IR absorp-
electron acceptor groups shift the bands to 2135- tion methods (Ref 5)
2166 cm- 1. It is claimed that for organic azide Refs: 1) F. Pristera, Appl Spectroscopy 7 (3),
measurement of band intensity is a more sensitive 115 (1953) & CA 48, 1683 (1954) 2) F. Pris-
indication of compound structure than measure- tera, Anal Chem 25, 844 (1953) 3) A.H.
ment of band position. Electron donor groups in Castelli et al, PATR 2021 (1954) 4) B.L. Craw-
the molecule increase band intensity and electron ford & D.L. Rotenberg, IEC 48, 759 (1956) &
acceptors lower it CA 50, 9875 (1956) 5) M. Leclercq, MP 43,
IR spectra of inorganiz azides are given in a 369 (1961) & CA 57, 6766 (1962) 6) J.
review by Yoffe (Ref 10) Simecek, Collection Czech Chem Comnumic
IR and Raman spectra of NF compounds are 27, 362 (1962) & CA 57, 647 (1963) 7) H.A.
reviewed by Moskvitina & Kuzyakov (Ref 14). Szymanski, “IR: Theory & Practice of Infrared
Their review contains 47 references Spectroscopy,: Plenum Press, NY (1964) 8)
Pristera has developed an IR method for M. Leclercq, MP 45, 207 (1963) & CA 63,
determining a, 0 & -y TNT as well as 2,4-DNT 2838 (1965) 9) Yu. N. Sheinker & L.B. Sen-
in mixtures such as found in exudates (Ref 1) yavina, Izv~adNauk, SSSR, Ser Khim 1964
Castelli et al (Ref 3) worked out a rapid IR (1 1), 2113 & CA 62, 9942 10) A.D. Yoffe,
method for determining NC, TA & 2-Nitro- Develop Inorg Nitrogen Chem 1, 72 (1966) &
diphenylamine in Casting Solvent CA 66, 34318 (1967) 11) R. Zirkind, 1 lth
 \

I 102

Sympos of Combust 613 (1966) & CA 68, which are sometimes charged with an inert re-
41732 (1968) 12) F. Pristera, Encycl of Ind fractory filler (chalk powder) and burn very
Chem Analysis 12 (1971), pp 453-60 13) V.I. slowly if at all. Sheets of cellulose acetate or
Slovetskii, UspKhim 40 (4), 740 (1971) & CA ethyl cellulose, 2 to 4mm thick, have been
75, 12493 (1971) 14) E.N. Moskvitina & widely used for that purpose but cellulose ace-
Yu.Ya. Kuzyakov, Kolebatel’nye Spektry Neorg tate is not very satisfactory with double-base
Khim 1971, 101 & CA 75, 55519 (1971) propellants because of the exudation of nitro-
glycerine during storage. With composite pro-
Influence Test. See Gap Test in Vol 1, p XIV pellants the fuel, with an inert filler substituted
for the oxidizer, is also often used. Restrictors
Infusorial Earth. See Kieselguhr in this Vol can be applied by dipping the grain or by
spraying the inhibiting material on. These two
Ingelite. See Antigel de Sflretsf in Vol 1, p methods are not very satisfactory because each
A466-R coat must be very thin to dry well and a
prohibitively large number of applications are
Ingold, C. K. (1893-1970). English physico- required to build up the desired thickness.
organic chemist whose pioneering research helped Preferably inhibitor sheets are bonded to the
to lay the basis of modern organic chemistry. grain, possibly under pressure at fairly high
His work on nitration reactions did much to temperature, with a suitable glue like poly-
elucidate the mechanism of these reactions, urethane, or a restricting tape is wrapped
particularly the nitration of aromatic compounds. around the grain
He became a fellow of the Royal Society in The mechanical and physical properties of
1924 & was knighted in 1958. He was the re- the inhibiting material must be fairly similar
cipient of many scientific honors & medals to those of the propellant in order to minimize
Refs: 1) “World Who’s Who in Science;’ (A G. the differential expansion. In this respect the
Debus, Ed), Marquis, Chicago (1968) 2) C & use of several layers with possibly different
EN 49 (3), 41 (1971) & CA 74, 106995 (1971) compositions is favorable. With long burning
timers (more than 20 see) the development of
Inhabited Building. In the American Table of a reliable inhibitor poses a fairly difficult
Distances for Storage of Explosives, an “Inhab- problem, especially with end-burning grains
ited Building” is defined as: “A building regu- The situation is greatly improved in this respect
larly occupied in whole or in part as a when the inhibitor is” not in contact with the
habitation for human beings, or any church, hot gases. This is the case with case-bonded
schoolhouse, railroad station, store or other grains where the thin chamber liner acts as
structure where people are accustomed to restrictor (Ref 2)
assemble, except any building or structure Inhibiting by Denigration. This consists of
occupied in connection with the manufacture, the removal of the nitrate. groups from the
transportation, storage, or, use of explosives” surface of the propellant grain by treating it
Refi American Table of Distances for Storage with ammonium hydrogen sulfide and ammo-
of Explosives as Revised &“ Approved by the nium polysulfide. Previous to this treatment,
Institute of Makers of Explosives, Sept 30, 1955 however, the surface of the grain is swelled
by a one minute dip in acetone (contg 5%
Inhibiting of Solid Propellant Grains. To pre- by wt of AcOH), followed by one hour
vent surface burrring and/or contact of the drying
propellant grain with its container, various The denigration solution is prepd by dissolv-
methods of deactivating and/or coating of the ing 8 parts by wt of ammonium hydrogen sul-
grain surface are used. This is called “lnhibiting” fide in 92 parts of alcohol (30% soln by volume).
the grain This a~ueous solution is circulated over the
inhibitors or restrictors are applied to those grains for about 2 hours during which time the
surfaces of the grain where burning is to be soln is kept up to strength by adding Hz S,
prevented. They consist of plastic materials gas. The grains are then removed from the
 I 103

denigrating bath and, after rinsing them quickly employed to coat the grain with inhibitor.
with water, placed in a dilute glycerin soln at Viscous gel lacquers were used in this process
40° for two hours. Finally the grains are dried with viscosities of 8,000-10,000 centipoises
by wiping and then stored. This method gives at the dipping temperature. The solvents were
grains with denigrated layers as thick as 0.0 18“. adjusted so that there was a sharp increase in
These layers do not burn during firing but are viscosity as the temp was lowered towards
left as a residue. Various kinds of grains were room temp. As the dipped grain is ‘tithdrawn
treated by this method, including Mk31 grains from the warm lacquer the coating sets due
and triangular catapult grains. The, powders to solvent evaporation and gelation caused
prepd by this method proved to be fairly non- by the temp drop. In this way running and
hygroscopic and stable in storage sagging are minimized and a substantial coating
can be applied with a single dip. lf a very thick
Spiral Wrapping bocess consists of wrapping
coat (such as O.10“) is required, 3 to 4 dips
around large cylindrical grains of powder (such
are necessary
as Mk31 ) a thin tape of inert, non-explosive
Most of the grains are 15 to 18” in length
material (such as cellulose acetate, ethyl cellulose)
and the major diameters range from 0.8” for
in order to create a protective, non-combustible
small experimental catapults to 3-3%” for Field
layer. Wrapping is done on machines which
Installations. Inhibitor thicknesses are between
resemble a shop lathe. Usually 6 layers of tape
50 and 100 roils
are applied to make a layer about 0.045 inches
thick Gel lacquer formuhztions used for dip coating.
The early catapult propellants were inhibited by
Inhibiting of Cast Double-Base Grains. A
good inhibitor should bond to the grain with dipping in a lacquer consisting of toluene 80P,
a strength equal to, the grain strength itself. acetone 20p and a total solids “content of 15-
It should also have about the same coefficient 187.. The grains were dipped twice and had a
of expansion as the grain material cured inhibitor thickness of 20 to 30 roils. As
the size of experimental slotted tube catapults
Alleghany Ballistic Laboratory found that
increased, coatings of 100 roils were required.
casting grains in convolute-wound or extruded
beakers is quite satisfactory. In the spiral This necessitated an increase of the solid con-
‘tent to 25-27%. As ‘this soln was too viscous
wrapping process they had to use solvent-type
adhesive:, but would prefer to use a non- some methylol was incorporated in solvent
formulation. In order to improve the room
solvent type
temp gelling characteristics an aliphatic hydro-
When using large grains with internal per-
forations, the problem of NG migration is carbon was added
not of great importance, because the outer With this system there is no serious curing
problem for coatings under 50 roils thick, but
inhibited cylindrical surface forms only a small
for coatings of the order of 100 roils, about
percent of the total operating surface. After
three weeks are required to remove the vola-
up to two years in storage at 120°F, booster
tile solvents
grains were still in good condition
Castable Cellulose Acetate Inhibitors for Rocket
I%opellants. During the joint development of the
Inhibiting of Double-Base Catapult Propellants propellant for the T34 Jato by PA & Hercules,
with Ethyl Cellosolve Gel Lacquers. Propellants it became desirable to investigate methods of
for slotted tube catapults are designed to pro- restricting the ends of the powder grains. Since
duce a const press system in the catapult it was difficult to obtain uniformly good
tube. Catapult propellants, usually have non- bonding and satisfactory inhibiting by cementing
circular cross-sections and are completely cellulose acetate sheets to the ends of large
externally inhibited prop grains, the possibility of using some form
An ideal inhibitor is one which burns of inert powder for this purpose was investi-
through at the same time that the powder gated. The inert casting powder adopted con-
web is exhausted so. that no residue remains sisted of 90$Z0cellulose acetate and 10%
in the catapult. A dipping process was dimethyl phthalate in 0.30” x 0.030” granulation
 ‘i

I 104

A layer of this inert powder was placed in Prop Meet),, but this method proved to be not
an extruded cellulose acetate tube, partly filled very satisfactory on account of the appreciable
with OGK casting powder (NC of 12% 88, 2- migration of NG into the inhibitor, which re-
nit rodiphenylamine 2,dioct ylphthalate 5 and sulted in its deterioration at elevated temp.
lead stearate 5%) and was then covered over Migration occurs also when using cellulose acetate
with more OGK powder inhibitors
OGK casting solvent (72% NG ,27% triacetin An attempt to prevent migration of NC by in-
and 1Y. nitrodiphenylamine) was then fed serting a layer of cellophane after the first
through the entire” mass, following which the cellulose acetate wrap proved to be unsuccessful
assembly was cured at 140° F. After curing the because of the poor bond between cellulose acetate
charge was sectioned and examined. The granules and cellophane
of inert powder had gelled and hardened, forming Refs:l ) 7th JANAF Meeting, April 16-18 (1951)
a well consolidated mass which was very well. 2] M. Barr?%e~A. Jaumotte, B.F. de Veubeke &
bonded to, and almost undistinguishable from, J. Vandenkerckhove, “Rocket Propulsion”,
both the OGK. powder and the extruded tube Elsevier Publg Co, Amsterdam., Netherlands (1960)
A solid casting was prepd consisting of inert
casting powder and OGK casting solvent. The Inhibitors. Substances which slow down or stop
chemical analysis of the cured charge gave NG a chemical reaction. For instance, some substances
28.0, 2-NDPhA 0.4, cellulose acetate 55.1, act as corrosion inhibitors, others are added to
DMePh 6.1, Triacetin 10.4%. The heat of com- explosives to prevent their decomposition in
bustion was 3790 cal/g. The heat of explosion storage (see below)
was 260 cal/g ,,
Strands of this material would not burn in Inhibitors in Explosives. Substances added to
the inert atmosphere of the Crawford type bomb, explosives in order to take up the nitrogen
but they burned in air at 70°F. at the rate of oxides fo~med during storage or to neutralize
0.023” per second. This compared with a burn- residual acids or acids formed during storage.
ing rate for H9 propellant of 0.097’’/sec at The presence ‘of N02 “and other nitrogen
1 atrn and 0.36”/sec, at 1000 psi & 70”F oxides and/or acids in explosives (especially
This cast cellulose acetate material has been in smokeless “powders and dynamites)is very
employed for end restricting 8%.” and 20” undesirable because they act as catalyzers
diameter perforated cast OGK grains and and promote further, more rapid decompo-
thermally cycled JATO motors at -65, +70, sition. Most of the stabilizers used in smoke-
+165”F. NO cracks or separations of the less powder, such as diphenylamine, centralizes,
cast acetate restrictions were observed but urethanes etc are really inhibitors because
some softening and deformation was noted. they react with NOZ and other nitrogen
after conditioning at + 165° F. These rounds oxides to form nitroso- and nitrocompounds.
functioned satisfactorily when fired at either Acid neutralizers such as chalk are added to
-65 or +165°F dynamites
Inhibiting Double Base Rocket Ropellants at
Picatinny Arsenal. Most of the work at Pica- Inhibitor Strips for Smokeless Powders. In
tinny Arsn in connection with inhibiting of order to control the burning area of large
solventless extruded or cast double-base pro- grain smokeless powders and to prevent the
pellant has been with convolute wrappings grains from coming into contact with the
of grains or tubes with cellulose acetate. There rocket motor walls, inhibitor strips (consisting
has been a trend toward use of extruded tubes of ethylcellulose (or cellulose acetate) 74,
made by the casting process dibut yl phthalate 4, diethyl phthalate 16 and
When convolute wrapping of the long grain dimethyl phthrdate 6%) are pre-glued to the
for the T200 Rocket (4.5” diam and 72” surface of grains. This is done by means of
long) proved unsuccessful, a procedure was adhesives consisting of solns of NC in ethyl
investigated for inhibiting with Thiocol compo- acetate, Cellosolve, mesityl oxide, Bu acetate
sition developed at PA (see 6th JANAF Sol etc, which act as’ a mutual plasticizer for the
 I 105
..
powder and the material of the inhibitor ous to handle and too unstable in storage. The
strip most frequently used initiating substances are:
Ref A.M. Ball, USP 2643611 (1953) & CA Lead Azide, Mercuric Fulminate with or without
47, 9016 (1953) Potassium Chlorate, Lead Styphnate, Cyanuric
Triazide, Tetracene and Diazodinitrophenol
Initial Velocity. Same as Muzzle Velocity–see The following substances are also good
under Ballisn”c Tests and Ballistics in Vol 1, initiating agents but have not found much use:
p B5-R & B7-L & additional French refs: Silver Azide, Cadmium Azide, Cupric Azide,
1) R. Rousselet et al, MAF 22, 171-190 Triazidotrinitrobenzene, Chloratotrimercuraldehyde,
(1948), Measurement of initial velocities of Nitrogen Sulfide & Hexamethylenetriperoxidediamine
projectiles at the battlefield Until WWI, Mercuric Fulminate was the prin-
2) R. Rousselet, MAF 22, 649-655 (1948), ciple initiating agent used, but Lead Azide has
Use of a fluxmeter by Grassot for measuring now replaced it. Lead azide is not the most power-
initial velocities of projectiles at the testing ful azide, but is more stable and less dangerous to
range handle than some of the other ones. Cadmium
3) M.C. Thatcher, MAF 23, 305-308 (1949), Azide, for example, is more powerful than Lead
Measurements of the initial velocities of pro- Azide but is unsuitable as an initiating agent
jectiles (Translated from the English) because it is difficult to prepare and is soluble
Pepin Lehalleur, p 110, gives initial velocities in water
for some French and foreign propellants Marshall (Ref 13, p 158) gives the effec-
tiveness of various azides and fulminates as
Initiating Devices. See Detonators, Igniters, initiators. No 1 is the most effective and No 11
Primers, and Other Initiating Devices used for is the least effective:
Nonmilitary and Milita~ firposes in Vol 4, 1) Cd Azide, 2) Cd Fulminate 3) Ag Azide
pp D733-D928 4) Ag Fulminate 5) Lead Azide 6) Cuprous
Azide 7) Cuprous Fulminate 8) Mercurous Azide
Initiating Explosives. (Initial Detonating Agents; 9) Mercuric Fulminate 10) Tellurium Azide 11)
Primary Explosives) (Ziindsprengstoffe in Ger) Tellurium Fulminate
Sometimes erroneously called Priming Com- For the preparation and properties of initi-
pounds, are substances used in small quantities, ating agents, look under the individual
which on being subjected to the action of compounds
flame (produced by primers or other means), Refs: 1) Commission des Substances Explosives,
heat, impact, friction or an electric spark, MP 12, 134–55 (1903–04) 1a) L. Wohler &
generate a detonation wave. The detonation of O. Matter, SS 2, 181, 203, 244& 265 (1907)
the primary explosive initiates detonation in a 2) L. Wohler & F. Martin, SS 12, 242–43 (1914)
larger quantity of explosive (“main” charge or 3) A. Stettbacher, SS 12, 341, 355, 381 & 391
“base” charge) which usually possesseshigher (1914) 4) R. Escales & A. Stettbacher,
brisance, power and velocity of detonation than “Initial Explosivstoffe”, Leipzig (1917)
the initiating explosive 5) Marshall 2(1917), 506–13 6) C.A. Taylor
The main requirements for initiating explo- & W.H. Rinkenbach, JFrankInst 196, 551 (1923)
sives are: 1) sufficient sensitivity to heat, 7) C.A. Taylor & W.H. Rinkenbach, Army
flame or impact etc that they can be readily Ordnance 5,463 (1924) 8) L. W6hler, SS
detonated, but not so sensitive as to make them 20, 145 & 165 (1925); SS 21, 1, 35, 55, 97 &
unsafe to handle and transport; 2) sufficient 121 (1926) 9) L. W6hler et al, SS 22, 95
stability at elevated temperatures that they & 135 (1928) 10) B. Cserneczky, SS 23,
will not decompose while stored in ammunition, 169 (1929) 11) A. Stettbacher, SS 23,
thus rendering it unusable. Brisance, power and 383–88 (1929) 12) A. Heinemann, Nitro-
velocity of detonation are of secondary imporx cellulose 1, 196 (1930) (A review of initiating
tance in these explosives expls) 13) Marshall 3 (1932), 158–62
There are many explosives which could serve 14) Stettbacher (1933), 324 15) R. Wallbaum,
as initiating agents if they were not too danger- SS 34, 126, 161 & 197 (1939) & CA 33, 7569
 I 106

(1939) 16) H. Muraour, MAF 18, 895 be a “sensitive” explosive. Thus the ease of
(1939) & CA-34, 4905 (1940) 17) Davi~ initiation is closely connected with explosive
(1943), 400–58(under Primers) 18) L.V.R. sensitivity, but it must be emphasized that
Clark, USP 2326008 & 2325742 (1943) & CA “explosive sensitivity” depends not only on
36, 488–90 (1944) 19) R. Schmitt, SS 38, ease of initiation but also on the ease of
133 (1943) & CA 38, 2822 (1944) 20) K.K. growth and propagation of whatever process
Andreev, DRAcadSci(Russia) 44, 18 (1 944) was “initiated.” It is entirely possible that
& CA 39, 813 (1945) 21) P6rez Ara (1945), highly localized regions of an explosive are
557 & 647 22) C. Francais, FrPat 856366 “initiated” but the processes in these regions
(1946) &CA 4? 2774 (1948) 23) Stett- die out without propagating
bacher (1948), 95 24) Bowden & Yoffe Because initiation is such a fundamental
(1952) 25) Bowden & Yoffe (1958) part of explosion and detonation phenomena
26) Baum, Stanyukovitch & Shekhter (1959) various aspects of initiation have already been
27) W.H. Rinkenbach in Kirk & Othmer, Vol described in previous volumes and in this
8 (1965), 583–93 (Initial Detonating Agents) volume of the Encyclopedia. Particularly per-
28) B.A. Bydal, “Percussion Primer Mixes”, tinent are the articles on Dej7agration, Vol 3,
Ordnance, Vol LVI, No 309, 230–33 (Nov– pp D38-40; Detonation (and Explosion), Initi-
Dec 1971) (A review of the history of initiating ation and Propagation, Vol 4, pp D402-4 19;
explosives from their discovery early in the seven- Hot Spots & Ignition in this Vol
teenth century up to the development of today’s In what follows we will give brief definitions
safer noncorrosive, nonmercuric mixes) or descriptions (whenever necessary) of various
29) O.E. Sheffield & W.R. Tomlinson Jr, modes of initiation of condensed explosives,
“Properties of Explosives of Military Interest”, ie, various external stimuli that produce initiation,
AMCP 706-177 (Jan 1971) 30.) Anon, and provide references to Encyclopedia articles
“Principles ofExplosive Behavior”, AMCP where these modes of initiation are discussed
706-180 (April 1972) in detail

Initiation by Booster. See below under Inittition,

INITIATION by Primers
In its strictest sense Initiation is the genera-
tion of initial conditions that lead to stable Initiation by Bullet Impact is a special case of
detonation. However, it is common usage also Initiation by Projectile Impact. See Bullet Tests
to refer to the first stages of deflagration and in Vol 2, pp B332-340 and Vol 4, p D153; al~o
explosion as initiation. Thus it is often difficult under Projectile Impact below
to differentiate between “initiation” and “igni-
tion.” It is generally accepted that initiation is Initiation by Electric Fields. Silver Azide can
a thermal process which requires an external be initiated by DC fields of ca 70v (rein field
stimulus (except for “spontaneous” ignition) to strength for explosion ca 250v/cm) at extremely
get it started. Regardless of the nature of this ex- low current flow (Bowden “& Yoffe “Fast Re-
ternal stimulus, a necessary condition for initi- actions in Solids Acad Press (1958) p 101).
ation is that heat generated in the explosive Maycock & Grabenstein [Science 152, 508
(that is “initiated”) exceed all heat losses by (1966) & CA 65, 562 ‘(1966)] have postulated
the explosive. Since heat generation (chemical that piezoelectric effects generated by compress-
decomposition) increases exponentially with ing explosive crystals may genemte sufficiently
rising temperature, but heat losses are roughly large electric” fields to initiate these crystals
proportional to temperature to the first power,
any stimulus that generates a high enough [nitiation by Electron Beams. According to
temperature in an explosive is apt to “initiate” Bowden & Yoffe (“Fast Reactions in Solids”
that explosive. Conversely, an explosive in Acad Press, 1958, p 114) the initiation of
which exothermic reaction is readily started lead & silver azides by an electron beam is
by a variety of external stimuli, is said to at least in part due to bulk heating of the
 I 107

explosives by the beam. Pulsed electron beams pressure produced by reflecting the oxy-acetylene
have been used to initiate explosives and detonation wave is only ca 0.2 to 0.3 kbars.
study their shock properties (J.H. Shea et al, Thus gas detonations initiate condensed ex-
ONR Symp Det (1970) p 351). See also . plosives (if at all) by some direct heat transfer
Electrons & Neutrons Action on Explosives in process. In oxy-acetylene detonations, the
Vol 5, p E77 equilibrium temperature (CJ temp) is quite
high ‘4500°K
Initiation by Electrostatic Discharge. This is The writer (unpublished results) was able to
described in detail under Electricity; Extraneous initiate Lead Azide pellets of ca 2.5 g/cc density
Hazards Associated With It in Vol 5, pp E36-54. with oxy-acetylene detonations. However ca 1.2
See also Initiation by Sparks g/cc PETN pellet could not be initiated under
these conditions. Gordeev et al [Nauchn-Tekhn
Initiation by Exploding Bridge-Wire is generally Probl Goreniya; Vzryva (1965) p 12 & CA 64
considered to be special case of Initiation by 1894 (1966)] succeeded in initiating liquid
Shock. For det~ls see Exploding Bridge-Wire mixtures of tetranitromethane (TNM) and ben-
Initiation in Vol 6, pp E355-56 and under Exploding zene with stoichiometric methane-oxygen
Bridge- Wire (EB W) Detonators in Vol 4, pp ‘ detonations. For 1.5 vol parts of TNM & 1 vol
D 80’7-810 and Electrical Explosion in Vol 5, p of benz the initial pressure, P., of the deto-
p E23. An additional reference is T.J. Tucker, nating gas mixture had to be greater than 2
Proc Symp on Behavior & Utilization of Ex- atm to initiate the liquid. Initiation delays
plosives in Engineering Design (1972), pp 179- decreased as PO increased; delays were 350, 10
182 & @ Usec for P. of 2, 12 & 24 atm. For
4:1 by vol TNM/benz initiation of the liquid
Initiation by Fission Fragments. All attempts was observed for PO>0.7 atm. At PO-0.7
to initiate explosives by nuclear fission frag- atm the initiation delay for this liquid mixture
ments such as ~-particles, protons, Ar or Hg was -70 flsec
ions, -prays, X-rays, mesons and pions have
resulted in failures [Bowden & Yoffe quoted Initiation by Heat. See Thermal Explosion
above, & J. Cerny & J.V. R. Kaufman; and Ignition & Hot Spots in this Vol
JChemPhys 40 (6), 1736 (1964)]
Inittition by Hot Fragments is probably the
Initiation by Flame. Various aspects of this primary initiation mechanism in the so-called
process were described under Burning and Com- Halved Cartridge Gap Test (see Vol 1, p XV)
bustion, Vol 2, pp B343-346; Dead-Pressed and in other systems in which initiation occurs
Explosives, Vol 3, p D20; Ignition in this Vol; by transmission across an air gap from a donor
Thermal Explosion in a future Vol to an acceptor charge. The hot fragments” are
products and reacting material thrown off by
Initiation by Friction. See Friction Sensitivity the donor; see also Detonation by Injluence
Tests in Vol 6, p F204-L and Hot Spots & in Vol 4, p 397-R
Impact in this Vol
Initiation by Hot Wire is the usual method of
Initiation (of Condensed Explosives) by Gas initiation in Electro-Explosive Devices such as
Detonations does not involve the same phenomena electric blasting caps, electric detonators and
as Initiation by I%imers or Boosters. The pres- squibs. In general this method is only applicable
sures generated in gas detonations are too low to the initiation of primary explosives (unless
to produce sufficiently intense shocks in con- very special conditions are used). Various aspects
densed explosives for shock phenomena to play of Hot-wire Initiation are described under Ignition
a major role in the initiation of the latter. Even in this Vol; Detonators, Igniters, Primers and
the energetic C2Hz + Oz detonation produces a Other Initiating Devices in Vol 4, pp D737-742,
detonation pressure of only ca 43 atm for an D806-807, D846-850 & D854-856 and Electro-
initial gas pressure of 1 atm. The max shock Explosive Devices in Vol 5, pp E63-68. Addit-
 I 108

ional references are: 1) F. Mauger “Initiation of RDX etc. For “insensitive” explosives such as
an Explosion by Hot Wire,” ARDE Report (B) TNT, ANFO etc an intermediate booster charge
9/60, Aug 1960 ,2) H.S. Leopold, ONR Symp (PETN, RDX, Tetryl, NC Dynamites etc) may
Det (1970) p 339 3) T.J. Tucker, Proc Symp be necessary between the primer charge and
on Behavior & Utilization of Explosives in the main charge. For details, see Minimum
Engineering Design (1972)pp 175-179 Ikiming Charges in Vol 8; Booster in Vol 2,
pp 243-246; Contact Detonation Sensitivity
Inihation by Heat. See Thermal Explosion in Test in Vol 4, pp D186-190; and the added
a future volume and Hot Spots & Ignition in reference of C. H. Johansson & T. Sj61in, ONR
this Vol SympDet (1965) p 435

Initiation by Impact is described in detail in Initiation by Projectile Impact is a complicated

this Vol under Impact. Tests in which initiation process which depends on a combination of
may occur as a result of dropping an explosive shock initiation, impact initiation and hot
device are described under Drop Tests in Vol fragment initiation effects. For fast projectile
5, pp D1549-1554 impact, shock initiation effects are predomi-
nant. With slow projectiles the initiation
Initiation by Influence usually called Sympathetic resembles Impact Initiation. Further compli-
Initiation, is the initiation of an explosive charge cations are introduced if the impacting pro-
by the detonation of a nearby charge separated jectiles are hot; a special case where
from the first charge by an inert medium; see the explosive is part of the projectile is the
Detonation by Irrjluence in Vol 4, pp 395-398 so-called Stisan Test—seeBarrier Tests & .i’%eir
and also Initiation by Hot Fragments & Initiation Comparison with Shooting Tests in Vol 4,
by Shock pp D1 45-147 and Detonation (and Explosion)
Experimental Procedures in Vol 4, pp 333-335
Initiation by Ionizing Radiation. See Initiation
by Fission Fragments Initiation by Radio Frequency (RF) Radiation.
RF radiation, ie, radio wave & radar transmitters
Initiation by LASER. See Initiation by Light can, under certain circumstances, initiate electro-
in this Vol explosive devices. This topic will be discussed
under Radio Frequency Radiation, Effects on
Initiation by Light. See Light, Initiation by in Explosives. Also see articles on Electromagnetic
this Vol Compatibility & Electromagnetic Field Hazard,
Simuhzted in Vol 5, pp E70-’71 and Electric
Initiation by Photochemica[ Effects. See Initiation Blasting Chps and RF Energy in Vol 5, p E25-L
by Light
Initiation by Shock will be described in detail
Initiation by hecursor is a phenomenon en- under Shock Sensitivity. Some of the tests
countered in low velocity detonations, LVD, for determining the shock sensitivity of explo-
in liquid explosives. It depends primarily on sives have already been given under Detonation
cavitation of the liquid by the shock traveling (and Explosion) Experimental Procedures in
in the container ahead of the shock in the Vol 4, pp D318-321 , pp D322-331 & D344.
liquid. For a description of this effect, see Some preliminary discussion of shock initiation
Low Velocity Detonation in this Vol is also given in Vol 4, pp D520-522

Initiation by Primers (and Boosters) is the Initiation by Sparks. Primary explosives,

standard method of initiating secondary explo- Black Powder & possibly some dynamites can
sives. Thus hot wires (or other means) are be initiated by sparks “of a non-electrical nature
used to initiate the primer charge (Lead Azide, such as those caused by metal-on-stone friction
Mercuric Fulminate etc) explosive whose deto- etc. Manufacturers of dynamite use non-
nation then initiates the main charge of PETN, sparking tools in their plants. This is probably
 . . . .. -
I 109

a carry-over from the days’ when Black Powder ether, quebrachitol, with 100 parts of hydriodic
was an important commercial explosive. Initi- acid (d 1.70), placing the mixture in a long-
ation by non-electric sparks is obviously a neck flask provided with a tube for conducting
special case of initiation by heat gas away. After one hour of heating at 130-
140° the temperature is raised to about 150°
Initrhtion, Spontaneous. This is really a and heating is continued for an additional 3
misnomer. What it refers to is the self-heating hours. The mixture is then poured into a
of an explosive as a result of autocatalytic beaker and allowed to crystallize. The crystals
decomposition eventually leading to a thermal are ground, washed with alcohol and ether,
explosion. “Spontaneous” initiation may also dissolved in water and filtered through activated
occur during crystal growth eg in Lead Azide; charcoal and concentrated to a syrupy consistency.
see Detonation (and Explosion), Spontaneous A mixture of alcohol 90% and ether 10% is then
in Vol 4, pp D561-563 added in order to precipitate inositol. The re-
Written by J. ROTH sulting crystals are washed with alcohol and ether
and dried. W. deC. Crater’ proposed nitrating
Innesco. Some Italian percussion fuses of the optically active inositols in order to prepare
WWH consisted of two parts–the “spoletta” the explosive hexanitrate (see below)
and the “innesco. ” The innesco was a Refs: 1) Beil 6, 1192-6, (587-8) & [1 157-9]
detonator holder without which the fuse 2) W. deC. Crater, USP 1850225&CA 26,2867
could not operate (1932) 3) A. P6rez Ara (1945), p 345
I Refi Ordnance Sergeant, August 1943 4) Hackh’s Chem Diet (1944), p 442

Inorganic High Energy Title of a

Oxidizers. Inositol Hexanitrate (IH), C6 H6 (ON02 )6, mw
book by E. W. Lawless & I. C. Smith, pub- 450.16, N 18.67%, OB to C02 + 10.7%, d
lished by Decker, NY (1968) and of the paper 1.41 pressed at 3,000 psi; mp 120-122° (dec),
by W. E. Batty in ChemInd (London) 1969 bp ignites at 195°. Colorless plates or prisms
(35), 1231-33; CA 72, 12354/w (1970). The (from hot alcohol). May be prepd by nitrating
paper is review of the book which emphasizes water-free inositol with a mixture of 1 vol
F-containing oxidizers cone HN03. and 2 vols of coned H2 S04. The
resulting crude hexanitrate is dissolved in
INOSITOL AND DERIVATIVES boiling alcohol and crystallized on cooling.
Inositol or Hexahydrohexamethylene. 1,2,3,4,5,6- The inositol trinitrate, which is formed as a
Cyclohexanehexol, Mesoinosit (Inosite, Cyclo- by-product of nitration, remains in alcoholic
hexanhexanol); Cc H6(OH)6, mw 180.16, d solution and does not contaminate the
1.524 at 15°/40 for the dihydrate, 1.752 hexanitrate. IH is insol in water; v sol in
anhydrous, mp (anh) 200-225°. White crystals, methanol and ethanol, acetone, ether and
usually obtained from seeds of various plants, coned H2 S04
such as barley, peas and beans. Soluble in w, It is an explosive, comparable in impact
insol in abs alc & eth sensitivity to MF and more brisant than
It is a cyclic hexahydric alcohol, which is tetryl, as determined by the sand test (52g
optically inactive. Exists also in two optical of sand crushed compared with 47 .7g for
modifications: tetryl or 109% of tetryl). Its thermal stability
d-Inosito[: mp 247°. Colorless crystals; may is low (Ref 4) and for this reason is not
be prepd by heating its monomethyl ether, suitable for milita”ry purposes, but can be
pinite, Cc Hc (OH)~. (OCH3 ) [described in used as a base charge in commercial blasting
Beilstein, 6, 1193 & (587)] with hydriodic caps (Ref 3)
acid. Pinite ocmrs in resins and leaves of nu- When dropped on a heated plate, IH
merous plants; for example, senna leaves and flashes but does not explode, although it may
the Madagascar rubber plant be detonated by a commercial blasting cap
I-fnositol: mp~238°. Colorless crystals; may Crater (Ref 2) prepared hexanitrates of
be prepd by ~eating 75 parts of its monomethyl optically active d- and 1-inositols by nitrating
 I 110

20p of these with 100 parts of mixed nitric- Inspection of Ammunition and of Explosives.
sulfuric acid at about 7°(450F). The resulting The process of examination of explosives etc,
products had nitrogen contents about 18.3%, usually of a visual, physical, chemical or
as compared with 18.67% theoretical. They are ballistic nature are performed by specially
explosives with properties resembling those of assigned persons, called Inspectors. The idea
inactive inositol hexanitrate. (The dextro- prod- of this inspection is to determine the quality
uct is a solid, while the levo-, product is a of the product from the point of view of the
liquid). They are better gelatinizes than NC specifications pertaining to it
or NC and have been recommended as ingre- Inspections may be divided into Initial, and
dients of double-base smokeless powder. They Periodic or Subsequent Inspections
can also be used in dynamites or other com- For more info regarding regulations & proce-
mercial explosive mixtures in combination with dures connected with the inspection and testing
NG or aromatic nitrocompounds. Crater has of expls for the Government, see the following
also claimed the use of IH in non-headache Refs
dynamites (Ref 5) Refs: 1) Anon, “Ammunition Inspection Guide,
The same inventor proposed to nitrate a War Dept Tech Manual TM9-I 904 (1944), 940 pp
mixture of 20p inositol and 80p of glycerin 2) Dept of Defense Military Standard, “Explo-
with the same mixed acid as used for nitrating sive: Sampling, Inspection and Testing”,
glycerin. The resulting product is fairly stable, Ml L-STD-650 (Aug 1962) 3) Dept of De-
giving a 12-minute KI test at 82.2°; nitrogen fense Military Standard, “Pyrotechnics: Sampling,
content 18.4% (Ref 2) Inspection and Testing”, Ml L-STD-l 234 (March
An interesting property of IH is that it can 1967) 4) Dept of Defense Military Standard,
be detonated by the flash of a match-head (eg “Propellants, Solid: Sampling, Examination and
Ba-nitrate/Mg powder/Pb-hypophosphite). Be- Testing”, Ml L-STD-286B (Dee 1967) & Notice 2
cause of this Crater (Ref 3) patented its use as (June 1971) 5) US Army Materiel Command
a base charge in electric blasting caps containing Regulation, “safety Manual”, AMCR 385-100
either a MF/KC103 initiating charge or a match- (April 1970), p 26-3 (High Explosives)
head. It can also be used in fuse-type blasting
caps if a match-type ignition composition is Instantaneous Fuse. This fuse, burning at the
placed over a prepd charge of IH (Ref 3) rate of 100 to 300 feet per second, was formerly
Ficheroulle & Kovache (Ref 6) propose a much used in blasting operations where a number
method of preparing IH that is essentially of charges had to be fired “simultaneously. ” It
similar to the one described above. They do, has now been replaced by detonating fuses and
however, suggest the addition of 85p of lactose electric detonators
to 15p of wet lH before drying as they consider Instantaneous fuse was made by wrapping
the drying of pure IH (without 85 of inert several strands of quick match in waterproof
material) to be dangerous tape. The fuse was fired by means of a per-
They find IH to be more impact-sensitive cussion cap in a special pistol
than Hexamethylenetriperoxy diamine and very The term is sometimes erroneously applied to
sensitive to friction. IH explodes violently Cordeau D;tonant or Primacord
when placed on a sheet of paper when one of Rejl Marshall 2 (1917) p 540
the corners of the paper is ignited and its flame
reaches the lH Instantaneous Photography. See High-Speed
lle~s:l) Beil 6, 1197 2) W. deC. Crater, USP Photography in this Vol and Cameras, High-
1850225 & CA 26, 2867 (1932) 3) Ibid, USP Speed Photographic in Vol 2, pp Cl 3-19
1951595 & CA 28, 3590 (1934) 4) J.D.
Hopper, PATR 857 (1937) “Investigation of Instrumentation and Instrumental Methods of
IH as a Military Explosive” 5) W. deC. Crater, Analysis also next topic). The principle
(see
USP 2340304 (1944) & CA 38, 4134 (1944) purposes of instrumentation in the chemical
6) H. Ficheroulle & A. Kovache, MP 32, 133 industry are to measure and control physical
(1950) & CA 48, 4454 (1954) 7) Nothing changes and chemical reactions. Instrumental
pertinent found in CA 1957-1971 methods of analysis concern the application of
 I 111

various instruments to the solution of specific article, each month 21) H.H. Willard et al,
problems of analytical chemistry. Under the Instrumental Methods of Analysis, Van Nostrand,
title come spectroscopy, polarography, X-rays, NY (1951) 22) D.F. Boltz, Selected Topics
photometry, supersonics, various electronic in Modern Instrumental Analysis, Prentice Hall,
devices; such as oscillographs etc NY (1952) 23) W.G. Holzbock, Instruments
Each of these subjects is mentioned under for Measurements and Control, Reinhold, NY
separate headings. References on instrumentation (1955) 24) E.B. Pierson, Technology of
run into the thousands. In the opinion of Dr. Instrumentation, Van Nostrand, Princeton, NJ
R. H. Miiller, there should be a distinct subject (1957) 25) P. Delahay, Instrumental Analysis,
known as analytical instrumentation, which Macmillan, NY (1957) 26) H.H. Willard et al,
should be concerned with a study of all known Instrumental Methods of Analysis, Van Nostrand,
physical phenomenon for their possible use in NY (1958)
analytical chemistry. General references on this
subject are given below Instrumentation for Studying Explosives. See
Refs: 1) M F. Behar, Manual of Instrumentation, under individual items, eg, Cameras, High-Speed
Instrument Publishing Co, Pittsburgh (1932) 2) in Vol 2, pp C 13-19; Chronographs in Vol 3i
R. H. Miller, IEC (Anal Ed), 11, (1939) (Review pp C305-3 19; Impact Machines under Impact
on photoelectric methods in chemical analysis, in this Vol; Pressure Transducers in a future
including 239 refs) 2a) R. H. Mtiller, Ibid, Vol etc. Three good general references on this
1.3, 667-754 (1942) (A review on instrumental subject are:
methods of analysis) (313 refs) 3) L.A. McCO1l, 1) NOLR 1111 (1952), Chapt 9 2) Cook
Fundamental Theory of Servomechanisms, Van (1958) pp 22-43 3) AMCP 706-180, Chapt 5
Nostrand, NY (1945) 4) D.P. Eckman, Principles
of Industrial Process Control, J Wiley, NY (1945)
5) H.W. Bode, Network Analysis and Feedback Intensive Incendiary Agent “(See also Incendiary
Amplifier Design, Van Nostrand, NY (1945) 6) Warfare in this Vol) is one that is merely ignited
Greenwood and Collaborators, “Electronic Instru- (not detonated) and burns in one compact mass
ments,” vol 21, MIT Radiation Laboratory Series, Ordinary thermite and magnesium belong to
McGraw Hill, NY (1948) 7) R.H. Miller, AnalChem this class. They burn long and intensively but
20, 389 (1948) (Instrumental methods of analysis) their action is confined to a small area. This is
8) R.H. Mi.iller & J.J. Lingame, AnalChem 20, sometimes preferred when dealing with objects
795 (1948) 9) A.L. Chaplin, Instruments 21, of low combustibility. The disadvantage of in-
532-40 (1948) 10) H.M. Schmitt, Automatic tensive agents lies in the fact that when they
Chemical Process Control, Minneapolis-Honeywell fall on objects which are not ignitable, no
Regulator Co, ,Phila (1949) 11) R.H. Mtiller, damage is done even if ignitable objects are
AnalChem 21, 108-115 (1949) (Instrumentation; located only a few feet away
12 refs are included) 12) A. Camp & L. Slater, Ref G.J. Fisher, “Incendiary Warfare,” p 32,
ChemEng 57, No 9, 108-111 (1950) 13) D.M. McGraw Hill (1946)
Considine & S.D. Ross, Chem Engrg Prog 46, “
518-22 (1950) 14) D.A. Smith & J. Procopi, Interferometers, Applications to the Study of
Instrumentation 4, 32-34 (1950) 15) J.A. Explosion and Propulsion Phenomena. Two
Parker, Instrumentation 5, 4-7 (1950) 16) R. monochromatic light beams arriving out -of-
Rosenthal, Instruments 23, 664-69 (1950) 17) phase at some surface will produce a “fringe”
E.F. Pollard et al, IEC 42, 748-52 (1950) 18) illumination pattern on that surface. This
M.F. Behar, Ed, The Handbook of Measurement phenomenon is called interference. If the light
and Control, The Instrument Pub Co, Pittsburgh beams are in phase the illumination intensity
(1951) 19) R.E. Kirk & D.F. Othmer, Eds, is the sum of the individual intensities, but
Encyclopedia of Chemical Technology, Inter- if they are half-a-wavelength out of phase, the
science, NY, v 7 (1951) pp 908-926; J-Procopi, illumination intensity ,decreasesand becomes
Instrumentation (11 refs) 20) R.H. Mi.iller, zero if the individual light beams are of
Analytical Chemistry, “Instrumentation”; Short equal intensity. In-between there are gradations
 I 112

of reinforcement and cancellation depending on surface of the target by means of a lens L1.
how much the two light beams are out-of-phase The reflected light is recollimated by L2, and
(Ref 15) then split by a beam splitter B1. Half the light
Interferometers are instruments for measuring traverses the delay leg and is recombined with
displacement (distance) by utilizing light inter- the undelayed half at beam splitter B2. The
ference phenomena. We will illustrate the photomultiplier then records a signal whose
operation of interferometers by describing a brightness depends on the relative phases of
method of measuring the velocity of a speciman the two beams. Since the delay leg is fixed
(with a reflecting surface), propelled by a and the wavelength of the input light is a
detonating explosive charge (free-surface velocity), function of free surface velocity (Doppler shift),
by using a Laser Interferometer the number of fringes recorded at the photo-
A laser interferometer is shown schematically multiplier is related to the free surface velocity.
in Fig 1. The parameter measured is the free The relationship can be derived as follows
surface velocity of the specimen material. The (Ref,1 7). The Doppler shift is given by
principle of operation is as follows. Light from
the single frequency gas laser is focused on the A~(t) = ‘ ~ (t) o)
-()”

SPECIMEN

REFLECTING
SURFACE
~ /

MIRROR
/
-
SHOCK
OIRECTION

L
L1
REFLECTING
;;&;;;~ERSp

---”
/’ PRISM

I
----
----- ----

B2 ~
I DELAY LEG
I
I

PHOTOMULTIPLIER
L
1

“sER-
Fig 1. Laser Interferometer System (The velocity of the reflecting surface is
related to the number of fringes observed by the photomult iplier)
 I 113

where A is the laser wavelength,the speed of

c to the study of shock waves. Bennett et al
light, and u(t) is the speed of the reflecting (Ref 15) gave the theory of interferometric
surface at time t. The delay lag length NA is analysis and described the procedure used by
them at Ballistic Research Laboratories,
Nh = CT (2) Aberdeen Proving Ground, to study air flow
around projectiles in free flight
where ~ is the time for light to traverse the Bundy et al (Ref 13) measured the velocity
delay leg. Differentiating Eq (2) gives and pressure of gases in a rocket flame by
determining the small shift in wavelengths of

[)
aN(t) = – f AA(t) (3)
the flame luminosity with a Fabry-Per~t inter-
ferometer
and substituting for AA in Eq (1) from Eq (3) Refs: 1) E. Mach, & L. Mach, WienAkadBer
, gives (Math-Phys Klasse) 98, 1318 (1889) 2) L.
Zehnder, Zeits f Instrumentenkunde 11, 275
(4) (1891 ) 3) L. Mach, Zeits f Instrumentenkunde
12, 89 (1892) & 14, 279 (1894) 4) C. Cranz,
The number of fringes AN as a function of Lehrbuch der Ballistik, J. Springer, Berlin, v 3,
time are thus related to the reflecting surfaces (1927) pp 271-279; Er~nzungsband (1936)
velocity by a constant k/(2r) pp 173-175 5) H. Schardin, Zeits f Instru-
The major advantages of the laser interferom- mentenkunde 53, 396 (1933) 5a) M. Tesson,
eter over previous free surface systems are the Etude G B Note No 2 (15 April 1940);
high time resolution and the high surface velocity Service technique des fabrication d’armement,
capability. The limitations in rise time are limited Section ballistique ext~rieure (Paris, France)
by the capability of the photomultiplier or 6) W. Kinder, Optik 1, 413 (1946) 7) J.
oscilloscope recording system. The bandwidth of Winckler et al, Phys Rev 69, 251 (1946)
each system is typically 600 MHz or a response 8) R. Ladenburg, Phys Rev 71, 464 (1947)
time of S1 nsec (Ref 13) 9) J. Winckler, RevScilnstr 19, 307 (1948) 10)
Many other interferometers have been described R. Ladenburg et al, PhysRev 73, 1359-1377
in the literature (see references). Among these (1948) 11) D.K. Weimer et al, JApplPhys 20,
are the Fresnel, Fabry & P&ot, Jamin, Rayleight, 418 (1949) 12) V.E. Bergdolt et al, PhysRev
Michelson and Mach-Zehnder. interferometers. 76, 879 (1949) 13) F.P. Bundy et al, JAppl
Some application of interferometers are given Phys 22, 1069-1077 (1951) 14) C. CandIer,
below Modern Interferometers, Hilger & Watts Ltd,
E. Mach and his son L. Mach were the first @ndon (1951) 15) F.D. Bennett et al, JAppl
to apply an interferometer to ballistics (Refs Phys 23, 453-469 (1952) 15a) G.D. Kahl &
3 & 4). They modified the Jamin Interferometer F.D. Bennett, JApplPhys 23, 763-767 (1952)
and used it to determine the densities of air 16) F.A. Jenkins & H.E. White, “Fundamentals
near a projectile. A schematic arrangement of of Optics,” McGraw Hill (1957) 17) L.M.
their apparatus is given in ~Ref 4, p 274, fig Barker “Fine Structure of Compressive and
105 and in Ref 10, p 1360. Zehnder (Ref 2) Release Wave Shapes in Aluminum Measured
modified Mach’s apparatus and the socalled by the Velocity Interferometer Technique,”
A4ach-Zehnder apparatus is still used Symp on High Dynamic Pressure, Paris (1967)
Bergdolt (Ref 12) used the Mach-Zehnder 18) AMCP 706180, PP 5-16 to 5-17
interferometer and a short duration light
source with a rotating mirror cameralto obtain Interior Ballistics. See Ballistics in Vol 2, p B7
inter ferograms of projectiles and the air flow
patterns around them Intermittent Detonator Device. An analytical
Ladenburg et al (Ref 10) described the & experimental investigation was conducted to
application of the interferometer techniques to determine the operating characteristics of an
the stud y of faster than sound phenomena. intermittent-combustion device employing gaseous
Weimer et al (Ref 11) applied these techniques detonative combustion. Gaseous propane & air
 I 114

were used as propellants m the experimental intensive properties of the system. Extensive
invest igation properties depend on the mass of the system
Results indicated that the intermittent- while intensive properties are independent of
detonation device was capable “of operating on mass
at least two “resonant” spark-energization fre- The internal energy, or rather the change
quencies – approx 20 & 50 cps. Reaction in internal energy is an important variable in
thrust, noise output, and actual combustion Hydrodynamics. It occurs in the Rankine-
frequency were noticeably greater at resonant Hugoniot (RH) equation (Vol 4, p D531-R,
conditions than at other operating points Eq 8 or p D605-L, Eq 13) and as parameter
Reloading of the tube with fresh charge in various equations of state for detonation
occupied most of the cycle time, which limited products (eg see Vol 4, pp D285-287 or pp
the operating frequency of the device. This D294-295 or p D275)
intermittent-detonation device – which consisted
of three assemblies: air maqifold, fuel injector, International Committee Tests. The tests designed
and detonation tube – did not appear promising by the International Committee for blasting
as a thrust producing mechanism because of its explosives are as follows:
low operating frequencies 1) preliminary Test. Same as International 75°
It was recommended that the investigation Test,’ ai described under Physical Tests in Vol 1,
.,
of intermittent-detonative combustion should be p XVIII
continued to determine the” conditions under 2) Failing Weight (Impact) Test. Ten tests
which resonant operation occurs.’ Also the with 0.05 to O:10g samples, using an apparatus
effects of varying the physical characteristics having an anvil 1.27cm(0.5”) in diameter, should
of the’ detonation device should be ‘determined show that the explosive is less sensitive than
experimentally ~cric Acid ,(PA)
Refi L.J. Krzychi, “Performance Characteristics 3) Friction Test.’ A small sample of explosive
of an Inte~ittent-Detonation Device”, NAVWEPS “rubbed in an unglazed porcelain mortar should
Rept 7655, US Ordnance Test Station, China not show greater sensitivity than PA at room
Lake, Calif (June 1962) temp
,.. 4) Sensitiveness to Ignition. The same tests are
Intermittent I Ilumi,nation: See Cumeras, High applied as given under Ignition Tests in this Vol.
Speed in Vol 2, pp C13-19 & High-Speed These include: Fuse Test, Red Hot Iron Basin Test,
Photography in this Vol and Red Hot Iron Test
Rejl Marshall (1917), 2, p 437
Internal Ballistics of Barrel Weapons and of ,
Solid Propellant Rockets (Vnutrenniya Ballistika International Heat Test. See Physical Tests in
Stvol’nykh Sistem i Porokhovykh Raket). Title Vol 1, p XVIII
of the book by M. E. Serebriakovj GosNauch
–TekhIzdatOboronghiz, Moskva (1962), 3rd International Regulations. Following is a list
edition, 703 pp of International Regulations and where they may
be purchased: ,,
Internal Energy is the energy contained within “The Internationrd Carriage of Dangerous
a system. It is an extensive property of the Goods by Road (ADR)” ~~
system and the increaie or decrease in internal “The International Regulations Concerning the
energy between two states is independent of Carriage of Dangerous Goods by Rail (RID)”
the way the change between states is brought (approx $6 each)
about ,, From: Her Majesty’s Stationary Office, 49 High
The First Law of Thermodynamics is usually Holbom, London, WC 1, England
written in the form dE = TdS–PdV where E, “International Maritime Dangerous Goods
the internal energy, S, the entropy, and V, the Code”, Volumes I, II, and III [approx $25
volume, are extensive properties of the system, per set, SrdesNo IMCO 1972.9 (E)] .
and P, the pressure, and T, the temperature, are From: Inter-Governmental Maritime Consulta-
 I 115

tive Organization, 101-104 Piccadilly, London, storage etc of explosives etc. For a summary of
WI V OAE, England labeling and shipping regulations for explosives,
“IATA Restricted Articles Regulations”, see Sax “Dangerous Properties of Industrial
16th Edition, ($6 per copy) Materials,” 3rd Edit (1968), pp 309-362
From: International Air Transport Assocsirtion,
PO Box 315, 1215 Geneva 15 Airport, Switzerland Intraplant Distances. All explosive operating
“Transport of Dangerous Goods”, Volumes I, buildings and service magazines must be separated
II, III, and IV ($7.25 per set) in conformity with the so-called “intraplant
From: United Nations, Sales Section, New York, quantity-distance tables.” If the hazards involved
NY 10017, OHM Newsletter, Vol III, No 4, require dividing an operating line into separate
July 1973, Department of Transportation, Office buildings, such hazards are great enough to re-
of the Secretary, Washington, DC 20590 quire the use of full intraplant distances between
Refi G, Cohn, Expls & Pyrots 7 (l), 1974 buildings unless effective separate barricades are
provided, in which case these distances may be
Interrupter Burner Test. In studying the effects of halved
burning surface, grain consolidation, inhibitor Each state has its own regulations regarding
effectiveness, etc on the intermediate stages of distances. For instance, the table on p 810 of
propellant combustion, it is frequently desirable TM 9-1904, gives the “Intraplant Quantity-
to interrupt the burning process. The Interrupter Distance Table” as prescribed by New Jersey
Burner is a cylindrical combustion chamber with State laws
a firing plug at one end and a, rupture disc at
the other end. The rupture ‘disc is designed to Intrinsic Pressure. See under Detonation (and
rupture at some pre-selected pressure generated Explosion), Equations of State, Introduction
by the burning propellant test sample. This in Vol 4, p D269-L
sudden release of pressure extinguishes
(“interrupts”) the burning of the test ‘sample Inulin (Alant Starch, Dahlin, Alantin). (C6 HIO 05 )6
Refi C. deFranco, PicArsn Testing Manual No Hz O, mw 990.86. hydroscopic powder or
White,
2-3 (1951) horny amorphous lumps; mp 178° (decomposes
beginning at 1600), d 1.35-1.4 at 20°/40. S1sol
Interstate Commerce Commission (ICC) Regu- in cold w, sol in hot w; S1sol in ale. May be ob-
lations. The transportation of explosives and other tained from the bulbs of Dahlia variabilis or
dangerous articles in interstate commerce within other plants. On nitration, it gives an explosive
the limits and jurisdiction of the United States, compound
is regulated by Federal Law, Act of March 4, Refs: 1) Beil, not found 2) Fieser & Fieser,
1909, Chapter 321, Sect 232 and 234 (35S 1134) “Org Chem~’ Heath& Co, Boston (1950)
as amended by the Act of March 4, 1921, Chapter p 406 3) CondChemDict, 8th Edit (1971), p
172 (41S 1444-1445) 471
Violations of this Act are punishable by severe
fines and imprisonment Inulin Trinitrate. [C6H702(ON02)3 ].n, mw
Under authority of the Act quoted above, the (297.14)n, N 14.14%, OB to CO, -24.2%;
ICC has published regulations which can be ob- colorless, amorphous solid; mp softens at 90°
tained from them by writing to Dept of Com- and melts at 102°, bp decomposes beginning
merce, ICC, Washington, DC about 110°. When heated rapidly, it ignites
Note: In addition to the regulations issued by without exploding at 228-230”. First prepd by
the ICC, the regulations of the Bureau of the nitration of inulin with mixed nitric-sulfuric
Explosives (for rail shipments) as well as various acid by W. deC. Crater of Hercules Powder
harbor, state, municipal regulations should also co
be consulted. This complicates the situation, as When mixed acid contg 48.50% HN03 and
the various States, municipalities etc pass laws 51.20% H2 SOq is used the resulting nitrate contains
that apply to the particular location, but there about 13 .75%N, while nitration with MA contg
are no universal laws governing the handling, 20.8% HN03 and 62.8% H2S00 gives a 12.80%N
 I 116

product 163g of crystals. These were dissolved in hot

Inulin nitrate is insol in w, eth, ethyl and methyl water and then cooled–the pure salt crystal-
ale, toluene and carbon tetrachloride, but dissolves lized out ‘
in acetone, ether & alc mixt, coned Hz S04, ethyl The salt is nearly insol in cold water; sol
acetate etc. It does not crystallize from solutions in hot w. It is a violent explosive
but forms a film Its silver salt, AgCl(NOz )2, mp (explodes
Inulin nitrate is compatible with NC, nitrostarch at 109-11OO). Pale yellow glistening leaflets;
etc may be prepd by the action of AgN03 on an
It is a fairly stable explosive, having an impact aqueous solution of potassium iododinitro-
sensitivity of about 30cm with a 2kg weight methane. Insol in w, (Ref 4)
Inulin nitrate was proposed as a base charge
Di-iododinitromethane. Iz C(N02 )2; dark-colored,
in blasting caps, as a sensitizer for ammonium
pungent smelling oil. Was obtained on acidifying
nitrate in dynamites and as an ingredient of smoke- an ice cold solution of potassium iodonitro-
less powdeis methane. It could not be properly examined
W. deC. Crater gives the following examples of
because it decomposed immediately with the
explosives using inulin nitrate primarily as a evolution of gas and iodine (Ref 4)
sensitizer:
Ammonium nitrate dynamite. N~N03 65, Iodotrinitromethane (Sometimes erroneously
lnulin nitrate (13 .75%N) 20, NaN03 11, Pulp called Iodopicrin), CI(N02 )3, mw 276.95, N
(such as wood pulp) 4. This dynamite has a 15.17%, OB to C02 & Iz +23.1%, mp 55-58°,
rate of detonation of 2310 m/see, weight per bp 48° at 13mm. Bright yellow leaflets; may
1% stick - 120g; cartridge cent 378 per 100 be prepd by the action of an ethereal solution
lb; sensitiveness (gap test) 4“; weight strength of iodine on the silver salt of nitroform
53.5%. It flows and packs easily, is not dusty, It decomp on storage (Ref 1). Its hydrolysis
does not freeze and does not cause headaches const is 4 x 10-7 (Ref 5). Insol in w; sol in
Base charge. A standard blasting cap shell hot bz, ligroin and ale. No mention of any
may be charged with . 16g of nitroinulin (13 .75%N) explosive properties (Refs 1, 3 & 5)
pressed under 7840 psi, and provided with a primer No further mention of explosive props of
charge of 0.3g of 80/20 fulminate-K chlorate mixt. iodonitromethanes were found in the CA
Such a cap was found to be satisfactory for the Formula Indices 19’20-1971
detonation of explosives Some interesting work on the decomposition
Refi 1) W. deC. Crater, USP 1992123 (1933) kinetics of IC(NOZ )3 has been reported. In the
gas phase this compd decomposes with homo-
& CA 27, 5190 (1933) 2) No further refs
geneous first order kinetics over the temp range
found in CA 1947-1971
of 100-160° (Ref 6). The activation energy -
Iodamide. N13; “see Nitrogen Iodide under Iodides obtained (E = 34.4 kcal/mole, log Z = 15.25)
in this Vol suggests that the ‘primary step is the rupture
of the C–N bond followed by a radical (non-
lODATED AND NITRATED PARAFFINS
chain) reaction (Ref 7). Addn of a large
Some paraffin compounds containing both excess of NO, one of the decompn products,
I and N02 groups are explosive, for example: increased reaction rate 20-30%, addn of a large
Iododinitromethane. CHI(NOZ)Z; mw 231.96, N excess of NOZ, another decornpn product,
12.07% lowered the reaction rate 10%. Addn of 12,
Its potassium salt, KCI(NOZ )Z, mp (explodes also a decompn product, had no effect on rate
violently at 1540); orange-yellow plates. It was (Ref 7)
first prepd by Villiers (Ref 2). Gotts & Hunter The strength of the C–I bond is claimed to
(Ref 4) dissolved 10g of K dinitromethane in be 34.8 kcal/mole (Ref 7)
300ml of water containing 4g of KOH (one Mass spectrometric studies fully confirmed
equivalent), cooled the solution and slowly the previous manometric studies quoted above
added powdered iodine (18g) to it with shaking. (Ref 8). In the liq phase the pyrolisis of
The solution was evaporated to a small bulk IC(N02 )3 at 80-140° has the same kinetic as
(50ml), which caused the separation of about in the gas phase. Replacing a NOZ group with
 I 117

F stabilizes the molecule. Thus the kinetic to analysis, consisted of iodine pentoxide. In
parameters for the decompn of FIC(N02 )2 are the gas phase, iodine, oxygen, nitrogen and
E= 39.7 kcal/mole &logZ = 15.7 over the nitrogen oxide were found. The reaction occured
range 170-214° (Refs 9 & 10) without time lag. The course of the curve and
Mass spectra of positive and negative ions the kinetics were independent of whether the
of IC(N02)3 have been obtained (Ref 11) reaction was followed by the pressure of the
R@:il) Beil 1, 79, [45] & [47] 2) Villiers, gases formed or by the change in weight of
BullSocChim 43, 332 (1885) 3) A.K. Macbeth the sample. The decomposition was described.
& D.D. Pratt, JCS 119, 357 (1921) & CA 15, by the unimolecular decay equation from the
1669 (192 1) 4) R.A. Gotts & L. Hunter, beginning of the reaction to 85% completion.
JChemSoc 125, 442 (1924) & CA 18, 1270 The value of the activation energy was 66.4
(1924) 5) L. Birckenbach” et al, Ber, 62, 206 kcal
(1929) & CA 24, 1311 (1929) 6) G.M. Nazin Explosion of ammonium iodate took place
et al, Combust Flame 12 (2) 102 (1968) & at a temperature of 185°C, ‘~ejvery much higher
CA 69, 4102 (1968) 7) G.M. Nazin et al, than for the other hrdates (8 1‘C for NW Br03
DoklAkadNauk 177 (6), 1387 (1967) & CA & 90° for NH4 C103). The explosion was pre-
69, 26568 (1968) 8) G.M. Nazin et al, ceded by a readily measurable and gradually
IzvAkadNauk, SerKhim (1968) 315 & CA accelerating decomposition. Contrary to the
69, 66758 (1968) 9) G.M. Nazin, Ibid, (1968) two other halates, self-heating, was not observed
2628 & CA 70, 6738 (1969) 10) G.M. Nazin, before the explosion. The explosion was ac-
Ibid (1968) 2801 & CA 70, 77061 (1969) companied by a violet colored flash and pro-
11) J.T. Larkins et al, OrgMassSpectrom 5 (3), duced a temperature increase of only 10”C
265 (1971) & CA 75, 12076 (1971) in the reaction zone. The “activation energy
of the process leading to explosion was 38.4
Iodates and Periodates. Many inorganic iodates kcal
& periodates are known. Although many iodates From these measurements it appears that
& periodates are thermally unstable only the the stability of the compounds does not follow
ammonium salts appear to be explosive. How- the expected order of chlorate < bromate <
ever iodates and periodates are powerful oxidizing iodate. This behavior, however, cannot be re-
agents and can react vigorously with many re- garded to be a characteristic property of
ducing agents (Ref 5) ammonium halogenates only, because according
Varhelyi & Kekedy studied the thermal de- to our experiments the same order of stability
composition of iodates & periodates by thermo- has been found in case of potassium halates. It
gravimetric methods (Ref 2). They found that is fairly difficult to propose a reliable reaction
. there is no similarity in the decomposition of mechanism merely from kinetic data
univalent iodates, but most divalent iodates . Solymosi et al suggest that the rate-control-
decompose similarly since their decomp temps ling step in the thermal explosion of N~ 103
are similar. The thermal stability (ie their re- is the rupture of an I–O bond
sistance to decomposition into iodates) increases They also make the statement (no data or
as follows: of the alkali periodates Li~aUC< refs) that ammonium halates (-C103, -Br03 &
Rb<Cs. The thermal stability of alkaline earth -103 ) are impact & friction sensitive. This is
periodates increases in the order Ca<Sr<Ba in line with the thermochemical calculations
and conclusions therefrom made by Shidlovskii
Ammonium lodate. NHq103; mw 192.96, N (Ref 4) for both NH.103 & NH.104
7.25’%, rhombic or monoclinic crystals, d 3.31;
sol in w; decomposes on heating Ammonium Periodate. N~ 104; mw 208.96,
Solymosi et al (Ref 3) studied the thermal N 6.7%; tetrag colorless crystals, d 3.06, sol
decomp & explosion of Ammonium Iodate. in w. Decomposes on heating
They found that the decomposition of am- Solymosi et al (Ref 2) imply that NM 104
1“ monium, iodate starts at 140°C. The reaction is more stable than N~ 103. However a serious
yielded a solid reaction product which according explosion occurred when N~ 100 was scooped
from one container to another (Ref 1)

I
 I 118

Hydrazinium Iodate. Nz H4” H103 has been Nitrogen Iodide is.an exceedingly sensitive
postulated to exist only in cold solutions explosive when dry. It explodes upon the
(Ref 4). In general, hydrazinium salts of slightest touch and also upon very mild heating
oxidizing acids are much less stable than the such as in a warm air stream. It must be stored
corresponding ammonium salts wet, preferably under ether (Ref 15). Because
Refs: 1) G.F. Smith, Chem’EngNews 29, 1770 of its phenomenal sensitivity N13 is not a
(1951) & CA 46, 3279 (1951) 2) Cs. practical explosive, but by the same token it
Varhelyi & E. Kekedy, Studia UnivBabes- has been studied rather extensively to deter-
Bolvai
. (Romania)
. SerChem No 1, 11 (1962) mine why it is so sensitive. Since these studies
& CA 61, 2698” (1964) 3) F. Solymosi et al, contribute to the understanding of explosion
ZPhysikChem (Frankfurt) 48 (3-4), 242 (1966) phenomena they are described below
(in English) & CA 65, 1442 (1966) 4) A.A. Bowden & Yoffe (Ref 12, p 73) state:
Shidlovskii, ZhFizKhim 39 (9), 2163 (1965) & “Nitrogen iodide (N13. NH3 ) is a very unstable
CA 64, 516 (1966) 5) &lX (1968) p 837 material and will explode under the action of
6) No refs to explosive iodates or periodates very weak shocks. Even at liquid air tempera-
found in CA 1947-1971 (other than N~ tures, initiation occurs at an energy of 0.6g/cm
compds) searching under iodates, periodates (Ref 4). The stability of nitrogen iodide under
& iodic acid normal conditions depends to a great extent on
the presence of ammonia which retards the
IODIDES decomposition of the pure N13 (Ref 8).
Most metals form iodides eg 1(1, Pb12, B13, Meerk2mper (Ref 9), has found that the sen-
Sn14 etc. The iodides of the transition elements sitivity to impact is also reduced in an am-
are usually in their lowest oxidation state eg monia atmosphere. Presumably the ammonia
FeIz, COIZ, Mn12, Cr12 etc. All of these metal is rapidly adsorbed on the freshly exposed sur-
iodides are stable and nonexplosive face of the crystals of nitrogen iodide and
Iodine forms numerous interhalogen compds, prevents the decomposition from spreading”
eg IBr, IC13, IF5 etc but these are not really Nitrogen Iodide & N13. NH3 can also be
iodides since the iodine in these compds (if decomposed and ignited by light (Refs 10 &
they are not covalent) plays the part of a 11). Light absorption is strong in the visible
“metal” ion and weaker (but constant) in the IR (Ref 12, p 104)
The only explosive iodide is Nitrogen Iodide Meerkdmper (Ref 9) irradiated nitrogen iodide
which is described below in low-pressure atmospheres of air or ammonia
Nitrogen Iodide (also known as Nitrogen Triio- at various temperatures and determined the
dide). N13; mw 394.77, N 3.55%; black tryst, quantum yield of the decomposition. He finds
explodes on heating, sublimes in vat, insol in that this value is not constant but increases to ‘ ..
w, decomp in hot water (Ref 15). Prepd by a limiting value as the irradiation is continued.
treating 12 with coned aq NH3, probably via This limiting value depends on the ambient
temperature. The results suggest that the decomp-
312 + NH3 = 3HI + N13
osition is mainly thermal due to the conversion
By passing NHs g over 12 a series of ammoniated of the light energy into heat. There is a small
N13 compds can be prepd. These lose NH3 (5 to 10%) photochemical effect particularly
under vac except that the last NH3 cannot be when the nitrogen iodide is irradiated with blue
removed in this mariner and the compd thus or red light
formed is N13.NH3 (Refs 1, 2 & 3) When the intensity of the light from the
Suspensions of N13 in NH3 at -78” give flash-lamp is sufficiently high nitrogen iodide
dark ppts with solns contg low concentrations explodes. The amount of light energy required
of NHz-. The ppt with AgNH2 is Ag , for ignition depends on the temperature (see
NHz. N13. It is explosive when dry, but inert Figure). Extrapolation of the curve back to
to excess Ag NH2 & stable iri Iiq NH3 or in zero light energy gives a value of 80”C which
H2,0 at OO. At room temp the HZO soln de- should be compared’ with 50° which is the
composes .(accelerated by light) to Ag, AgI, PjH3. ‘dark’ ignition temperature
& N (Ref 13)
 I 119

If a tube filled with Xenon is used instead

0 of the spark in air the explosion begins 3.7
0 psec after the first appearance of light. This

‘R
0 value of 3.7 #see means that ignition takes
00 place ca 0.5 ~sec after the flash has reached
000 its maximum intensity. Again it is clear that
only a small part of the incident light is used
for igniting the nitrogen iodide
The results described above, in particular

L
0
the relation between ignition energy and
‘N \ temperature, suggest a thermal mechanism for
\\ the initiation. fie light will not be absorbed
I I I
\,
in a uniform manner in the surface layers.
-h -60 -40 -20 20 ‘LO 55 80
However, a rough estimate of the thickness
Temperature ‘c
of the surface layer which is heated to the
Figure. Relation between the light energy re- ignition temperature may be obtained by
quired for ignition (joule) and temperature assuming that the whole of the surface layer
(“C) for nitrogen iodide (Ref 9) is heated to a uniform temperature. If d is
the thickness of this surface layer, then
Again quoting Bowden & Yoffe (Ref 8,
pp 105-106): “The time at which the explo- d= E
sion occurs relative to the duration and the AATgC
intensity of the light flash has been determined
where E is the energy absorbed, A the surface
by means of spark photography. Meerk~mper
area of the nitrogen iodide on which the light
(Ref9) finds that explosion occurs just before falls, AT the temperature difference, g the
or at the time of maximum intensity of the
density of the nitrogen iodide and C the specific
light flash. This means that only a fraction of heat. Experimentally it is found that E/A =
the total light energy is used for ignition. This 8 x 10-2 J/cm2
result is similar to that observed for Silver Since ignition occurs in less than 50 #see
Azide. The light energy, E, passing into the for a flash of 200 #see duration, it is assumed
surface layer which is used for ignition is such that only the energy E/3A is used for ignition
that
Et = const = 1.35 x 10% Jsec/cm2 E
— = 2.7 x lo-2J/cm2
where t is” the time between the beginning of 3A
the light flash and the beginning of the explo- = 6.4 x 10-3 cal/cm2
sion. For a light flash lasting 200 #see, the For an ignition temperature of 80”C, AT =
energy E = 0.023 J/cmz, and the time t = 50 60”C, g = 3.5 g/cm3, and C = 0.12 cal/g/°C,
psec. This time is close to that required for d = 2.6 x 104 cm or if the ignition temperature
the lamp to reach its maximum intensity is taken as 55”C,
Nitrogen iodide also explodes when it is d = 4.4 x 104cm
irradiated with light from a spark discharge in
air. A glass plate placed between the spark and This value for the thickness of the hot layer
the nitrogen iodide sample hinders the passage is in agreement with the size of hot spot nec-
of the shock wave from the spark. The duration essary for initiation by shock.
In view of the assumption made, however, this
of the spark (4 pF, 12kV) “is ca 200 #sec.
agreement should not be regarded as providing
The light-time curve for such a spark rises
positive evidence for the thermal theory of
very rapidly and explosion begins 6 ~sec after
initiation
the beginning of the light from the spark.
Nitrogen iodide cannot be ignited under con-
When the discharge is from 0.4 pF at 38 kV
centrated ammonia solutions even with a very
the time from the beginning of the spark to
strong flash. Under pure water local explosions’
explosion is 4 ~sec
 I 120

do occur, but the explosion is not propagated The activation energy for Reaction (2) is
to the surrounding material. These observations 18-19 kcal/mole. It has been assumed that this
may be explained in terms of the thermal is the energy required to remove ammonia
theory. Water prevents the propagation of from the surface of the solid NH3” N13. After
explosion simply by abstraction of heat. In the removal of the ammonia the N13 that is left
case of ammonia solutions, the inhibition is is unstable and decomposes with the liber-
probably due both to cooling and to reaction ation of heat. The explosion then grows from
with hydrogen iodide. The removal of hydro- this hot “region; the reactions proposed being
gen iodide prevents the secondary reactions either
with nitrogen iodide from taking place and so N13 + NH3”N13 = NH3 + Nz +212 +21+ 33.1 kcal
reduces the heat liberated during reaction” (3)
Poole has ignited Nitrogen Iodide by a or
single ~-particle from a radium source (Refs N13 + NH3N13 = NH3 + N2 + 312 + 68.1 kcal (4)
5 & 14)
Bowden &Yoffe have suggested (Ref 12, If iodine atoms are produced as in Equation
pp 127-128 & Ref 14) that the abnormal (3) these could react further with ammonia to
sensitivity of N13 or N13“NH3 is due to its give ammonium iodide according to the equa-
being inherently unstable, and that the very tion (see Equation (1))
slight external stimuli (slight touch, warm 8NH3 +61= 6NH41 + Nz
air, irradiation etc) primarily act to remove ~ It is clear from the results described above that
adsorbed NH3 from the iodide surface. the presence of ammonia can under certain con-
Apparently this adsorbed NH3 stabilizes the ditions prevent the explosion of nitrogen iodide
iodide and its removal causes the iodide to when the decomposition is brought about by
decompose spontaneously heat, light, shock, or ionizing radiation
Again we quote Bowden & Yoffe:
The retarding action of ammonia has also
“Nitrogen iodide will explode when heated in been observed k the decomposition of a
air at 50°C. The equation representing the number of ammonium salts, eg ammonium
decomposition is (Ref 4)
perchlorate (NW CIOa ) and ammonium nitrate
8NH3N13 = 5NZ + 6NH41 + 912 (1) (NH. N03) (Ref 10)”
Garner & Latchem (Ref 6) found that when R@fil) F.D. Chattaway, JCS 69, 1572 (1896)
nitrogen iodide (N13” NH3 ) is dried over a layer 2) C. Hugot, CR 130, 505 (1900) 3) F.D.
of P205 at a pressure of 2 x 10-3cm Hg, Chattaway & K.J.P. Orton, AmChemJ 24, 344
thermal decomposition could be studied at (1900) 4) J. Eggert, ZElektrochem 27, 287
temperatures below O°C. However, when the (1921) & CA 16, 1013 (1922) 5) H.H. Poole,
pressure fell below 2 x 10-3 cm Hg, explosion SciProcRoySoc (Dublin) 17, 93 (1922) & CA
of the nitrogen iodide took place at tempera- 17, 1583 (1923) 6) W.E. Garner & W.E.
tures as low as -1 1‘C. At low pressures Latchem, TransFaradSoc 32, 567 (1936) 7)
Meldrum (Refs 7 & 9) has shown that the F.R. Meldrum, Ibid, 34, 947 (1938) 8)F.R.
equation representing the decomposition is Meldrum, ProcRoySoc Al 74, 410 (1940) &
different from that given above, CA 34, 3568 (1940) 9) B. Meerk~mper,
ZElektrochem, 58, 387 (1954) & CA 49, 2194
2NH3N13 = 2NH3 + Nz + 312 (2) (1956), 10) L.L. Bircumshaw & B.H. Newman,
Ammonia and water vapor retard the decompo- ProcRoySoc A227, 115 (1954) 11) J. Berch-
sition of the nitrogen iodide, a pressure of 10-3 told, ProcRoyPhotographic Soc of Great Britain
cm Hg of ammonia being sufficient to stop (1953) p 250 (published 1955) 12) Bowden
the reaction & Yoffe (1958) 13) J. Jander & E. Schmid,
The main effect of gas pressure is to slow ZAnorguallgemChem 292, 178 (1957) & CA
down the rate of diffusion of ammonia away 52, 6037 (1958) 14) F.P. Bowden & A. D.’
from the decomposing surface and so increase Yoffe, Endeavour 21, 125 (1962) & CA 58,
the stationary concentration of ammonia at 1294 (1963) 15) Sax (1968) p 969-R
this surface
 I 121

Iodides in Smoke Compositions. DeMent claims IODOBENZENE AND DERIVATIVES

mixts of elements or cmpds consisting of or Iodobenzene or Phenyl Iodide. Cb H~ I;
contg halogens, halide-forming elements or mw 204.02; pale-yel liq, fr p -31.4°, d
groups, an oxidant & a combustible materird, 1.832 at 20°, refractive index 1.621 at 20°.
such as tion, produce’ smokes of a large variety It is almost insol in water, but sol in ale,
when ignited. More than 370 formulations are eth & chlf. ,Iodobenzene is readily prepd by
described. Suggested uses include military reaction of iodine with benzene in the
screening & signaling presence of an oxidizing agent, or from
Refi J. deMent, USP 2995526 (1961) & CA benzenediazonium sulfate & potassium
55, 25100 (1961) iodide
Refs: 1) Beil 5, 215, (118) [167] & {571}
lodine. Iodine added in quantities 1 to 5% to 2) Kirk & Othmer II (1966), 864
a liquid organic peroxide climates the danger l-Azido-2-iodobenzene, Cc Ha N3 I; mw 245.03,
of explosion and fires in its use, storage and N 17.15%; strong oil, bp 90-91° at
smelling
shipment. Before use of the peroxide, the 0.9 mm Hg, d 1.8893 at 25°, refractive
iodine is removed by an oxidizing agent or index 1.6631 at 25°; prepd by diazotizing
other suitable means aniline with NaN3. No expl props are
Refi H.C. Stevens, USP 2415971 (1947) & reported. The l-Azido-3-iodo~ and l-Azido-
CA 41, 3114 (1947) 4-iodo-derivs are also known (Ref 2)
Refs: 1) Beil 5, (142) 2) Beil 5, 278 &
lodine Azide. See under Azsiies, Inorganic in (143)
Vol 1, Pp A542-543 Mononitroiodobenzene, C6 HQ NOZ I; mw
249.02, N 5.63%. The following isomers
lodine Pentafluoride. The controlled reaction are known:
of IF5 with sulfoxide, Me2S0, was found
dimethyl l-Nitro-2-iodobenzene, citron-yel ndls, mp
to be quite violent. Although small scale tests in the 54”, bp 288-89° (sublimes), d 1.9186 at 75°
cold (0°) proceeded without incident, delayed violent (Ref 1)
explosions occurred upon scale-up or upon l-Nitro-3-iodobenzene, monoclinic trysts, mp
allowing the temp to rise to 10-15° 36-38°, bp 153° at 14 mm Hg, d 1.9131at 75°
Refi E.M. Lawless, ChemEngNews_47 (13), (Ref 2)
8 & 109 (1969)&CA 71,40907 (1969)1 l-Nitro-4-iodobenzene, dk-yel ndls (from ale),
mp 172°, bp 287° at 726 mm Hg, explodes
Iodoazide. See under Azides, Inorganic in Vol
on heating in a tube at 605° (Ref 3)
1, Pp A542-543 Refs: 1) Beil 5, 252, (133), [190] & {621}
2) Beil 5, 253, (133), [191] & {622} 3) Beil
5, 253, (133), [191] & {623}
Iodosoazidobenzene. See “Benzene and Deriva-
Dinitroiodobenzene, (Oz N)z Cb H3 I; mw
tives” under Azido Halogen Derivatives of
294.03, N 9.53%. Six isomers are known:
Benzene in Vol 2, p B44-R
1,2-Dinitro-3-iodobenzene, It-yel ndls (from
ale), mp 138°, distils without decompn (Ref 1)
Iodoxyazidobenzene. Ibid
l,2-Dinitro-4-iodobenzene, yel pltlts (from
ale), mp 74.5° (Ref 2)
Iodoazidoethane. N3 CH2 CH2 I; no explosive
l,3-Dinitro-2-iodobenzene, orn-yel tablets
props mentioned in Beil 1, (33)
(from ale), mp 113.7° (Ref 3)
Iodoazoimide. N13” 2NH3. See Iodides in this l,3-Dinitro-4-iodobenzene, yel trysts (from
Vol. This name is used by Antelman (JChem- alc or be~ene), mp 88.5-90° (Ref 4)
Educ 30, 134 (1953) & CA 47, 5741 (1953)) l,3-Dinitro-5-iodobenzene, golden-yel plates
in describing some spectacular lecture demon- (from 60% ale), mp 99° (Ref 5)
strations of incendiary & explosive reactions l,4-Dinitro-2-iodobenzene, It-yel prisms (from
alc & eth) or almost colorless ndls (from ale),
mp 117.4° (Ref 6)
 I 122

Other props & methods of prepn are given Diodomethane or Methyleneiodide, CH2 12, mw
in the Refs 267.87; colorl liq or leaflets at 0°, mp 5–6°, bp
Refs: Beil 5, 270 2) Beil 5, 270 & [202] 180° (decomp), d 3.325; sol in alc or eth; sl
3) Beil 5, 270 & (139) 4) Beil 5, 270,
sol in w. Prepd by reacting methylene chloride
[202] & {641} 5) Bei15, [202] 6) Beil with NaI. Not explosive by itself but if mixed
5, (139) with K or K-Na alloys it explodes on shock
Refs: 1) Beil 1, 71, (18), [37] & [38]
1,3,5-Trinitro-2-iodobenzene or Picryl Iodide, 2) CondChemDict (1971), p 573
(0, N)3Cb Hz I; mw 339.02, golden-
N 12.39%; Iodoform or Triiodomethane, CH13; mw 393.78;
yel tetragonal ndls, mp 164-65°, d 2.285 at yellow leaflets, mp 115°, bp 260° (decomp),
22.5°; was first prepd from 2-chloro-l,3,5- d 4.08; sol in w, ale, eth & chlf. Prepd by
trinitrobenzene & KI in the presence of ale. heating acetone (or methanol) with iodine in
Other props & methods of prepn are given the presence of alkali. There is considerable con-
in the Refs. No expl props are reported fusion ti” the literature whether iodoform is an
Ref Beil 5, 275, [207]’ & {647) explosive. Beilstein (Ref 1), Sax (Ref 2), and CA
Iodochlorobenzene HCI salt or p-chloro 1947– 1971 do not mention any explosive pro-
Phenyliodide hydrochloride, (C1C6H41)HC1, perties. Ref 3 states that iodoform decomps
yellow needles (from chlf); sol in chlf, glac violently at 400°F. Friction makes a mixt of
HAc & benzene; S1sol in eth & petr eth; CH13+AgN03 decomp explosively (Ref 1)
decomp slowly in stoppered dark vessel – Refs: 1) Beil , 73, (18), (19), [38], {102} &
rapidly in sunlight. Decomp suddenly <97> 2) Sax (1968), 840-R 3) CondChem-
between 110° & 136°. Prepd by reacting Dict (1971), 473-L
phenyl iodide (in chlf) with chlorine Iodoni&omethane, CHZ1N02; mw 186.9, N 7.50%;
Cc H5 ICr04 yel ppt which turns orange-red prepd by reacting methyliodide in eth with AgN02
on drying explodes at 66-67° (no prep & a trace of iodine. Its Na salt, NaCH(I)N02,
given) white powder, explodes on heating
Refi Beil 5, 218 Refi Beil l,79& {115}
Iododinitromethane, CH1(N02)Z, mw 231.9, N
1-lodo-2-Ethoxy-3 Butene, CH2 ICOOC2H5CHCH3; 12. 1%. Its K-salt, prepd by slowly adding iodine
mw 225.96. In the course of prepn by Petrov’s to K-dinitromethane in aq KOH, orange-yellow
method (Ref 1), the reaction can violently explode platelets (from w); explodes violently at 154°.
under certain undefined conditions. Ref 2 relates The Ag-salt, pale yellow leaflets, insol in w, ex-
that several runs on a O.16M scale were completed plodes at 104–106°
without incident. However, during a 1M run, the Rejl Beil 1, 79 & [45]
reaction exploded while ethanol was being dis- Iodotrinitromethane or Iodopicnn, Ci(N02)3;
tilled under S1vac at 35°. Controlled attempts to mw 277.0, N 1s.’i!~o; no explosive props mentioned
determine the cause were unsuccessful for it or its salts
Refs: 1) A.A. Petrov. ZhurObshchelKhim Refi Beil 1, 79 & [47]
(JGenChem) 19, 1046–62 (1949)&CA 44,
1003 (1950) 2) J. Trent & P.G. Gassman,
C&EN 44, No 43, 7 (1966) 2-lodo-2-nitro-1,3-indandione,

C6H4 {~> CHI(N02); mw 317.05~ N 4.42%,

IODOMETHANE AND DERIVATIVES OB –80.7%, mp 1280. Vanag & Lipman (Ref
Iodomethane or Methyliodide, CH31, mw 141.95; 2) warn that an explosion might take place when
colorl liq, mp –66. 10, bp 42.50, d 2.279; sol in iodonitroindandione is prepd by heating iodine
alc or eth; S1sol in w. Prepd by reacting MeOH with the silver salt of 2-nitro-l ,3-indandione in
with NaI in the presence of sulfuric acid. Not a sealed tube at 130°. The silver salt of 2-nitro-
explosive 1,3-indandione decomposes explosively at 239°
Refs: 1) Beil , 69, (17), [35] & {93}. Refs: 1) Beil 7, 694, (375) & [632] (describes
2) CondChemDict (1971), p 576 its parent compound 1,3-indandione 2) G.Ya.
 I 123

Vanag & M.M. Lipman, DokladyAkadNauk 68, l-Azido-2-iodosobenzene, known in the form of
693–6 (1949) &CA 44, 1947 (1950) its salts, some of which are very unstable (Ref 1)
l-Azido-3-iodosobenzene, yel amorphous mass,
explodes at 1250. Its Formate explodes at 78°
lodonitrophenols (Ref 2)
The 2-Iodo-4, 6-dinitrophenol, C6H 3N2 05 I; mw l-Azido-4-iodosobenzene, explodes on heating
310.02, N 9.04%; mp 106– 107° has been prepd to 130° or in the presence of coned nitric or
(Ref 8). No explosive props are mentioned. sulfuric acid. Its Chromate salt explodes by
Other Iodo-dinitrophenol isomers are described friction or by heating to 71°. Its Formate salt
in Beil; none is explosive: explodes at 85° (Ref 2)
4-Iodo-2,3-dinitrophenol (Ref 1) Other props & methods of prepn are given in
5-Iodo-2,44initropherrol (Ref 2) the Refs. It is claimed as a fusehead constituent
6-Iodo-2,4-dinitrophenol (Ref 3) by Ingram (Ref 3)
4-Iodo-2,5dinitrophenol (Ref 4) Refs: 1) Beil 5, (142) 2) Beil 5, (143)
3-Iodo-2,6dinitrophenol (Ref 5) 3) L.K. Ingram, USP 2241406 (1941) & CA 35,
The 3-Iodo-2,4, 6-trinitrophenol or 3-Iodopicric 5318 (1941)
Acid, C6H2N3071; mw 355.02, N 11.84%; is
also known; mp 197°. It is prepd by nitrating Mononitroiodosobenzene, 02 NC6H410; mw
iodophenol with mixed acid. No explosive props 265.02, N 5.17%. Three isomers are known:
are mentioned for it or its salts (Refs 6 & 7) l-Nitro-2-iodosobenzene, orn colored prisms
Refs: 1) Beil 6, 263 2) Beil 6, [252] (from chlf), mp – decomp at 100°. Its salts
3) Beil 6, 263, (129)& [252] 4) Beil 6, are unstable on heating (Ref ,1)
263 & [252] 5) Beil 6, 264 & [252] l-Nitro-3-iodosobenzene, yel solid, mp, decomp
6) Beil 6, [283] 7) H.H. Hodgson & F.H. on heating at low temp. Its Chromium salt,
Moore, JCS 1927, 630 &CA 21, 1974 (1927) 0zNC6H@rl q, orn pdr, explodes on heating
8) D.B. Murphy et al, JACS 75,4289 (1953) to 95° (Ref 2)
&CA 48, 12075 (1954) l-Nitro-4-iodosoberrzene, solid, mp – explodes
at 82–83° (Ref 3). Its salts are unstable on
heating
IODOSO COMPOUNDS Other props & methods of prepn are given
These are substances of the type Ar10. Ap- in the Refs
parently only aryl iodoso compds are known Refs: 1) Beil 5, 252 2) Beil 5, 253 & {622}
since no alkyl iodoso compds were found in 3) Beil 5, 254, [191] & {624} 4) L.K.
the literature. Vibration spectra of severalf ArIO Ingram, USP 2241406 (1941) & CA 35, 5318
compds are given in Ref 2. Individual explosive (1941)
iodoso compds are described below. No other
refs to explosive iodoso compds were found in
CA 1947–1971 Dinitroiodosobenzene, (02 N)2C6H3 IO, and
7iinitroiodosobenzene, (02 N)3C6H2 IO, derivs
Iodosobenzene, C6H5 IO; mw 220.02; yel, amor- sere not found in Beil
phous pdr; sl sol in hot water & ale; almost insol
in eth,acet, benzene, petr eth & chlf. It explodes l-Iodoso-2-chlorbenzene, C1C6H410; mw 254.5,
on heating to 210°, and explodes in the presence white-yellow powder, v S1sol in eth, chlf, berrz
of coned nitric acid. Iodosobenzene was prepd or petr eth; somewhat sol in w. Explodes mildly
by oxidation of iodobenzene with ozone at 83–85°. Prepd by passing chlorine into o-
Refs: 1) Beil 5, 217, (118), [166].& {575} chloroiodobenzene and then treating with dil
2) C. Furlani & G. Sartori, AnnChim (Rome) NaOH. The 3-chloro isomer, bright yellow needles,
47, 124 (1957) & CA 51, 8533 (1957) decomps at 100° & the 4-chloro isomer, bright
yellow amorphous mass, decomps at 116–1 17°
Azidoiodosobenzene, N ~C6H410; mw 261.03, Refi Beil 5, 220 & 221
N 16.10%. Three isomers are known:
 I 124

1-lodoso-3-iodobenzene, IC6H410; mw 345.9, salt also explodes spontaneously

bright yellow amorphous powder; insol in usual Refi Beil 5, 392
org solvents; explodes mildly at 124° on rapid
heating; on slow heating it melts (decomp) at
207°. Prepd by passing chlorine thru a chlf Iodotoluenes and Derivatives
soln of m-diiodobenzene Iodotoluene, non-explosive
CH 3C6H41, is a stable
Rejl Beil 5, 225–226 compd; so are its mononitro derivatives. Higher
nitro derivs or azido derivs were not found in Beil
1,3-Di-iodosobenzene, OIC6H410; mw 361.9, Refi Beil 5, 31Q & 337
bright yellow amorphous powder, almost insol in
all solvents; explodes around 108°. Prepd by
passing chlorine thru a glac HAc soln of m- IODOXY COMPOUNDS
diiodobenzene As in the case of iodoso compds, the only
Refi Beil 5, 226 iodoxy compds reported in the literature are
Ar102 & not Alk102. Vibration spectra of
several Ar102 compds are given in Ref 2. In-
m-lodosotoluene, CHSCGHQIO; mw 234.0, dividual explosive iodoxy compds are described
amorphous powder, sol in cold glac HAc.
yellow below. No other refs to explosive iodoxy compds
Decomp at 180–85°; explodes at 206–07°. were found in CA 1947–1971
Prepd by passing chlorine thru a soln of m-
iodosotoluene in chlf. The ortho & para isomers Iodoxybenzene, C ~~ 102; mw 236.02; ndls
decompose with gas evolution at 170–75° & (from benz), mp – explodes at 236–37 0; almost
175–78°, respectively, but no mention is made of insol in chlf, acet & benz; v d sol in petr eth;
their exploding S1sol in hot water & glac acet acid. It can be
Ret Beil 5, 310, 311 &313 prepd by oxidation of iodobenzene with various
agents. Iodoxybenzene explodes in the presence
4-lodoso-3-nitrotoluene, 02 NC6H4(CH3)IO; mw of coned H2 S04 or phosphorus pentachloride.
280.12, N 5.03%, red powder; explodes mildly The Perch lorate salt is expl
at 129°. Prepd by passing chlorine thru a chlf Refs: 1) Beil 5,218, (118), [167] & {576}
of 4-iodo-2-nitrotoluene and neutralizing with dil 2) R.L. Datta & J.K. Choudhury, JACS 38, 1079
NaOH. The Chromate salt, [02 NC6H3(CH ~)1- (1916) &CA 10, 1749 (1916)
(OH)]2 Cr04, red-orange crystals, explodes at 94°.
The Formic acid salt, 02 NC6H3(CH3)I(CH20) ~, Azidoidoxybenzene, NSCGHQIOZ; mw 277.03,
orange-colored powder, explodes mildly at 72°. N 15.17%. Three isomers are known:
The Acetic Acid Sait, 02NCGH3(CH3)I(C2H302)2, 1-Azido-3-iodoxybenzene, brownish ndls (from
bright yellow needles, explodes at 200° glac acet acid), mp – explodes violently on heating ,
Refi Beil 5, 337 to 157° or by friction (Ref 1)
1-Azido-3-iodoxybenzene, brownish ndls, mp –
2-lodoso-4-nitrotoluene, O NC H (CH )10, insol explodes on heating to 175–80°; sol in water &
powder; explodes at 180–81 . Prepd as above glac acetic acid (Ref 2)
from 2-iodo-4-nitrotoluene 1-Azido-4-iodoxybenzene, trysts, mp – ex-
brn
Refi Bed , 338
plodes on heating to 170°, or in contact with
coned H2S04 (Ref 3). The Chromate of the
I
4-lodoso-1-propylbenzene, CH3CH2CH2C 6H410;
1,4 compd is a very dangerous, deep-red material
that explodes at 71° or upon being rubbed lightly.
mw 262.0; decomp on storage; explodes at 105°.
Its Formate (in the form of plates) explodes at
Prepd by passing ~hlorine th-m” a ~ln of 4.iodo.
1-propylbenzene in chlf & petr eth and then 85°. Its Nitrate melts at 102° with decomposition.
treating with a dil NaOH soln. Its Perchlorate The iodoxyazidobenzenes are claimed by Ingram
(Ref 4) to be useful as fusehead ingredients
salt, C9H1 1 I(OH)C104 explodes at 73° and also
explodes spontaneously on storage. The Chromate Other props & methods of prepn are given in
the Refs
 I 125

Refs: 1) Beil 5, (142) 2) Beil 5, (143 sol in w, alc or glac HAc. Prepd by heating
3) Ivl.O. Foster & J.H. Schaeppi, JCS 101, 1359 p-chloroiodosoberuene in w
(1912) &CA 7,330 (1913) 4) L.K. Ingram, Ref: Beil 5, 221
USP 2241406 (1941)& CA 35, 5318 (1941)
1-lodoxy-2,5dichlorobenzene, C12C6H3102;
mw 304.91, white needles (from hot w). Ex-
Mononitroiodoxybenzene, 02 NC6H4102; mw plodes mildly at 230°. Prepd by treating 2,5-
281.02, N 4.99y0. Three isomers are known: Dichloro-1 -iodosobenzene with steam
1-Nitro-2-iodoxybenzene, tablets (from glacial Rejl Bed 5, 222
acetic acid), mp – explodes violenfiy at 2 10°;
almost insol in eth, pet eth & benz; d sol in glac
acet ac, water & alc (Ref 1) 1-lodoxy-4-bromobenzene, BrC6H4102; mw
1-Nitro-3-iodoxybenzene, plates (from w), mp – 314.93; leaflets (from glac HAc), explodes at
explodes on heating to 21 5–18° (Ref 2) 240°; d sol in glac HAc. Prepd by heating
1-Nitro4-iodoxybenzene, wh plates, mp – explodes p-bromoiodosobenzene in w
at 212–13°; v sl sol in glac acet ac (Ref 3) Refi Beil 5, 224
Methods of prepn & other props are given ‘in
the Refs
Refs: 1) Beil 5, 253 & {622} 2) Beil 5, 1-lodoxy-2,5-dibromobenzene,. Br # ~ S102; mw .
253 & {223} 3) Beil 5, 254, [191] & {624} 393 .38; white amorphous powder, explodes at
2 18°; SI sol in hot w; sol in hot glac HAc. Prepd
Dinitroiodoxybenzene, (02 N~ C6H3102; mw by treating 2,5-dibromo- l-iodosobenzene with steam
326.02, N 8.59%. Two isomers are found in Rejl Bed 5, 224
Beil
1,3-Dinitro-4-iodoxybenzene, plates or prisms
(from w) or prisms (from aq HN03), mp – ex- 1-lodoxy-3-iodobenzene, lC6H4102; mw 361.93;
plodes on heating to 140–60°. Can be prepd colorless needles (from boiling w or glac HAc), ,,
by oxidation of 1,3-dinitro-4-iodobenzene (Ref 1) explodes at 2 16–1 8°. Prepd by treating m-
1,4-Dinitro-2-iodoxybenzene, trysts, mp – iodoiodosobenzene with steam
explodes on heating rapidly at 150 ; was prepd Refi Beil 5, 226
by reaction of HOC1 & 1,4-dinitro-2-iodobenzene
in glac acet ac (Ref 2) 1-lodoxy-4-iodobenzene, IC6H4102; mw 361 .93;
Refs: 1) Beil 5, [202] & {642} 2) BeiI 5, small needles (from glac HAc), explodes around
{642} 232°. Prepd by treating p-iodoiodosobenzene
with steam
~ini&~id~XYbenzene, (0’3N)sCIjHz10z, not Ret Beil 5, 227
found in Bed

1,3 Di-iodoxybenzene, 102 CCH.410*; mw 393.93;

1-lodoxy-2-chlorobenzene, C6H4(C1)102; white tablets, explodes very violently at 261° or
mw 270.5; needles (from w), explodes at 2030; on impact; v sl sol in w or glac HAc. Prepd by
sol in w, alc & glac HAc. Prepd by heating o- heating m-diiodosobenzene with steam
chloroiodosobenzene in w or alc Refi Beil 5, 226
Rejl Beil 5, 220
1-lodoxy-3-chlorobenzene, C1C6H4102; mw
270.47; color] crystals, explodes at 233°; d sol 2-lodoxytoluene, CH3C6H4102; mw 250.05;
in w, alc or glac HAc. Prepd by heating m- white crystals, explodes at 210°. Prepd by
chloroiodosobenzene in w heating o-iodosotoluene in w. lts Hydrofluoride
Refi Beil 5, 220 salt, C 7H 710F z, colorless leaflets, explodes
1-lodoxy-4-chlorobenzene, ClC6H4102; mw mildly at 180°
270.47; colorl crystals, explodes at 243°; S1
 I 126

4-hi~xytoluerre, CH3C6H4J02; mw 250.05; 2-lodoxy-1,3,5-trimethylbenzene, (CH 3) SC ~z Ioz;

prepd as above from p-iodosotoluene. It, melts mw 278.1 O; needles glac HAc), explodes
(from
with decomp at 229° at 195°; S1sol in glac HAc or ale. Prepd by
Rejl R.L. Datta & J.K. Choudhury, JACS 38, heating Iodomesit ylene and treating it with steam
1079 (1916) &CA 10, 1749 (1916) Ref: Beil 5, 409

4-lodoxy-1,3-dimethylbenzene, also called asym 4-lodoxy-1-tert-butylbenzene, (CHs)@bH@z;

Iodoxy-m-xylene, (CH ~)2C6H3 102; mw 264.07; mw 292.12; crystalline,, explodes at 201°; sol
small crystals (from glac HAc) or amorphous in glac HAc; insol in w. Prepd by reacting p-
powder (from w), explodes at 195°; sol in hot tert-butyl-iodo-chlorobenzene with Na hypochlor-
w or HAc. Prepd by passing chlorine thru a ite soln
soln of asym iodo-m-xylene in pyridine Rejl Beil 5, 417
Ret Bed 5, 376

5-1odoxy-1,3dimethylbenzene, also called asym 4-lodoxy-1-isoamylbenzene,

Iodoxy-m-xylene, (CH3)2 C6H ~102; mw 264.07; (CHS)ZCHCHZCHZC 6HQIOZ; mw 306.15; tablets
leaflets (from w), explodes at 2160. Prepd by (from w or glac HAc), explodes at 200–03°. .
steam distilling asym iodo-m-xylene. Datta & Prepd by oxidation of p-iodoso-isoamylbenzene
Choudhury claim that both the 4 & 5-Iodoxy- with a Na hypochlorite soln
isomers explode at 193° (Ref 2) Ret Beil 5, 435
Refs: 1) BeiI 5, 377 2) R.L. Datta & J.K.
Choudhury, JACS 38, 1079 (1916) & CA 10,
1749 (1916) Ion Exchange is defined in the Condensed
Chemical Dictionary (Ref 31) as:
“A reversible chemical reaction between a
4-lodoxy-l-methyl-2-ethylbenzene, solid (ion exchanger) and a fluid (usually a
CH3C6H3(C2H5)102; mw 278.10; white leaflets, water solution) by means of which ions may
explodes at 229°. Prepd by heating 4-Iodoso-l- be interchanged from one substance to another.
methyl-2 -ethylbenzene in w The superficial physical structure of the solid
Ref Beil 5, 396 is not affected. The customary procedure is
4-lodoxy-1-methyl-3-ethylbenzene, to pass the fluid through a bed of the solid,
CH3C6H3(C2H5)102; mw 278.10; white leaflets, which is granular and porous, and has only a
explodes at 229°. Prepd by treating correspond- limited capacity for exchange. The process is
ing methyl-ethyl-iodobenzene with Na hypo- essentially a batch type in which the ion
chlorite soln exchanger, upon nearing depletion, is regen-
Ref Bed 5, 396 erated by inexpensive brines, carbonate solu-
tions, etc. Ion exchange occurs extensively
in soils
4-lodoxy-1-propylbenzene, CHsCHzCHzCIjHQIOz; Ion exchange resins are synthetic resins
mw 278.10; leaflets (from w), explodes at 185– containing active groups (usually sulfonic,
200°. Prepd by storing corresponding iodoso carboxylic, phenol, or substituted amino
compd in w groups) that give the resin the property of
Refi Bed 5, 393 combining with or exchanging ions between
the resin and a solution. Thus a resin with
active sulfonic groups can be converted to
5-lodoxy-1,2,4-trimethylbenzene, (CHS)SC6HZIOZ; the sodium form and will then exchange its
mw 278.10; small needles (from glac HAc), ex- sodium ions with the calcium ions present
plodes mildly at 2 12°; S1sol in chlf; insol in eth in hard water. “Amberlite” resins are of this
or benz. Prepd by heating the corresponding type I
iodoso compd in w Some specific applications of ion exchange:
Ret Beil 5, 404 water softening; milk softening (substitution
 I 127

of sodium ions for calcium ions in milk); re- includes: concentration of dihrte solutions,
moval of iron from wine (substitution of fractionation of ions having similar analytical
hydrogen ions); recovery of chromate from properties, removal of interfering ions etc.
plating solutions; uranium from acid solutions; Chromatographic technique is one of the
streptomycin from broths; removal of formic branches of ion exchange technique. The ion
acid from formaldehyde solutions; demineral- exchange technique has found extensive ap-
imtion of sugar solutions; recovery of vahrable plication in the purification of water for
metals from wastes; recovery of nicotine from laboratory uses, to replace the more expensive
tobacco-dryer gases; catalysis of reaction be- distilled water
tween butyl alcohol and fatty acids; recovery Refs: 1) B.A. Adams & E.L. Holmes, JSCI 54,
and separation of radioactive isotopes from 1-6T (1935) 2) R. Griessbach, AngewChem
atomic fission; chromatography; establishment 52, 215 (1939) 3) H.L. Tiger & S. Sussman,
of mass micro standards; in cigarette filters IEC 35, 186 (1943) 4) O. Samuelson, Studies
to remove polonium from smoke” on Cation Exchange Resins, Thesis, Horsal,
The discovery of the phenomenon of ion Sweden (1944) 5) S. Sussman & A.B. Mindler,
exchange is attributed to H.M. Thompson & ChemInds 56, 789 (1945) 6) I.M. Kolthoff &
J.T. Way, British agricultural chemists. They E.B. Sandell, “Textbook of Quantitative Inor-
reported in 1848 the exchange of Ca and NW ganic Analysis,” Macmillan, NY (1945), p 116
ions in soils. No practical application of this 7) L. Winklander, Kgl Lantbruks-J15gskol, Ann
discovery was made, however, until the German 14, 1 (1946) (Sweden) 8) Anon, Resinous
chemist R. Cans proposed (in about 1910) to Reporter 9, No 4, p 1 (July 1948) 9) R.
apply the ion exchange principle to water Kumin, IEC 40, 41-45 (1948) (Ion exchange
softening. The first successful organic ion ex- with 123 references) (and in January numbers
change materials appeared on the market about of succeeding years, under Unit Operations)
1935, and about the same time I.G. Farben- 10) F.C. Nachod, Ed, Ion Exchange; Theory
industrie started a systematic research program and Application, Academic Press, NY (1949)
Since that time, the ion exchange industry, 11), R. Kunin, AhalChem 21, 87-96 (1949)
using various resins, has expanded enormous] y. (Ion exchange in analytical chemistry; 54 ref-
Among the scientists who have contributed to erences are included) 12) R. Kunin & R.J.
the ion exchange industry, the following may Myers, Ion Exchange Resins, J Wiley, NY
be mentioned; O. Liebknecht & R. Griessbach (1950) 13) R. C)da & H. Shimzu, Ion Ex-
of Germany, P. Smit of Holland, B.A. Adams change Resins, Gakujutsu Pull Co, Japan (1950)
& E.H. Holmes of Great Britain, H.L. Tiger, 14) R.E. Kirk & D.F. Othmerm, Encyclopedia
S. Sussman & A. Mindler of the United States of Chemical Technology, Interscience, NY, v 8
and L. Wiklander of Sweden (1952), pp 1-17; R. Kunin, Ion Exchange, with
The ion exchange substances used commer- 39 references 15) R. Kunin, IndEngChem 58
cially at present (in particular, ion exchange (1 1), 104 (1966) & CA 66,12376 (Review of
resins) are ionic solids in which one of the ion exchange technology & theory) 16) P.
ionic species (either an anion or cation) is a Miro Plans, IngQuim (Mex) 11 (1 19), 44 (1966)
highly cross-linked, polymeric, high molecular & CA 66, 59134 (1967) @eview in Spanish)
weight, non-diffusible ion, whose multivalent 17) R. Kunin, EncyclIndChemAnal 2, 346 (1966)
charge is balanced by relatively small diffusible & CA 66, 72047 (1967) (Review with 31 refs)
ions of the opposite charge. These exchangers 18) R.M. Wheaton & A.H. Seamster, Kirk-Othmer
constitute a class of electrolytes having prop- EncyclChemTechnol, 2nd ed, 11, 871 (1966) &
erties that are in many respects similar to true CA 67, 25983 (1967) (60 refs) 19) R. Kunin
solutions of electrolytes & R.L. Custafson, IndEngChem 59 (11), 95 ~
The chief advantage of an ion exchange (1967) & CA 67, 118546 (1967) (146 refs)
technique lies’ in simplicity and rapidity with 20) S.B. Applebaum, “Demineralization by
which various separations or concentrations Ion Exchange: Water Treatment & Chemical
may be achieved. The application of ion ex- Processing of Other Liquids,” Academic, NY ,
change technique in analytical chemistry (1968) & CA 69, 108144 (1968) 21) R.
 1 128

Kunin & R.L. Gustafson, IndEngChem 60 (11) detonation of solid explosives in a high vacuum.
57 (1968) & CA 70, 5452 (1969) (285 refs) The salient feature of these observations is the
22) K. Chandrasekharanj ChemAgeIndia, 19 (8), very high velocity, 20 km/see, of the leading
666 (1968) & CA 70, 39192 (1969) (42. refs) products emitted from the ends of charges of
23) J.A. Marinsky, Ed, “Ion Exchange,” vol 2, explosives which contain hydrogen. These authors
Dekker, NY (1969) & CA 70, 91128 (1969) propose two mechanisms which might account
24) R. Kunin & R.L. Gustafson, IndEngChona for these high-speed emissions. They obviously
61 (12), 38 (1969) & CA 72, 68578 (1970) favor mechanism 1). We quote:
(370 refs) 25) G.V. Samsonov et al, “Ion “1. The mechanism of ambipolar diffusion
Exchange: Sorption of Organic Substances,” can be invoked to double the speed of the
Leningrad, Nauka (1969) & CA 73, 29355 ionized portion of the cloud. In ambipolar
(197.0) (in Russian) 26) G. Kuehne, Fortschr diffusion, a pressure gradient in the plasma at
Verfahrenstech 1966-1967, 8, 545 (1969) (Ger) the surface of the explosive will tend to accel-
& CA 73, 38854 (1970) (323 refs) 27) R. erate the electron gas at several thousand times
Patterson, “An Introduction to Ion Exchange,” the rate for ions. Any tendency for the elec-
London, Hayden (1970) & CA 73, 91824 trons to move ahead of the ions, however, is
(1970) 28) K. Stambert, “Construction- quickly balanced by an electric field caused
Technological Problems of Ion Exchange Ap- by the separation of charges. The electrons,
plications:’ Berlin, Akad-Verlag (1970) & CA being highly mobile in comparison to the
74, 32962 (1971) (in Ger) 29) K.M. Saldadze, ions, will quickly achieve a near equilibrium
Plast Massy 1970, 282 (Russ) & CA 74, 76873 between the influences of the pressure gradient
(1971) (71 refs) 30) G.V. Samsonov & N.I. and electric field. However, the same electric
Nikitin, Eds, “Ion Exchange & Ion Exchangers,” field acts on the ions but in the same direction
Leningrad, Nauka (1970) (Russ) & CA 74, as the pressure gradient. This subjects the
103454 (1971) 31) CondChemDict, 8th Edit, ions to a total force away from the surface
(1971), p 474 double that on a neutral species. An order of
magnitude calculation shows that a charge
Ionic Energy in Propulsion. See Propulsion, separation of even a tenth of a percent
Ionic in future Vol creates an electric field which would produce
forces on the charged particles many orders of
IONIZATION IN DETONATION AND SHOCK magnitude greater than the pressure gradient.
WAVES. See Detonation (and Explosion); The difference in arrival times of various species
Electrical, Electromagnetic Effects Accompanying (hydrogen, lithium, sodium) in the pink glow
It in Vol 4, pp D258-264; Detonation, ,F1ash- is presumably due to the fact that the same
Across, Heat Pulse and Hyper- Velocity Phenomena pressure and electric field act on both light
in Vol 4, pp D348-349; Detonation (and and heavy species in the detonation “plasma:’
Explosion); Phenomena Accompanying It in Vol accelerating the lightest species the most
4, p D471; Detonation, Plasma In in Vol 4, pp 2. The mechanism proposed by Johansson
D471 -474; Detonation Velocity, Injluence of and Selbert (Ref 3) which invokes elastic
Magnetic, Electro Magnetic and Electrical Fields collision between heavy molecules in the
as well as of Electrons on in Vol 4, pp D668- detonation products and lighter molecules
671; and Heat Pulse in this Vol in the ambient gas. Although this is an
Since the appearance of Vol 4, relatively attractive hypothesis, it appears doubtful
little has been published on ionization in deto- that the lighter molecules actually come from
nation waves, or ionization in shocked condensed the ambient gas for two reasons: (a) the
media. However, there is considerable new in- intensity of the light emitted when these
formation on shock ionization of gases. We molecules impinge on a surface ought to in-
discuss these phenomena below crease as the number of available molecules
Ionization in a Detonation Wave. Hay et al increases; however, over a million-fold increase
(Ref 9) obtained high-speed framing camera in ambient pressure (10-7 to 10-1 torr) no
pictures and time-resolved spectrograms of the obvious increase in Iuminosit y was observed;
 1 129

(b) velocities of the sodium atoms or ions, son & H.L. Selberg, “Transient High Temperature
which certainly do not originate in the Gas Layers in Detonation,” Proc 4th IntlConf
ambient gas, are very nearly as high as those Ionization ,Phenomena in Gases, Uppsala, Aug
of the hydrogen atoms, molecules or ions” 17-21, 1959, IVD 1114 (1960 4) Ya. B.
The use of,ionization pins or pin switches Zel’dovich et al, Do~AkadNauk
in the measurement of detonation velocity was SSSR, 138, 1333 (1961) 5) R.J. Eichelberger
described in Vol 4, pp D632-638. Their prin- & G.E. Hauver, Les Ondes de Detonation, Paris,
ciple of operation is the closure of an electric (1962) p 363 6) S.D. Hamann & ,M. Linton,
circuit by the ionization associated with a TransFaradSoc 62, 1, (1966) 7) S.D. Hamann,
detonation wave. The latest pin switch tech- Effects of Intense Shock Waves in Advances
niques are described in Ref 11 in High Pressure Research 1, ed by R.S. Bradley,
Shock Ionization in Condensed Media. Dremin Academic Press, London & NY (1966) 8) V.V.
et al have studied shock polarization of both Yakushev et al, JETP, Letters, 7, 165 (1968)
polar & nonpolar liquids. They conclude that 9) J.E. Hay et al, 5th ONRSympDet’ (1970)
these polarizations are ionic in nature. We p 559 10) A.N. Dremin & V.V. Yakushev, Ibid,
quote from “a recent article by Dremin & p 399 11) J.P. Sumner, Proc Symp on Behavior
Yakushev: & Utilization of Explosives in Engineering, Design,
“It has been found in studying polarization Albuquerque, NM (1972) p 230
of liquid dielectrics in shock waves,’ that liquids
involving polar molecules, such as water, acetone, Shock Ionization of Gases. If temperatures
chlorobenzene, brornobenzene, iodobenzene, behind a shock front are in. the range of
nitrobenzene, and others (Ref 5) give polari- 15000-20000”K the gas through which the
zation signals. When shock waves are propagated shock is moving will be appreciably ionized.
over nonpolar liquids such as benzene, carbon The establishment of ionization equilibrium
tetrachloride, etc, no polarization signals appear is the rate-determining step in this process
(Ref 8). In this connection, an assumption arose and consequently controls the thickness of
that with decomposition of nonpolar molecules the wave front (Ref 6)
of a liquid behind the front of ‘a shock wave The ionization process is quite complex,
into polar fragments, a polarization signal may and to avoid even further complications, the
be obtained from propagation of a second following discussion will be limited entirely
reflected shock wave over a shock-compressed to the shock-ionization of monatomic gases.
substance (Ref 8). Carbon tetrachloride was the One compelling reason for doing this is that
liquid used” complications due to dissociation (eg of Nz
On the’ basis of their results as well as the or more complex polyatornic molecules) are
results of others, Dremin & Yakushev conclude: thus avoided. Furthermore for ,a given driver
“The electrochemical nature of signals ob- shock, the highest temperatures, and conse-
served for all liquids studied is’ evidence that the quently the greatest likelihood of ionization,
electric conductivity arising on shock compression occur in monoatomic gases since such gases ,
cannot “soak-up” energy in internal modes,
is” of an ionic nature. Hamann and coworkers
(Refs 1, 2, 6 & 7) came to the same conclusion ie, in rotation Ior vibration. In what follows
when studying the conductivity of water, meth- A represents an atom of gas (Argon by
anol and acetone in shock waves preference since much of what follows is
The persistence of transparency on shock derived from studies of shocked Argon). The
compression of water, methanol and dichlorethane main steps in the process are represented by
within the range of pressures corresponding to the following equilibria:
good conductivity (Ref 4) is another evidence A+ A= A++e–+A (1)
in favor of the ionic nature of these liquids A+v=A-l–e– (2)
under the given conditions” A+e–=A++2e– (3)
Refs: 1) H.G. David & S.D. Hamann, TransFarad- Electron avalanching via (3) is the main process
Soc, 55, 72 (1959) 2) H.G. David, S.D. Hamann, for producing A+ ions. However this requires the
TransFaradSoc, 56, 1043 (1960) 3) C.H. Johans- presence of “priming” electrons which can be
 I 130

produced by A + A collisions in the shock gas and Cv is the const vol heat capacity of
(step (l)) orphotoelectrically byth’e absorption the equilibrium gas. From kinetic theory Cv =
of sufficiently energetic radiation to photoionize 312 R/M, which, combined with Eq (2), leads
A (step (2)). However, under shock conditions to:
where ionization is observed, the best evidence %P2U2–dl /M = 3/2(l+@AT/M (6)
suggests that steps (1) & (2) cannot provide a
sufficient number of “priming” electrons for because at equilibrium there are (1 –a.) moles
step (3). This discrepancy is still unresolved (Ref A, cx moles A+ & CLmoles e– or a total of
6). Biberman & Yakubov (Ref 4) have suggested (1 + CY,)moles of “monoatomic” gas. Here I,
that absorption of resonant radiation from the is the first ionization potential of A, ie we
equilibrium region produces many A atoms that are neglecting all but singly ionized species.
are electronically excited; such atoms are then Since AT = T–TO and if T > To (T -10000
readily ionized by electron impact and thus to 50000”K which is much greater than
lead to electron avalanchitig To = 300°K), Eq (6) gives,
Equilibrium calculations based on combining T s p2U2M/3(l+a)R – 2/3uIl/ -
the Saha equation (in terms of the internal (7)
(l+ci)R
partition functions’ of A, A+ & e–) with the
conservation conditions for the shock are fairly and after rearranging, combining terms, &
involved (Ref 1). We chose instead to derive eliminating T via Eq (4):
the following set of equations for an idealized ~
case, which, though they overestimate the degree [#2-3 (1-#)#] =
a = 211
of ionization and underestimate the temperature, (8)
~ [4g–3]
point out the shock and gas parameters that 211
control the ionization of monoatomic gases
and
Consider a perfect gas of molecular weight
T = u(1 –p)U2 M/ [1+U2MK(4U–3] R
M which has been shocked and has attained
211 (9)
ionization equilibrium with the fraction of
atoms ionized designated by u. For a shock Eq 8 immediately tells us that the degree of
pressure P, much greater than ambient pressure, ionization depends strongly on the shock velocity
gas density p in the shock and p. ahead of the U. For strong shocks p = constant = 0.9
shock and a shock velocity U, the conservation (see Fig 6 of Ref 2) for all monoatomic or
conditions lead to: even polyatomic gases. Thus the only important
shock parameter is U. Similarly the only im-
P = pou2(l–po/p)= po@-J2 (1) portant gas parameters are the molecular weight
where p ~ l—pop, and M and the first Ionization potential 1,
It is instructive to examine the noble gases in
AE = %P(l/po–l/p) = %/.J2U2 (2)
terms of Eqs 8 & 9. In the series He to Xe,
combining Eq (1) with the perfect gas law gives M increases and I ~ decreases, thus at a given U
‘P = po@J2 = p(l+@RT/M (3) and a nearly constant ~,, the degree of ioni-
or , zation ct is much greater for Xe than for He..
T = p@J2M/p(l+cx)R = In fact u increases regularly in the series
(4) He< Ne < Ar < Kr < Xe. Temperature of the
/.t(l –#)U2 M/(1 +o,)R
shocked gasesalso increases in the same manner
If we assume that a negligible amount “of energy
birt not as greatly as u because the additive term
is used in electronic excitation of the A atoms,
in the denominator of Eq 9 increases progress-
then the incident shock energy AE is used to
ively’ from He to Xe and tends to counteract
ionize some of the A atoms and to heat the
the increase in M in this progression
mixture of ionized and neutral atoms. This energy
For strongly shocked Argon (see Table 1),
balance is expressed by:
calculations based on Eq 8 give a’s that are
, AE– AI=cVAT (5) 30 to 40% higher than the more accurate
where AI is the total ionization energy of the (partition function) calculations of Reynolds
 I 131

Table 1.
Comparison of Approximate and Exact Calculations (Ref 2) for Shocked Argon
u P/PO p/pO(Ref2) P # (Ref 2) a Eq 8 ~ (Ref 2) T Eq 9 T (Ref 2)
mm/#see
8 10 9.00 0.900 0.889 0.454 0.322 19000 2310iI
9.5 0.895 0.436 20200
9.0 0.889 0.410 21500
8.5 0.882 0.393 22800
9 10 9.63 0.900 0.896 0.574 0.417 22200 25500
9.5 0.895 0.552 23600
9.0 0.889 0.518 25200
10 10.5 10.1 0.905 0.901 0.736 0.523 23800 28350
10.0 0.900 0.709 25300
9.5 0.895 0.681 26900

& Seely (Ref 2). This is to be expected since terms in @ with measured shock temperatures
we neglected the energy used in electronic Shock temps and shock velocities in Ar
excitation of Ar atoms and this neglect were measured by the writer (Ref 3) &
shows up as increased ionization. Our calcu- Zatsepin et al (Ref 7). Velocities and temps
lated temperatures (see Table 1) are about 10% of shocks in Kr & Xe were also measured by
lower than Seely’s (Ref 2) if plpO is the same the writer (Ref 5) and shock temps in Xe by
in both calculations. Presumably this better Zatsepin et al (Ref 7). The shock velocity of
agreement between temperature and CY.’S is due 8.3 mm/psec reported for Ar in contact *with
to the following compensating effect. Inclu- Comp B (Ref 3) is incorrect. This is an
sion of electronic excitation would make it average velocity of the propagation of intense
appear as an additional negative term in Eq luminosity and/or ionization which changes
(7) and would tend to reduce T. However, in- very little over at least 10cm travel from the
clusion of electronic excitation makes CI smaller. Comp B face except in the region very close
Thus the first right-hand term of Eq (7) becomes to the Comp B. Unfortunately it is the shock
larger and the second (negative) term becomes velocity in this close-in region that we need
smaller, both of which tend to increase T and since peak temp is achieved within 1 ~sec of
counteract the direct effect of including a the shock entry into the Ar. Our best estimate
negative term for electronic excitation of U for Ar in the close-in region is -lOmm/
There are no direct measurements of the de- ~sec. The values of U for Comp B driven Kr
gree of ionization of strongly shocked noble & Xe, to be used in Table 2, are also estimates
gases. Thus the validity of the above discussion for the close-in region. They are quite tentative
can only be tested indirectly by comparing since they are ‘based on few data
computed shock temperatures (which contain

Table 2.
Shock Temperatures of Noble Gases
Uncorrected Corrected
Gas ‘ohs ‘ohs (p/pO)calc T talc T CdC
(mm/#see) (“K) (“K) (“K)
Ar -10 28500 10.1.(a) 25300 (C) 28700 (d)
Kr - 7.6 -37500 8.6 (b) 32600 (C) 37600 (d)
Xe N 6.8 -47500 7.8 (b) 40200 47000 (d)
(a) Ref 2
(b) Assumed to be the same as for Ar (Ref 2) at the corresponding U
(c) According to Eq 9 with a obtained via Eq 8
(d) All U’S arbitrarily reduced by a factor of 1.4
 I 132

Agreement between experiment and computa- is only half as hydroscopic as Blk Pdr and can
tion is good if one assumes that, as appears to be made only one-fifth as hydroscopic by the
be the case for Ar, all “accurate” et’s are 40% use of chemically pure instead of spec grad
smaller than the corresponding LX’Scomputed K nitrate
via Eq 8. A presumably exact calculation (no Refi S. Livingston, PATR 647 (March 1947)
details given) by Zatsepin et id (Ref 7) gives a
shock temp of ‘37000 ”K(?) for a shock in Xe Ipatieff, V.N. (1867-1952). Vladimir Niko-
moving at U = 6.8 mm/psec and ‘29000°K laevich Ipatieff, of Universal Oil Products Co
for shock in Ar moving at 10 mm/psec and Northwestern University, was born in
Moscow and attended military schools under
Written by J.. ROTH the czarist regime. His work carried him to
a high position in the Russian army and to
Refs; 1) J.W. Bond, Jr, “The Structure of, a recognition as one of the outstanding scien-
Shock Front in Argon,” LA-1693, LASL (1954) tists of Russia
2) C.E. Reynolds & L.B. Seely, Nature 199 Although he had been interested in chem-
(4891) 341 (1963) &CA 59, 7009 (1963) 3) istry since boyhood, his studies in organic
J. Roth, JApplPhys 35 (5), 1429 (1964) 4) chemistry began at 27 when he presented a
L.M. Biberman & I.T. Yakubov, Soviet Phys- thesis dealing with the addition of hydrogen
TechPhys (English Transl) 8, 1001 (1964) bromide to unsaturated hydrocarbons, a
5) J. Roth, unpublished result (1965) 6) Ya. reaction which soon led to the proof of
B. Zel’dovich & Yu. P. Raizer, Physics of Shock structure of isoprene. He studied in both
Waves and High Temperature Hydrodynamic Germany and France and on returning to ‘ .
Phenomena, Vol 2, Acad Press (1967) Chapt VII Russia he presented a thesis on the synthesis
Sect 10-12 7) Yu. A. Zatsepin et al, ZhEksp- of isoprene. His work on decomposition of
TeorFiz 54, 112 (1968) & Soviet Phys JETP organic compounds at high temperatures with
27 (1) 63 (1968) special catalysts, he began about 1900. His
work on the dehydration and dehydrogenation
of alcohols and their combination in the
Ions; Action on Explosives. Kallmann & preparation of butadiene from alcohol” has
Schr3nkler (Ref 2) claim that Mercuric Ful- formed the base for much of the synthetic
minate, Azides & even TNT were initiated by ‘ tubber development in the US. He later
the action of H, Ar &“ Hg ions. This was not developed, the first high pressure bomb for
substantiated (Ref 3). Nitrogen Iodide is catalytic reactions, then found promoters
definitely initiated by cx-particles (Refs 1 & which aided the catalysts in their activity.
4) but it is atypical, see Iodidis and Initia-” From these discoveries branched his work
tion in this’ Vol in hydrogenation (both organic and inor-
Refs: 1) H.H. Poole, SciProcRoySoc (Dublin) ganic), isomerization, polymerization, con-
17, 93 (1922) 2) H. Kallmann & W. densation, cyclization, alkylation, and related
Schr%dcler, Naturenwissenichaften, 21, 379 reactions
(1933) & CA 27, 5979 (1933) 3) Bowden It was at his brother’s home that the
& Yoffe (1958) p 113 4) F.P. Bowden & Czar had taken refuge and was assassinated
A.D. Yoffe, Emleavour 21, 125 (1962) & at the time of the revolution in Russia.
CA 58, 1294 (1963) Dr. Ipatieff managed to continue his research
under the new regime but this became in-
IPA Composition. Recognizing that the creasingly difficult and he finally left Russia
hygroscopicity of Black Powder is due permanently, abandoning all his financial
largely to the charcoal, a non-hydroscopic assets. Through the efforts of Gustav Egloff
igniter-type pdr was developed. It was of Universal Oil Products and Ward Evans
found that substituting Tetranitrocarbazole of Northwestern University, who arranged
(See Vol 2, PC48-L) for charcoal results in for him to carry on work here, he came to
a compn, designated ‘IPA Composition, which the United States in 1931. He was denounced
 I 133

by the Soviet government for his refusal to colloid which binds the solid particles of the
return to that country and the honors which system together and prevents diffusion of water
had been conferred upon him were withdrawn # ;.. +,. a.. . U1-$ +La
A.
111 LU U1 UUL
-.,.,4..,.+.
LILG ~LUUU&L3.
n+t. c.. ~lllli,l~(ll
UL1lG1
. . .. . . . . .

Among his many honors were election to advantages of slurry explosives are substantially
both the American and Russian Academies increased safety, greater overall economy, more
of Sciences, the Willard Gibbs Medal of the favorable fume characteristics, and ease of
Chicago Section of the ACS, the Berthelot varying the energy and density to enable custom
Medal, the Lenin Prize, and honorary doctor’s designing of the explosive for each specific
degrees. Out of the income from a trust fund application to ensure optimum energy/cost
set up by Dr and Mrs Ipatieff the Ipatieff ratios. These and many other favorable char-
Prize was established several years ago which acteristics have enabled slurry explosives to
would encourage work in the field of catalysis replace conventional explosives in mining,
and high pressure quarrying, and construction operations around
At both the Universal Oil research laboratory the world
and the Ipatieff Catalytic Laboratory at North- Prior to its merger into IRECO Chemicals,
western (an extension of the original labora- Intermountain Research and Engineering Corn-
tory set up by Ipatieff) Dr Ipatieff was active pany (IRECO-founded in 1958) pioneered the
almost to, the time of his death early development of slurry explosives under a
Ref Anon, Chem & Engr News 30,5300 (1952) contract from the Iron Ore Company of Canada
(IOCC) who owned the original Cook and Far-
I RECO Chemicals. IRECO Chemicals was ‘or- nam invention
ganized in Salt Lake City, Utah, in 1962 from Although the original slurries had been .
a merger of Intermountain Research and Engineer- licensed by IOCC to major explosives manu-
ing Company and Mesabi Blasting Agents, Inc, facturers around the world, progress in the
for the purpose of commercializing slurry explo- marketplace for the first two years was slow.
sives. Slurry explosives were invented by Dr. In December 1959 HZECO conducted a test
Melvin A. Cook and H. Earl Farnam, Jr, in at the US Steel Pilotac operation on the
1956 and represent a major breakthrough in Mesabi Iron Range in northern Minnesota at
explosives technology, the magnitude of which the request of IOCC to promote the use of
can be compared with dynamite’s victory over slurry in open-pit blasting. The results were so
Black Powder in the 1860’s spectacular that a group of IRECO scientists
Slurry explosives are based upon a system quickly founded a manufacturing and sales
consisting of oxidizing agents and nonexplo- company called Mesabi Blasting Agents, Inc, or
sive fuel materials. The explosive energy derived MBA (in 1960), obtained a sublicense from
from these unique explosives is the result of IOCC, and began to manufacture and sell
extremely rapid reduction-oxidation reactions slurries on the Mesabi Iron Range. Within a
between the fuels and oxidizers upon initiation year MBA had successfully promoted the use
by a high explosive booster. A slurry explosive of slurry explosives in the mining industry
can be visualized as a colloidal system which me first-generation slurries were called Dense
comprises basically two phases, a dispersion Blasting Agents, or “DBA’s,” and comprised two
phase and a dispersed phase. The fundamental types: slurries sensitized primarily with coarse
concept which led to the discovery of slurry “Pelletol” TNT and slurries sensitized with
explosives was that an aqueous oxidizer solu- aluminum. Second-generation slurries, designated
tion (eg ammonium nitrate) could be used as the IREGEL 300 series, were introduced in
the dispersion medium of a colloidal system to 1969 as a replacement for the DBA’s except
disperse the required fuel (aluminum) and for DBA-221W, the first and only slurry yet to
thereby achieve a multiplicity of beneficial be completely qualified by the US Military
results The IREGEL 300’s were significantly
A particularly significant feature of the slurry stronger and more water resistant than their
explosives is that they are easily made water DBA counterparts by virtue of lower water con-
resistant by means of a suitable hydrophilic tent, ensured continuity of aqueous oxidizer-
 I 134

salt solution phase, and better thickening. In of being detonated after placement in the borehole.
1971 IRECO achieved another first with their By adjusting the settings on the control panel the
introduction of IREMITE, a cap-sensitive series pump truck operator can deliver a wide range of
of slurry explosives designed for use in small- explosive strengths and densities to meet individual
diameter bore-holes as a replacement for blasting requirements
dynamite. These versatile small-diameter products ‘The first SMS system was established for the
offer distinct safety, fume and performance ad- Kaiser Steel iron ore operation at Eagle Mountain,
vantages and are available in a wide range of California. The first SMS system outside North
diameters, densities, and energies and are suf- America was established in early 1965 at Phalaborwa,
ficiently revolutionary in concept to have the Sorth Africa, for the Palabora Mining Company.
same effect in the small-diameter applications as Shortly thereafter the SMS system was established
the SMS system (see below) did in large open-pit in rapid succession for mining operations through-
mining out the world
Yet another economically attractive series of In 1966 fifty percent of the capital stock of
slurries called the 2REGEL 600 series was intro- IRECO Chemicals was acquired by the Rio
duced in the US in late 1972. This series is also Tinto-Zinc Corporation, Ltd, a worldwide associ-
being manufactured today in Canada, South ation of mining and related industrial enterprises
Africa and Australia such as ore processing, smelting, fabricating metals,
In order to initiate slurry explosives and and the production of chemicals. Since that time
other modern blasting agents, IRECO Chemicals IRECO Chemicals has continued to grow and is
developed and patented the Procore booster–a today the ,wodd leader in the research, manufacture
booster designed for maximum safety with a and marketing of slurry explosives with operations
cap-sensitive core protected by a noncap-sensitive in important mining centers the world over
explosive shell comprising cast TNT or composition Written by M. GARFIELD COOK
B. These boosters are characterized by extremely
high detonating pressures. Because the booster Irradiation of Explosives with High Speed
requirement, as measured, for example, by the Particles was studied by Bowden & Singh.
minimum booster (MB) required to detonate a They subjected to irradiation a number of
blasting agent, varies as the reciprocal of the sensitive explosive crystals (such as Pb, Ag &.
detonation pressure (ie MB = K/pz ), Procore Cd azides, Ag acetylide and nitrogen iodide)
boosters are very efficient. For instance, the MB by electrons, neutrons, fusion products and
with a Procore booster is much smaller than the X-rays. All these substances were exploded by
MB with a gelatin dynamite or low-density an intense electron stream but it was shown
(powder) high explosive. “Quickness” (or absence that this was due to a thermal effect. Fission
of a transient build-up of detonation) in a products exploded nitrogen iodide but in the
booster is another important factor, which is other substances some changes within the
possessedalmost ideally by the original “Pentomex” crystals took place but no explosions. The
(cast pentolite) and the present Rocore boosters. experiments showed that, in general, the
Rocore boosters are “usedextensively in blasting activation of a small group of adjacent
operations around the world to initiate all types molecules was not enough to cause explosion
of modern blasting agents. They are manufidctured Also see articles on Initiation and on
in a wide variety of sizes and weights to meet Nitrogen Iodide (under Iodides) in this Vol
individual requirements Refs: 1) F.P. Bowden & K. Singh, PrRoyS
One of the most significant events in explosives A227, 23-30 & 33-5 (1954) & CA 49, 4991
history has been the development of the IRECO (1955) 2) Bowden & Yoffe (1958) Chapt VII
Chemicals Site-Mixed-Slurry (SMS) system, com-
monly referred to as the pump truck system, Iron Acetylide. See Acet ylides and Carbides
which is today the safest blasting system known. (Inorganic) in Vol 1, p A76-R
Nonexplosive raw materials are carried by the
pump ‘truck from the storage area to the borehole Iron Azide. See List of Inorganic Azides
site where they then become an explosive capable in Vol 1, p A543
 I 135

Iron Picrate. See Picrates ,, Isoamylureidoacetyl Azide. See iso-Amyl- ,,

ureidoacetyl Azide in VO1 1, p A399-R
Iron, Powder for Pyrotechnics. Sidorov et al
claim a spark-forming composition for ppg ,.,
fireworks which forms bright sparks of dif. 2-lsocyanate Benzoyl Azide. See 2-Azido-
ferent colors, containing a thermal mixt & formylphenylisocyanate in Vol 1, p A638-R
a metal powder, eg (Y~wt): ,N~ CIOq 55 t 5,
urotopine 14 I 2, iditol 8 * 2, metal powder !.

(Fe or steel chips, powdered Al or its alloy Isocyanic Acid. See Cyanic Acid in Vol 3,
.’ .,.,
with Mg) 23 t 5 (Ref 2) p C582~L
,.
The use of iron in smoke screens and in
signaling Cornpns is claimed by &M@..
Refs: 1), J. deMent, USP 299.5596 (1961) &, ,, Isobutane. See iso-Butane
,, in Vol 2, p B368-L
CA 55, 25100 (1961) 2):A.I. Sidorov et al, .“’
USSR P 201179 (1967) & CA 68, 61135
(1968) 3) US Spec MIL-I-12058B (Nov Isobutanediol. See iso-Butanediol in Vol
1969), Iron Powder for Pyrotechnics, ,[ 2, p B370:L ‘ “
.,
,,
Isano Oil. Isano oil, a“ conjugated triple-bonded
glyceride, when heated; sufficiently, reacts” Isobutanol. See under Butanol and Derivatives
exothermically with violence. Its uses & them ‘ in Vol 2, p B372-R e
reactions are described .‘ ,, .,,
Refi J.A. Kneeland et al; JAmOilChemistsSoc
35, 361 (1958) & CA 52, 15096 (1958) Isobutyl Alcohol. See under Butanol and De-
,’ rivatives ~ Vol 2, p B372-R
;.
Isazaurolin. (6-Oximino-A2 -dihydro-l’,2,4,5-
oxtriazin in Ger). (HO. N):~.NH.NH
Isobutyryl Peroxide. See Di-iso-butyryl Per-
O–N~H
oxide in Vol 5, p D1201-L
mw 116.08, N 48.27%; mp turns orange ca
85° and puffs off ca i 12-113° with loud :‘
report. Colorless needles which become
2-lsocyanatobenzoylazide. See 2-Azidoformyl-
yellowish on drying and then yellow-orange
phenylisocyanate in VO1 1, p A638-R
on storage. Was prepd by Wieland & Hess
(Ref 2) by treating methyl azaurolic acid ,,4 “
with coned HCI
Dissolves in dil miner~ acids (colorless) and Isocyanogen Tetraazide. (N3 )2 C :NN:C(N3 )Z, mw
in alkalies (orange-red). It’ is a mild explosive. 220.13, N 89.09%, OB to C02 –29. i%, mp 89°.
. Forms salts, as for instance Prepd by reacting tetrabromoisocy anogen,
Hydrochloride. C2H002Nq .HC1; “mp (dec 148- Br2C:NN:CBr2, dissolved in Me2C0 ‘with aq
150°) prisms (from abs alc with small amt of NaN3. Its use as an initiating explosive is
,,
eth); very sol in w; insol in alc claimed
Rejs: 1) Beil 27, 783 2) H. Wieland & H. Hess, Refi C.J. Grirndman & ,W.J.’ Schnabel, USP”
Ber 42, 4188-89 (1909) ‘ 2990412 (i961) & CA ,55, 25256 (1961)
,,

Isoamylamine. See under Amylamine in Vol Isomelamine. See Cyanuramide in Vol 3,

1, p A395-R ‘ p C589-L :.
,. ,:.>

Isoamylpicrate. See iso-Arnylpicrate in Vol lso-Me-NENA. Designation of N-@-Nitroxy-

1, p A399-R propyl)-nitramine or l-Nitramino-2-propanol
Nitrate described in Vol 1, p A253-L
 I 136

Isomers. Compounds having the same empiri- Isonitraminoacetic Acid. See Nitrosohydroxy-
cal formulas but ‘different molecular arrange- aminoacetic Acid under Hydroxylamine De-
ment, as well as different chemical and rivatives in this Vol
physical properties, are known as isomers
For instance, ortho, rneta and para-mononi- I ,,, ,
trotoluenes all have the same empirical formula, a-lsonitraminoacetoacatic Acid, Ethyl Ester.
C, H, N02, but the N02 group is attached to See 2-(Nitrosohydroxyhunino) -3-butanone-l -ic
different carbons of the benzene ring Acid, Ethyl Ester under Hydroxylamine Deriva-
tives in this Vol
Isomers of Trinitrotoluene. Severrd”isomers are
known: alpha, beta, gamma, delta, epsilon and
‘& ,
zeta (see Trinitrotoluenes, described under
a-lsonitraminopropionic 2-(Nitroso-
Acid. See
Toluene and Its Derivatives)
,- hydroxyhmine)-l -propanoic Acid under Hydroxyl-
The most important of these’ explosive iso-
amine Derivatives in this Vol
mers is the rdpha-trinitrotoluene, known as
TNT. In ,crude, commercial TNT, 4 to 5% of,
impurities are present, consisting mainly” of, a
Isooilefin Polymers of molecular wt 50000 to
mixture of beta-, or 2,3,4-, and gamma, or ‘
100000, such as Zsobu@lene polymer, were
3,4,6 -trinitrotoluenes. These impurities may
patented as thickeners for flammable naphtha
be removed by treating the crude TNT ~~
used in incendiary bomb mixts. Up to 25%
an aqueous solution of sodium sulfite. Ac,
may be incorporated. Small amts of metal
cording to Davis (Ref 3) the beta- and gamma-
soaps may replace part of the polymer. Ther-
isomers react with lead oxide in alcohol to
form lead dinitrocresolates, while alpha-TNT., rnite mixts, Na, K and P may also be included
in such an incendiary ffler
remains unaffected under similar conditions
Rejl H.H. Cooke, E. & J. Holzclaw, USP’S
Refs: 1) M. Copisarow, Chem News 118, 13-14
2445311 & 2445312 (1948) & CA 42, 7985
(1919) & CA 13, 791 (1919) 2) M.M. KOS-
(1948)
tevitch, Trinitrobenzene & Trinitrotoluene, Paris
(1927) 3) Davis (1943) p 147
Isonitramines are compounds having a general Isopicramic Acid. See 2,6-Dinitro-4-amino-
formula, R.N(OH).NO or likely phenol in Vol 1,, p A243-R
o
RN’-}NOH
where R stands for a radical, CH3–, C6H5 n Isoprene (2-Methyl-1,3-butadiene) Peroxide,
CH3C6H4– etc. They may be prepd by Polymeric. “(No formula given).
Resin~us
treating ketones or nitroparaffins in alcoholic substance; ,decomp slightly above 0[ Reported
solutions with nitrous oxide (N2 O) in the in Ref 2 as a highly explosive substance. May
presence of sodium ethylate be prepd by the reaction of isoprene with
For discussion of the; nomenclattire of ‘ molecular oxygen
isonitramines see Ref 3 ., Refs:
- . 1) Beil, not found 2) K. Bodendorf,
Metallic sits of these compounds were ArchPharm 271, 1 (1933) & CA 27, 4472
proposed by von Herz to be used in detona- (1933), 3) W. Kern et al, Makromol Chem
tors & percussion caps. Lead Methylene 3, 223 (1949) & CA 50, 1431 (1956) 4)
diisonitramine is specifically mentioned (Refs Tobolsky & Mesrobian (1954) 31 & 178
1&2)
Refs: 1) E. von Herz, BritP 241892 (1924) &
CA 20, 3574 (1926) 2) E. von Herz, USP Isopropyliden-di-cyclohexyliden-triperoxyd.
1625966 (1927) & CA 21, 2065 (1927) 3) One of the Ger names for the “Acetone Com-
Sidgwick (1937) p 455 pound”of 1,1‘-Bis(hydroperoxycyclohexyl)-
peroxide described in Vol 2, p B144-R
 I 137

Isopurpuric Acid or Picrocyaminic Acid. (or Iso-Trioil Resulting from Nitric Acid Purification
llicyandinitro-oxy-~-phenylhydroxylamine) of Crude TNT”, PAT R-DB-TR: 16-58 (Jan 1959)
CN
02 N
t-l
Hol
N02

4 CN
OH
mw 265.14, N 26.42Y0. It is an unstable com-
lsotrotyl is a yellow materird, mp 57-58°,
containing about 98% of alpha-TNT and its
isomers. It is prepd by nitrating the so-
pound of dark-yellow color, isolated for the called “liquid TNT,” containing 16.9-17.470
first time by Borsche and B6cker in fairly N with mixed nitric-sulfuric acid. It has been
pure state. It may be prepd by mixing its suggested that “isotrotyl” consists of addition
potassium salt with an ice-cooled aqueous compounds of the isomers instead of free
solution of phosphoric acid isomers. Since the alpha, beta and gamma
The salts of isopurpuric acid are easier compounds are practically of the same value
to prepare, are more stable and some are as explosives, this low-melting explosive
explosive, for example: (isotrotyl) was found to be useful as a con-
Potassium Isopurpurate. C~Hz 06 N5 K, mw stituent of blasting explosives, such as
303.24, N 23.1 O%. Brownish-red crystals; Roburite, Bellite etc. It was also used to
may be prepd by adding slowly, with agita- lower the melting points of other explosives,
tion, a solution of 10g of KCN in 40rnl eg TNX or PA
of Hz O to 10g of PA dissolved in 170ml Refi 1) M. Copisarow, ChemNews, 118, 13-14
of alcohol. The temperature should be kept (1919) & CA 13, 791 (1919)
below 30°. Stirring is continued for a while
after completing the addition of KCN and a-lsoxaloleazide. See under a-Isoxalolecarboxylic
then the mixture is left to stand. After Acid below
this, the precipitate is filtered off and
crystallized from about 1‘%1 of hot water. a-lsoxazolecarboxylic Acid and Its Explosive
The salt is fairly sol in w and easily sol Derivatives. i3N:CHCH:~C02H; mw 113.07,
in most organic solvents. It is a violent N 12.39%; pale yel trysts; mp 149°; bp (loses
explosive, very sensitive to impact and C02 on heating above its mp)
friction First obtained but not identified by Testoni
It puffs off at 215° & Mascareli (Ref 1) from products of reaction
Refs: 1) Bed 15, 61 2) W. Borsche & E. between acetylene and fuming nitric acid.
Bbcker, Ber 37, 4396 (1904) 3) L. Cody, Quilico & Freri (Ref 2) prepd it in the same
Traits th60rique et pratiques des mati&& manner and assigned to it the above structural
explosives, Namur (Belgium) (1907), p 562 formula
4) Not found in recent CA’s Quilico & Freri (Ref 3) used this acid to
prepare the “a-isoxazole hydrazide,
6N:CHCH:tC0HNNH2; mw 127.10, N 33.06%,
lso-Trioil. A product resulting from the purifi OB to CO ~ -106.8%; mp 141-42°, which on treat-
cation of crude TNT by recrystallization from ment with NaNO ~+HCl gave the explosive cx-
nitric acid. This process has been used in Europe Isoxazoleazide, 0N:CHCH:dCON3; mw 138.09,
on a production scale; however, the Sellite puri- N 40.58%, OB to C02 -73.9%, mp 37° (decomp);
fication process was selected for use in the USA. bp (explodes violently on heating above its mp)
Isotrioil has been found to be a satisfactory sub- Refs: 1) Testoni & Mascereli, Gazz 32 (l), 202
stitute for TNT in Dynamite consisting of (1902) 2) A. Quilico & M. Freri, Gazz 59,
RDX 78, TNT 15, cornstarch 5 & polyisobuty- 93041(1929) & CA 24, 3484 (1930) 3) M.
lene 2% and for DNT in the M-1 Propellant con- Freri, Gazz 62, 457-63 (1932) & CA 26,
sisting of NC 84.5, DNT 9.9, dibut ylphthalate 5954 (1932) 4) No further refs found under
4.9 & diphenylami,ne 1.WO Isoxazole derivs or Isoxazolecarboxylic acid
Refi J. Cussen, “Utilization of By-Product in CA 1947-1971
 I 138

Isoxazoleazo Derivatives of Trinitromethane IT or lncT. Abbreviation for Incendiary Tracer.

Prepared from Acetylene. In studying the See Incendiary Warfare in this Vol
reaction products of nitric acid with acetylene,
Quilico isolated an explosive product of yellow
color corresponding to the formula C4Hz 07 N6,
mw 246.10, N 34.15% ITALIAN EXPLOSIVES AND RELATED ITEMS
He assi ned to it tentatively the structural Introduction
formula -N:NC(NO,), and named During WWII, the Itaiians had several large
it cx-isoxazoieazotrinitromethane. The compd military explosives and ammunition plants and
melts with decompn at 78°, when heated some of its mining expls plants manufd military
cautiously, but when heated rapidly or struck expls. They produced materials of good quality
it explodes with a flame and in quantity nearly sufficient to conduct the
Refs: 1) Beil 1 {902} 2] A. Quilico, Gazz 62, war :
503-18 (1932) & CA 26, 5953-4 (1932) 3) List of Principal Italian Factories Manufacturing
No other refs found under Isoxazole derivs in Explosives and Related Items (Obtained thru the
CA 1947-1971 courtesy of Dr Omero Vettori, Director of
Cheddite Factory, near Aulla (Massa Carrara)
4-(3-lsoxazolyl)-3-furazancarboxylic Acid was (April 1975)’
prepd in complex sequence of reactions by Note: The firms marked with an asterisk are
Qualico & Freri (Ref 1). It melts ‘at 133° & still in production
decomposes ‘190° Section A, ,– Explosives and Propellants
Its Ag salt explodes weakly when heated. *1) B .P.D. (Bombrini-Parodi-Delfino), now
(No formulas for the acid or its salt are given) SNIA VISCOSA; factory in Colleferro, near
t?efs: 1) A. Qualico & M. Freri, Gazz 76, 3 Rome (Production of TNT, Propellants, Hunt-
(1946) & CA 41, 381 (1947) 2) No further ing Powder and Missiles)
refs found in CA 1947-1971 2) ACNA (Aziende Colori Nazionali Affini);
factory in Cengio (TNT)
3) SGEM (Societ~ Generale Esplosivi Muni-
I Isp. Abbreviation for specific impulse (some- zioni); factories in:
times called specific thrust) is the propulsive a) Carrnignano (TNT, PropeH”ants– for
impulse delivered by a propulsion engine per cannons and rifles) (destroyed)
unit weight of propellant. In the US the units *b) Pallerone, near Aulla (Double-Base
of Isp are lb-see/lb. It is related to measurable Propellants) (This factory is now the pro-
quantities by perty of the Italian A~y) ‘
c) Villafranca Lunigiana, near Aulla (Pro-””
&p = [Ve+ (pe–pa)f4J&J
/g pellants for cannons’ and rifles) (destroyed)
where the subscripts (e) refer to exit quantities, d) Avigliana, near Turin (RDX, PETN, ‘
and the subscript (a) refers to ambient quanti: Dynamites and Propellants) (Closed)
ties; V = product stream velocity, p = static e) Bussi e Pratole Peligna (RDX) (destroyed)
pressure, A = area, h = rate of mass flow & 4) Unknown Name Firm; factory in Narpi
g = gravitational acceleration (Ref 1). Typical (PETN) (This factory is now ‘tie property ,of the
values of Is for “ordinary” systems ‘is 200- Italian Army)
270 lb-see/l E and 270-400 lb-see/lb” for “high- *5) SIPE (Societ2 Italiano, Proilotti Esplodenti);
energy” systems (Ref 2). Theoretical calculations factories in:
of Isp (based on thermodyna~ci & thermochemistry) *a) ,Sp@nberto, near Modena (NC, PETN, “
are in good agreement with experimental mea- Fuse, Detonating Fuse, Primer & Dynamite)
surements (Ref 3) *b) Gallicano, near Lucca (now called SIPE
Refs: 1) O.E. Lancaster, Edit,’’Jet Propulsion NOBEL) (Biack Powder)
Engines,” Princeton Univ Press (1959) pp 440-441 *6) SGEM Factory at Orbetello (now SIPE
2) Ibid, p 453 3) Ibid, pp 464-475 4) AlSO NOBEL) (Dynamite Detonating Fuse, ,Industrial
see articles on Propulsion, “on Propellants & on Explosives, Blasting Caps, Shell Loading, “Deto-
Rockets nators)
 1139

7) Stacchini, Factory in Saliera Apuana, near (Shell Loading, Shell Manufacture, Mines, Ex-
Aulla (Black Powder) plosives Manufacture) (Now closed)
8) AFE (Azienda Forniture Esplodenti), ~ 12) Ditta $knmel, Factory in Castagnole
Factory in Stazzema, near Viareggio (Black Paese, near Treviso (Shell Loading, Assembly)
Powder) *13) Ditta La Precisa, Factory in Teano, near
*9) Polverificio Benedetto Cocciuti, Factory in Naples (Shell Loading, Primary Explosives,
Viterbo (Black Powder, Industrial Explosives, Primers, Caps)
Safety Fuse) *14) Cheddite Italia, Factory in Aulla (Massa
*10) Army Factory: Capua (Pirotecnico Eser- Carrara) (Shell Loading, )Usernbly, Detonating
cito) (Caps, Primers, Small Arms Ammunition) Fuse, Industrial Explosives, such as Cheddites)
11) Nobel SGEM Factory in Taino, near Section C – Industrial Explosives
Varese (Detonators, Blasting Caps, Primers, *1) Dinamite S.p.A. (Societii per Azi6ne),
Fuses, Primary Explosives (now closed) Factory in Mereto di Tombs, near Udine (Dy-
*12) Army Factory (Spolettificio Terre Annun- namites, DNT, PETN, Industrial Explosives, De.
ziata) (Fuze Production) tonating Fuse, Blasting Machines)
*13) S.R.C.M. (Societ?i Romana Costruzioni *2) Pravisani Esplosivi, Factory in Sequals,
Meccaniche), Factory near Rome (primary near Udine (Dynamites and other Industrial
Explosives, Hand Grenades, Caps, Primers) Explosives)
Section B – Shell Loading Piirnts: *3) SES (Societ~ Esplosivi Sicilian), Factory
*1) Army Factories in: in Latina (Industrial Explosives)
a) Piacenza (exploded in 1940) Section D – Small Arms Ammunition and Weapons
b) Noceto, near Parma (Laboratorio *1) Beretta Armi listed in Catalog
Caricamento Proiettili Esercito) *2) OTO MELARA, Factory in La Spezia
c) Baiano di Spoleto (Laboratorio Carica- (Manufacture of camons and missiles)
mento Proiettili Esercito) *3) Army Arsenals in Naples, Turin and Pia-
*2) Mangiarutti, Factory in Codroipo (Shell cenza
Loading, Industrial Explosives, Detonating Fuse) *4) BREDA MECCANICA BRESCIANA in
*3) Ditta Fratelli Rovina, Factory in Spilim- Brescia (Rifles and Pistols)
bergo (Shell Loading and Unloading) *5) Army Factory in Terni (Cannons and
*4) Ditta Fincati, Factory in Rossano Veneto other Weapons)
(Shell Loading and Unloading) *6) SMI (Societ2 Metallurgic Italiana),
5) Ditta Amelotti, Factory in Rivalta Scrivia Factory in Carnpotizzoro (Small Arms Ammu-
(Shell Loading) (Closed) nition)
6) Polverificio Stacchini, Factory in Bagni 7) Leon Beaux (Small Arms Ammunition
di Tivoli near Rome (Shell Loading and Load- including 20-mm (Now closed)
ing of Propellants) *8) Giulio Fiocchi Lecco (Small Arms Am-
*7) B.P.D. (Bombrini-Parodi-Delfino), now munition)
SNIA VISCOSA, Factory at Ceccano (Shell
Italian explosives, ammunition and weapons
Loading)
(small arms and artillery pieces) have always
*8) Sorlini Ing. Antonio, Factory in Ghedi,
been considered of very good quality. With the
near Brescia (Shell Loading, Compression of
exception of T4 (Cyclonite or RDX) and Tri-
Explosives, Industrial Explosives)
tolita (Cyclotol), which the Italians developed
*9) Sorlini Luciano, Factory in Carzago della
and used before both Great Britain and the
Rivera (Dynamites, Industrial Explosives, Deto-
USA, there are no high explosives of unusual
nating Fuse, PETN)
interest or originality y. However, there are
10) Ditta Vulcania, Factory in Fascia d’oro,
several explosives similar to the German
near Brescia (Shell Loading, Industrial Explo-
Ersatzsprengstoffe (Substitute Explosives),
sives, TNT Purification, Compression of Explo-
which were developed in Italy due to the short-
sives) (Now closed) .
age of aromatic compounds
11) Ditta Federico Marzan, Factory in
In the following pages are listed Italian ex-
Peschiere del Garda, near Verona (now SAIMA)
plosives, some of them obsolete. We are able
 I 140

to bring the list up to date due to the assist- Acido d’argento. See Azotidrato d’argento
ance of Dr Omero Vettori of Aulla (Massa
Carrara) and the appearance in 1974 of the Acido azotidrico (Hydrazoic Acid) is briefly
monumental work of Dr Camillo Belgrano, described in Ref31, p 429
“Gli Esplosivi”, contg 695 pages. It is the
2nd, greatly enlarged, edition of his 1952 Acido nitrico-sulforico (Nitric-Sulfuric Acid)
book (Ref 13). The new edition is listed as is described in Ref 31, pp 159–64
Ref31
ACIDO PICRICO O TRINITROFENOLO
Alphabetical List of Italian Explosives and [Picric Acid, abbrd PA or Trinitrophenol
Related Items (TNPh)] , also “called in Ital Melinita o Pertita,
Acapnia is one of the smokeless propellants, H0.C6H2(N02)3. Its prepn, props, uses and
listed in Belgrano (Ref31, p 581) and by analytical procedures are described by Belgrano
Molina (Ref 1, p 409). See under Polveri da (Ref 17, pp 281–87). Its props are: Density
Caccia (max) 1.68, Explosion Temperature 310°,
Temperature of Explosion 3200°, Heat of
Acardite or asym-Diphenylurea, described in Explosion 1040kcal/kg, Volume of gas at 0°
Vol 1 of Encycl (Ref 24, p A47-R), was de- & 760mm 675 l/kg, Specific Pressure 8900
veloped in Germany under the name of atm/kg, Trauzl Test 3 15CC,Detonation Velocity
Ahzzrdit. It has been used, accdg to Belgrano 7100m/s and Impact Sensitivity with 2kg wt
(Ref31, p 218) as a stabilizer in some Italian 40cm. Straight PA has been used for loading
smokeless propellants 100mm, 120mm & 149mm Shells and ‘in com-
posite expls, such as MABT, MAT, MBT,
Accenditori (Lighters) are devices serving to Polvere verde & Victorite (Ref 28, p 318)
light fuses (micce). In the catalog of Monte-
catini of 1959, Accenditori “Pirea” Monte- Acido di piombo. See Azotidrato di piombo
catini (p 40) and Accenditori “Dardo” Monte- (Lead Azide, abbrd as LA)
catini (p 41) are described
Acido stifnico o Trinitroresorcina (St yphnic
Accenditori in bacchette (Lighter Rods). Accdg Acid, abbrd as StA), (HO)2C6H(N02)3. It
to Belgrano (Ref 31, p 530), it is a fuse of diam is described in Ref 31, pp 453 to 455 and in
5 .5–5 .6mm and ca 10cm long ftied with a Ref 28, p 318. Used in the form of its lead
very slow-burning powder contg a finely pul- salt Stifnato di piombo (qv), meaning Lead
verized mixture of KN03 79.00, beech carbon Styphnate, abbrd LSt
3.75 & sulfur 17.25%
Afocite. A blasting expl compn existing in two
Accanditori Elettrici (Electric Lighters). A formulations: 1) AN (Ammonium Nitrate)
brief description is given in Belgrano (Ref31, 58–62, KN (Potassium Nitrate) 28–31, carbon
pp 514–1 5). In catalog of Montecatini of 1959, 7–9 & sulfur 2–3%; 2) AN 58–62, KN 3 1–38,
p 31, are briefly described Accenditori elettrici charcoal 3.5–4.5, sulfur 2–3 & moisture 1.5%
ritardati (Delay Electric Lighters) (Ref 28, p 318). The 1st formulation is also
given by Belgrano (Ref31, p 340)
Aceenditori Militari (Military Igniters). The
following items are described in TM9-1985-6 Ager (Esplosivi) expls are based on AN (or
(1953) (Ref 16): other inorg nitrates) and aromatic nitro-compounds.
a) Chemical Delay Igniter (pp 173–74 with Three compns are listed in the catalog of Scciet3
Fig 245) Vulcania at Brescia which gives their props &
b) Time Delay Igniter (Lead Shear Wire) (pp compns with numerical values: Ager C – Trauzl
174–75 with Fig 246) test value 320cc & detonation velocity 2800m/s;
c) Friction Delay Igniter-Miccia 40 and 60 suitable for use in quarries, with rocks of medium
(p 175 with Fig 247) hardness. Ager D – Trauzl value 400cc & deton
d) 50-Day Clock (pp 175–76 with Fig 248) vel 4700m/s; suitable for hard rocks. Ager E –
 I 141

Trauzl value 450cc & deton vel 3823m/s; suit- (Trinitronaphthalene) was used in some compns
able for work in hard ground. All three expls in lieu of TNT (Ref 28, p 319 and Ref 31, p
are nonpermissible (See also Ref 31, p 336) 367)

Albite. A white fusible mixture consisting of Ammondinamite. See “under DYNAMITE

AN 60, NGu (Nitroguanidine) 20 & GuN
(Ch.sanidineNitrate) 20%, introduced during Ammondite. Same as Ammonite No 1
WWI by Manuelli & Bernardino and used as
bursting chge in some shells (Ref 4, pp 342–44). Ammongelatina. See under DYNAMITE
The compn of Albite used during WI for
loading shells was AN 58.6, NGu 19.1 & GuN Ammonite No 1. A blasting expl consisting of
22.3% (Ref 24, Vol 1, p A120-L; Ref 28, p AN 88, DNT (Dinitrotoluene) 3, NG 3, vege-
318&Ref 31, p254) table flour 5 & DPhA (Diphenylamine) 1‘%
(Ref 28, p 319)
Alfa. Sporting propellant similar to Schultze’s
smokeless powder (Ref 31, p 581) AN–FO (Ammonium Nitrate–Fuel Oil), called
in Italy NA –OC (Nitrato ammonico-Olio
Alti esplosive. High Explosives (HE’s). See combustibili). Belgrano (Ref 31, pp 3 18–19)
Esplosivi alti gives a standard compn consisting of “prilled”
AN of density 0.70–0.75, 94.4 and combustible
Aivisi esplosivi. See Esplosivi Alvisi oil 5.6’ZO,Trauzl test value 295cc and detonation
velocity ca 400m/s
Amatolo, described in Ref 4, pp 240–41, is
similar to Amer or Brit Arnatol described in Anigrina Iamellare. Single-base smokeless,
Ref 24, Vol 1, pp A158-L to A164-L. Most sporting proplnt with NC completely gela-
popular was the mixture “tipo 60/40” (called tinized (Ref 31, R 580)
Esplosivo 60/40), which contd AN 60 & TNT
407.. Its deton vel is 6500m/see, and it was ANS (Esplosivo). Same as ASN
used cast-loaded in shells. Less powerful
(deton vel 4500m/s) was “tipo 80/20”, which Antifiama (Antiflame or Flame Suppressor) and
was used press-loaded in sea-mines (Ref 4, p Refrigerenti (Cooling Agents). Belgrano (Ref
241 ). Still less powerful was a 90/1 O mixt 31, pp 2 19–20) lists: vaseline, mineral oils,
with deton vel 2500m/s, used in mining opera- acardite, NGu (Nitroguanidine), Nitronaphthalene,
tions (Ref 28, p 319 and Ref 31, p 243) (Com- inorganic chlorides, Amm sulfate, oxalates of
pare with MNDT, MST and Nougat) Amm, Na & K and K tartrate as cooling agents
or flame suppressors for Dynamites
Ammonaftite. Mining expl contg AN 76.7,
NG 15.0, Collod Cotton 0.3 & grain flour Antigrandine: Esplosivi, Cannoni e Razzi.
8.0% with 0.5% of yellow ocher incorporated (Antihail: Explosives, Cannons and Rockets).
(Ref 31, p 83) As bursting charge explosives for antihail pro-
jectiles, TNT and some Cheddites were used in
Ammonal, described in Ref 4, pp 237–40, Italy. An antihail cannon is illustrated on p
was similar to Austrian, Brit, German, French 337 of Ref 31, whereas a rocket is on p 626
and Amer Ammonals described in Ref 24, Vol Addnl Ref porn CA: L. Peseni, ItalP 518413
1, pp A287-L to A292-R. The Ital Army used (1955) & CA51 , 17170 (1957) (Antihail
during WWI the mixture: AN 71 –72, Al powder rockets designed to reach an altitude of 1800m
22 & tar (bitume) 6–7%, under the name are supplied with BkPdr mixture contg KNOs
Nitramite (Ref 4, p 238). Several formulations 24, charcoal 5 & sulfur 0.65kg)
used during WWII contd AN 46–64, Al 17–22,
TNT 15–30 & carbon 35Z0.Such a compn was Antigrisou (Esplosivi) o Esplosivi antigrisutosi
known as Toluol-ammonal or T-ammonal. TNN (Permissible Explosives). The following are
 I 142

listed in Ref 31, p 326: Antigrisou A?0 – 12.7-mm APIT (Armor-piercing Incendiary
AN 80.57, DNN (Dinitronaphthalene) 6.36 & Tracer) (White Tip) (p 72, Fig 85); 12.7-mm
AChl (Ammonium Chloride) 13.02%; Anti- HE (High Explosive) (p 72, Fig 86)
~“SOU IV.2 – AN 81.49, DNN 11.11 & ACM In “MUNIZ1ONAMENTO ITALIANO”
7.40%; Anti@”sou IV 3 – AN 82, TNN (Tri- (Addnl Ref C) under Cartucce (plural Cartucci)
nitronaphthalene) 5 & ACM 13% are listed Cartucce Cal 6.5 per Moschetto (Car-
Requirements for Italian permissible explosives bine) Mod 91/38; Cartucce Cal 7.35 per Fuccile
are given by Belgrano (Ref 31, pp 327–29), (Rifle) e Moschetto (Carbine) Mod 38; Car-
while tests are described on pp 329–32 tucce Cal 7.65 per Pistola Berretta; Cartucce
Cal 8 per Mitragliatrice (Machine Gun) Mod 35
Antisanzionite. See ASN e Breda Mod 37; Cartucce Cal 9 per Mitraflia-
trice Mod 38; Cartucce Cal 9 per Pistola auto-
Antonite (Esplosivi ). Mining expls manufd by matic Berretta Mod 34; Cartucce Cal 10.35
the Societ~ Vulcania at Brescia. Two compns per Pistola Mod 39; Cartucce Cal 13.2 per
are listed in their catalog of 1960; in Ref 24, Mitragliera d’Aereo (Aerial Machine Gun)
Vol 1, p A473-L; and in Ref 31, p 317: Actually cartucci are complete rounds of
Antonite per cava – for work in quarries – small-arms ammunition, while cartocci are
consists of AN & TNT in proportion to make complete rounds of artillery ammunition
O content 5.9% by weight; Trauzl test value
340cc and deton vel 3400m/s Armi subacquee (Underwater Weapons). They
Antonite per galleria – for work in tunnels – include: siluri (submarine torpedoes), bombe
consists of AN & TNT in proportion to make torpedini di profunditii (depth bombs), mine
O content 3.08%; Trauzl value 4 15CCand deton subaquee (underwater mines), etc. Their teste
vel 4000m/s (warheads) can have as bursting charge (carica
esplosiva) Tritolital (TNT 60, RDX 20 & AJ
Aquila. A smokeless, sporting proplnt with 20%); Tritolito (RDX 40 or 60 incorporated
completely gelatinized NC (Ref 31, p 580) in fused TNT 60 or 40%) or Torpex (RDX 44,
TNT 38 & Al powder 18%) (Ref 31, p 382)
Ares. A powdery mining expl based on AN &
a combustible (Ref 31, p 317) Artifici da guerra – Military Pyrotechnics.
See under PIROTECNIA
Aria liquida e Ossigeno Iiquido (esplosivi].
Liquid Air and Liquid Oxygen Explosives, such ARTIGLIERIA ITALIANA – Italian Artillery
as Oxyliquit or LOX have been used in high Its history is described in the book of
mountain hydroelectric works by the Ital Corps Generrd Carlo Montu (Ref 3). Artillery pieces
of Engineers (Genio Militare) (Ref 15, p 38 & used during WWI & WWII are described by
Ref 31, p 305) the late Col J.B. Jarrett in Ref 5a (illustrated)
It would be well to remember that Italian
ARMI PORTATILI MUNIZIONI (Small-Arm practice is to refer to the caliber in millimeters
Ammunition). The ammunition used during followed by the tube length in calibers. Thus,
WWH was similar to British and German ammo. 65/17 means a 65-mm bore diam and a tube
The following types are described in TM 9- 17 calibers long
1985-6 (1953) (Ref 16, pp 65–72): 6.5-mm Following Chart is copied in abbreviated
Ball (p 67, Fig 76); 7.35-mm Ball (p,67, Fig form from Ref 5a, p 668
77); 7.7-mm Ball (p 68, Fig 78); 7.7-mm API
(Armor-piercing Incendiary) (Blue Tip) (p 68,
Fig 79); 7.7-mm APIncendiary (Green Tip)
(p 69, Fig 80); 8-mm Ball (p 69, Fig 81);
8-mm AP (Armor-piercing) (p 70, Fig 82);
12.7-mm Tracer (Red Tip) (p 70, Fig 83);
12.7-mm Incendiary (Blue Tip) (p 71, Fig 84);
 I 143

CHART I
Breakdown of Important Data Concerning the Most Used Italian Pieces
Range
Designation (f::c) (yds) Ammunition
:65/17 1,140 7,100 *’ HE, AP-HEC&BC, Hollow chge
75/13 1,240 9,000 HE, AP-HEC&BC, Shrapnel
75/18, Model 34 1,300 10,300 HE, AP-HEC&BC, Shrapnel, HoI chge
(This piece was found on 3 carriage models, and was also used on the Semovente or S.P. M13/40 tank version)
75/27, Model 11 1,640 11,100 HE, AP-HEC&BC, Shrapnel, Hol chge
(A modification of this weapon was seen on S.P. carriages)
75/34 1,650 13,500 HE, AP-HEC&BC, Hollow chge
(streamlined shells)
77/28 1,762 ,, 7,300 HE, shrapnel and case shot
(Originally Krupp 1896 design)
100/17, Model 14 1,400 10,100 HE Shrapnel, Hollow chge
105/28 1,880 15,000 HE (several patterns flatbased
and streamlined)
149/12, Model 14 1,100 7,500 HE and Shrapnel (several patterns of HE)
149/13, Model 14 1,100 9,600 HE and Shrapnel (several patterns of both)
149/17 1,660 ‘ 12,500 HE, Shrapnel (several patterns)
149/40 (Modern gun) 2,600 23,900 HE (2 patterns)
152/ 13 Howitzer 1,300 10,400 HE (several patterns)
152/37 2,270 21,800 HE (several patterns)
210/22 1,870 . 17,400 HE and an AP (likely anti-concrete)
(Not seen in Africa)
305/8 1,300 12,000 HE (base fuzed and Shrapnel)
(Skoda mortar 1916 and not seen in Africa)

Antiaircraft Artillery (AA Guns)

—
Vertical
Range
(feet)

2-cm Breda . 2,755 7,000 HE, SD and AP

2-cm Scotti 2,720 7,000 HE, SD and AP
37/54 Breda 2,620 13,500 HE – time fuzed
HE – PD fuzed
75/27 Krupp .1,500 HE and AP
75/46 Ansaldo, Model 34 2,350 27,200 HE and AP ,
75/50 Skoda 2,690 30,000 HE
75/53 French, Model 30 2,280 31,000 HE
76/40 Ansaldo 2,460 31,000 HE
90/53 Ansaldo 2,500 39,300 (?) HE and AP
 I 144

Following addnl info is taken from p 669 tillery projectiles used during WWI was: AN 65,
of Ref 5a: TNT 20, Na nitrate 10 & DCyDA 5% (Ref 4,
CHART H p 244)
Antitank (A/T Guns)
ASN of Tonegutti, proposed after WWI consisted
47/32 Breda
of AN 70, PETN 20 & DCyDA 10%. It melted
47/32 Austrian Boehler
at 115° and was suitable for cast-loading shells
47/50 Schneider (French captured)
(Ref 4, p 245 & Ref 24, Vol 1, p A496-L).
75/27 Series, using AP, Hollow charge
ASN of Tonegutti, proposed before WWII, con-
75/46 AA Dual purpose
sisted of AN 60, PETN 20, DCyDA 10 & GuN
90/53 AA Dual purpose
(Guanidine Nitrate) 10%. It hasa low mp (104”)
100/17 series, using AP, Hollow charge
due to the presence of DCyDA & GuN. It was
Seacoast Guns used during WWII for loading Naval shells. When
57/30 used in underwater ammunition, such as torpe-
57/43 does, depth charges & sea mines, its efficiency
120/21 was increased by incorporating some Al powder
Same ammunition
120/25 } (Ref 28, p 320 and Ref 31, p 181 under Anti-
120/40 sanzionite)
149/35
152/32 Aster. A smokeless, sporting proplnt with NC
Same ammunition
152/50 } completely gelatinized (Ref 31, p 580)
280{9 (two versions)
280/10 Astralite 1 e 2 were ltal AN+TNT+NG+woodmeal
280/1 1 Same ammunition expls manufd during WWI by the Societ?i Dina-
280/16 1 mite Nobel, Avigliana (Ref 15, p 32)., They
305/17 were used as fillers for trench mortar shells
305/50 and hand grenades. The expls were similar to
381/40 German Astralits listed in Ref 24, Vol 1, pp
420/12 A497-R & A498-L. Belgrano (Ref 31) lists
Abbreviations: on p 122 the ballistic mortar strength of Astralit
AP = Armor-piercing antigisou ? crirsse as 4.75% of Gelatina 92/8
A/T = Antitank (Sprenggelatine), but gives no compn
HE = High Explosive Accdg to Ref 28, p 320, Astralites are now
HEBC = High Explosive, Ballistic Cap used in mining operations
HEC = High Explosive, Capped
Hol chge = Hollow (or Shaped) Charge Avigliana 3. See Nitramite
PD = Point Detonating Fuze
SD = Self-destroying Azotidrato d’argento (Silver Azide–SA)o
SP = Self-propelled Acido d’argento, AgN ~, is “described in
Belgrano
Note: In the opinion of Col G.B. Jarrett, the (Ref 31, pp 449-51). Trauzl vahre for 2g
Italian artillery support to other arms per- sample 22.5cc, Detonation Velocity 5700m/see,
formed poorly during WWII, even though the Temperature of Explosion 3545” & Detonation
Italian gunners were usually very brave men. Temperature 297° (Ref 31, pp 447 &45 1).
Briefly, their troubles lay in poor design of Small quantities of SA are used in primers
both carriages and ammunition (Ref 3, pp 663– (Ref 28, p 318) (See also Ref 24, Vol 1, p
64) (See also CANNONE) A597-R to A601-R)

ASN (Antisanzionite) o Esplosivo ASN (Called AZOTIDRATO DI PIOMBO (Lead Azide-LA)

ANS inRef 31, p 181). A castable AN expl o Acido di piombo, Pb(N S)z, is described by
compn contg DCyDA (Dicyandimide) for lower- Belgrano (Ref 31, pp 439–49). Its props are:
ing the mp of AN. Compn of a fdler for ar- Density (max) 4.79, Explosion Temperature

I
 I 145

327°, Temperature of Explosion (Flame Tem- & deton vel 3550m/see; used in galleries not
perature at Explosion) 3350°, Specific Volume contg fuedamp
310 I/kg, Heat of Formation –364kcal/kg, Impact BM. as. per uso a cielo aperto – reddish pdr
Sensitivity with 2kg wt 8cm, Trauzl with IOg consisting of AN, with cyclic aliphatic compds &
sample 115CCand Detonation Velocity 5300 metallic pdrs; Trauzl value 470cc & deton vel
m/see. It was manufd by Nobel SGEM at 41 00m/see; used in open-cut quarries with rocks
Tiana, near Torino and by Bombrini-Parodi- of medium hardness
Delfino SA at Colloferro-Roma. LA nearly BM. ac. per uso a cielo aperto – brownish-yel
entirely replaced MF (Mercuric Fulminate) as pdr consisting of AN & TNT; Trauzl vahse 450cc
an initiating detonating agent of priming compns. & deton vel 3800m/see; used in open-cut
It can be used alone but is preferable to use it quarries
with LSt (Lead Styphmte) which is more sen- BM. 57. per uso a cielo aperto – grayish-black
sitive to flame initiation (Ref 28, p 318) (See pdr based on AN; Trauzl value 370cc & deton
also Ref 24, Vol 1, pp A545-L to A563-L) vel 2050m/see; used in open-cut quarries with
materials of medium hardness, such as limestone,
clay, soil for cement, etc
Balistite (Ballistite). A double-base propellant Super BM. per galleria – green pdr, d plastic
with high NC content was invented in 1887– contg aromatic nitrocompounds with org nitrates
1888 by A. Nobel. Several formulations were and plasticizers; Trauzl value 420cc & deton
developed later and used in many countries. vel 5000m/see; used for blasting in galleries
The varieties used in Italy are listed in Ref 24, contg no firedamp
Vol 2, pp B8-R & B9-L. Balistite al 60, which BM. a2 – brown pdr contg AN, TNT & thermite;
contd NG 60 & NC 4070 with 1–2!Z0stabilizer Trauzl value 440cc & deton .vel 3000m/see;
added, was too erosive for use as a proplnt in used in open-cut quarries with soft & medium
guns, but proved to be very suitable for use as hard rocks; also in agriculture, such as for de-
a bursting charge in some smaller caliber shells, struction of tree stumps, etc
such as 37/40mm HE and 37/40mm HEAP Super BM. Cava – gray pdr of density 1.20;
(High-Explosive Armor-Piercing) compn not given; Trauzl value 5 10cc & deton
Belgrano (Ref 31,) lists on p 205: Balistite vel 4600m/sec; used in quarries for blasting
ordinan”o cent ains NG 50 & CC (Cotone col- very hard materials such as granite
lodio) 50%; Balistite a basso titolo cent NG 42 BM. 2 per gallerk – gray pdr contg inorganic
with CC & other ingredients; Balistite attenuata nitrate, org nitrocompounds and Al pdr; Trauzl
cent NG 25, Pirocollodio 60 & liquid DNT 15Y0. value 450cc & deton vel 41 00m/see; used in
Every compn contained ca 0.5% DPhA (Diphenyl- gallerias contg no firedamp
amine) added (See also Ref 4, p 181) Note: BM is mentioned in Ref31, p 317 w/o
giving compn or props
Bassi esplosivi. See Esplosivi bassi
Boceda. Sporting smokeless proplnt with com-
Barsaglio. Target pletely gelatinized NC (Ref31, p 580)

Bicchiere. Projectile’s Case or Body. See Bombs atomica is briefly described by Belgrano
PROIETTO O PROIETTILE (Ref31, pp 5 19–20). General description is
given by C.G. Dunkle in Ref 24, Vol 1, pp
Blasting Gelatin. See Gomma A A499-L to A500-L. Historical development is
discussed on p A500-L, under “Atomic (or
BM (Esplosivi Mangiarotti). A series of mining Nuclear) Energy”
expls manufd by the Societ2 Mangiarotti,
Codroipo (Udine). The following formulations BOMBA (plural Bombe) – Bomb (Bombs),
are listed in their catalog of 1960: Conventional
BM. 1. per galleria – gray powder consisting of Italian bombsof WWII are described in
TNT, AN & thermite; Trauzl test vahse 440cc OP 1668 (Ref 8, pp 1–27) and in TM 9-
 I 146

1985-6/TO 39 B-lA-8 (Ref 16, pp 1–27). They Following are Italian terms for bombs and
were constructed of more than one piece, being for ‘some grenades:
assembled by screws or rivets, or welded. They
were usually filled thru the base, which was
closed by a base plate, attached by screws or Bombs a mano Hand grenade,
rivets. The bombs were generally constructed Bombs a mano contro Anti-tank grenade
of sheet steel but in some cases afuminum alloy i carri armati
was used. Demolition bombs were usually Fragmentation grenade
Bombs a mano dirompente
constructed of mild steel, while armor-piercing
bombs (AP) were made of hardened steel. The Bombs antisommergibile; Depth bomb or
anti-personnel (A/P) bombs differed from demo- (bombs da getto; depth charge
lition bombs in construction; in one type (Type bombs di profondit~ o
F) the filling was enclosed in a sheet container, bombs torpedine)
on the outside of which a steel strip was wound Bombs da demolizioni Demolition bomb
spirally, while in another type (Type Mtr) the Bombs da tromboncino Rifle grenade
ffling was contained in a sheet-steel case which
Bombs dirompente Fragmentation bomb
was enclosed in a larger container. The space
between the two containers was ftied with steel Bombs fumogena Smoke bomb
fragments Bombs incendiaria Incendiary bomb
The majority of bombs contained tail fuzes
Bombs leggiera Illuminating bomb
but quite a number contained nose fuzes. Some
medium and large bombs, eg, 100, 250, 500, Bombs luminosa Flash bomb :
800 and 1000 kg, contained both tail and nose Bombs perforate Armor-piercing bomb
fuzes
The principal bomb ffling was cast Tritolo Granata bombs Demolition bomb
(TNT); however, quite a few bombs were fdled Bombs da esercitazione Practice bomb ~
with Amatol; and, in the case of shaped-charge
bombs, with a mixture of T4 (RDX) 60, TNT
38 & wax 2%
The bombs were either grdvanized or painted
to protect them from corrosion. The follow-
ing colors were used to identify different types:
Color of
Type of Bomb Body Nose
Fragmentation (F) Blue Red
High Explosive (HE) Grey Red
Anti-personnel (A/P; Black Red
or
Blue
Incendiary (IB) Reddish Red
brown
Gas (G) Bright Red
Yellow
Practice Grey Grey
 I 147

Table

Listing Names, Dimensions, Explosive Charges and

Fuzes Used in Italian Bombs of WWI I

American Italian Overall laximum Type of Weight o Total Fuze

Designation designation Length liameter Filling Filling Weight
of Bombs of Bombs [inches) [inches) (kg) (kg)
2 kg A/p F 6.0 4.5 TNT 0.38C 1.72 Tail, Type K
2 kg A/P Mtr 6.0 4.5 TNT 0.22C 1.87 Tail, Type K
3 kg A/P Mtr 12.1 8.2 TNT 0.17 3 Nose, Type M
4 kg A/P Manzolini 12.3 7.3 TNT 0.67 3.68 Manzolini Types
(Thermos) I&II
12 kg A/P F 32.4 17.3 TNT 1.93 12.20 Nose, Type F
12 kg A/P Mtr 3.5 3.5 TNT 1.90 12.88 Nose, Type J
14 kg Frag I 22.1 4.2 TNT 2 14 Nose, Type I
14 kg Frag H 22.1 4.2 TNT 2 14 Nose, Type I
24 kg GPHE — 30.5 6.4 TNT 12 24 Tail, Type N-1
40 kg GPHE — 32.3 9.0 TNT Unknow: 40 Tail, Type N-3
50 kg GPHE — 40.5 9.9 Amatol 29.20 59.31 Tail, Type C or Y
100 kg GPHE — 51.3 10.7 TNT 50.6 100 Tail, Type C or Y
(appr)
100 kg GPHE — 51.3 10.7 Amatol 49.5 100 Tail, Type C or Y
(appr)
250 kg GPHE — 73.8 17.6 TNT 125.7 259.1 Nose, Type A and
Tail, Type O
500 kg GPHE — 96.6 18.0 TNT 216 508 Nose, Type A and
Tail, Type O
800 kg GPHE — 127.8 18.0 Jnknown 357 821.6 Nose, Type A and
Tail, Type O
1000 kg GPHE — 140.0 20.5 TNT Unknowx 000 Nose Fuze Only
appr)
500 kg GPHE — 93.7 18.1 TNT 247.0 Jnknown Nose and Tail
Time Bomb Fuzes
15 kg SAP — 31.0 4.7 TNT 5.2 15.5 Tail, Type N
31kg SAP _ 31.7 6.4 TNT 10.5 31.0 Tail, Type N-2
(appr)
100 kg SAP — 50.5 9.9 Amatol 27.3 109.0 Tail Fuze, Type
C-1 or Y-1
104 kg SAP — 43.0 10.0 TNT 104.0 Tail, Type C
(~pr)
12kg Sm — 47.0 5.2 ;m compl — 28 Nose Fuze
0.5.kg Inc 1P 6.1 2.75 :otton Tail, Type K
vicks (a~p~)

n
;asoline
0.5 kg lnc IT 5.1 2.5 rhermite — Tail, Type K
(a~p~)
0.5 kg Inc FI 4.9 2.5 Phosph — Tail, Type K
(a~p~)
1 kg Inc I&II 6.1 2.7 vlg powd 0.08L Tail, Type K
rhermite 0.47: (a~pr)
(Continued)
 I 148

Table (Italian Bombs) (Continuation)

American Italian Overall Maximum Type of Weight of Total Fuze

Designation Designation Length Diameter Filling Filling Weight
of Bombs of Bombs (inches) (inches) (kg) (kg)
~.
2 kg Inc 12.2 2.7 Thermite 0.321 2.12 Tail, Type K
oil 0.339
2 kg Inc 11 12.2 2.7 Mg, HgO Unknown Unknown Tail, Type K
& MNB
20 kg Inc — 34.0 6.3 Thermite 10.58 20.17 Tail, Type E
70 kg Inc — 47.2 9.9 Thermite 36.6 74.5 Tail, Type E
100 kg Spec — 532.0 10.7 TNT Unknown 113.0 Nose, Type X &
(Combination .
A{P bomb& 8~fl Tail, ”Type Z
bomb container)
15 kg Gas — 31.0 4.7 DPhCIAr 3.65 16 Tail Fuze
TNT 1.7
(burster)
25 kg Gas Furretta 32.7 6.3 Lacrym 10.0 25 Tail, Type K
40 kg Gas (C40 P) 32.3 9.9 DPhCIAr 6.5 47 Tail Fuze
(A) Burster 13.0
40 kg Gas (C40 P) 32.3 9.9 Mustard 14.7 40.6 Tail Fuze
(B) Burster 0.18
55 kg Gas — 32.3 9.8 Phosgene 20 55 Unknown
Burst er 18
100 kg Gas (Cloo P) 50.2 10.7 DPhCIAr 14.3 101.9 Tail Fuze
Burster 28.7
250 kg Gas — Unknown 18.0 Mustard 214 264 Nose Fuze
(appr)
500 kg Gas (500T) 96.6 18.0 DPhCIAr 210 298 Nose, Type T
5 kg Vento – 17.4 5.2 Sm or Unknown 5.2 Nose, Type S
-Markerfa) Inc
160 kg A/S (Cs) 69.8 13.3 TNT 99 176 Nose & Tail Fuzes
160 kg HE 62.4 12.6 TNT Unknown 163.5 Nose Fuze
3kg AA (c;) 13.5” 3.2 Amatol 0.40 3.0 Nose, Type I
20 kg AA (Cv) 30.7 5.5 Unknown Unknown Unknown Nose, Type I
3.5 kg HoC – 18.8 6.0 RDX 60 22 3.5 Tail Fuze
TNT 38 (appr)
wax 2
5 kg HoC — Unknown Unknown Unknown Unknown Unknown Tail Fuze
25 kgHoC — Unknown Unknown Unknown Unknown Un~own Tad Fuze
50 kg HoC — Unknown Unknown Unknown Unknown Unknown T~ Fuze
100 kg HoC — Unknown Unknown Unknown Unknown Unknown Tail Fuze
3omb Con- — 5 ‘6” 11 AP or Unknown 23 –
airier (b) Inc (empty)
‘arachute Martellona 36.9 4.0 Unknown Unknown Nose, Type L
‘Iare (appr) (po~der)
‘arachut e — 12.5 1.45 Unknown Unknown Unknown Friction Igniter
~lare (cardboard) for Nose
 ,

I 149

Abbreviations: AA Antiaircraft; AP Arrnor- Fuze) (p 51); one CLDNF (Clockwork Long-

piercing; A/P Antipersonnel; appr approxi- Delay Nose Fuze) (p 52); one CLDTF (Clock-
mately; A/S Antisubmarine; C, CS and CV work Long-Delay Tail Fuze) (p 53); one Tail
Italian designations for bombs; Compn Compo- Fuze for Hollow Charge Bomb (p 56); one
sition; Design Designation; diam diameter; Hydrostatic Tail Fuze–’’Grand Daddy” (p 57);
DpHCIAr Diphenylchloroarsine; F Ital designa- one MINF–’’Orphan” (p 58); and one Mecha-
tion (See note c); Frag Fragmentation; GP nical Anti-Disturbance Fuze—’’Manzolini”
General purpose; GPHE General purpose high (pp 59-60)
explosive; HE High Explosive; HoC Hollow Italian terms for Fuzes are given under
(shaped) charge; Inc Incendiary; Lacrym Spoletta (plural Spolette)
Lacrymator; MNB Mononitrobenzene; Mtr
Italian designation (see note d); Phosph Phos- Booster Charge. See Carica di rinforzo
phorus; SAP Semi-armor-piercing; Sm Smoke;
Spec Special Borani - Propellenti liquidi per razzi (Liquid
Notes: Rocket Propellants) consist of liquid hydrogen
a) The Vento Marker was used in conjunction with boron or other light element, such as
with chemical bombs to indicate the force and beryllium (Ref31, p 129)
direction of the wind at ground level. Two
fillings were used, a smoke falling in the daytime BOSSOLO (plural Bossoli). Accdg to the
and an incendiary filling for use at night “Military Dictionary ”,, listed here as AddnlRef ~
b) The Bomb Container was a bomb-shaped A, it can be translated as Cartridge &se, Shell
hollow body of sheet metal, holding 8 columns Gzse or Shrapnel. This signifies that the term
of A/P or hcendiary bombs bossolo has several meanings and the same con-
c) “F” Bomb consisted of a thin steel cylin- clusion can be drawn after reading the following:
der surrounded by a tightly coiled spring of Belgrano (Ref 31, p 611) describes only
rectangular cross section. The object of the bassoli da caccia which are cardboard or plastic
spring was to provide shrapnel effect. In cartn”dge cases used in sporting (hunting) am-
fragmentation, the bomb usually broke into munition
pieces about 1“ x 0.2” x 0.18“ Accdg to “MUNIZIONAMENTO ITALIANO”,
d) “Mtr” Bomb consisted of two cylinders of “ listed as AddnlRef C, bossoli for small arms’
sheet metal, The imer cylinder contained the ammunition are cartridge cases, usually made of
explosives, and the outer cylinder was threaded brass, provided with percussion primers at their
at the top to take a screwed circular cover. base. These bossoli serve as containers for, pro-
Between the two cylinders were small steel pelling charges (cariche di lancio). In case of
pellets embedded in concrete fixed or semi-fixed artillery ammunition, such
as for granata perforate (armor-piercing shell),
Bomb Fuzes – Spolette per bombe bossolo is a brass tube located inside a cartridge
Italian Bomb Fuzes used during WWII case and attached at its perforated base to a
were mechanically operated, except for Time percussion primer. The bossolo is loaded thru
Fuzes (Spolette a tempo) tised in 500-kg its upper open end with an easily ignitable
Time Bomb. Most of the fuzes functioned on mixture, usually Black Powder (polvere nera,
impact. Normally the fuzes were made of abbrd as p.n.), which serves to ignite on striking
brass, steel or Al and were coated with shellac the percussion primer with a trigger, the pro-
or varnish to prevent corrosion. Both nose pelling charge (carica di lancio) in the cartridge
and tail fuzes were used case. This type of bossolo may be called a
Technical Manual TM 9-1985-6 (Ref 16) Powder Tube or an Igniter Tube (Compare
lists twelve types of MINF (Mechanical Impact with Igniter Tubes described in Ref 24, Vol 1,
Nose Fuzes) (pp 29–39); nineteen MITF (Me- p A385-L and in Vol 2, p C75-R)
chanical Impact Tail Fuzes) (pp 40–49 & 54– (See also under CARTOCCIO)
55); three MTNF (Mechanical Time Nose Fuzes)
(pp 49–50); one ETNF (Electrical Time Nose Burster. Charge. See Carica di scoppio
 I 150

C (Polvere). A smokeless propellant with NC Gmnone automatic – Automatic Gun

of 12.570 N completely gelatinized with ether- Cannone corrtro i cam” armati – Antiarmored Vehicle Gun
alcohol (Ref 31, p 580). Do not confuse with Cannone da campagna – Field Gun; Field Piece
Miscela C (qv) Cannone da carro armato – Armored Vehicle Gun; Tank Gun
Cannone da costs – Coast Artillery Gun
C-2 (Polvere) o Cordite Italiana. A double- Cannone da esercitazione – Drill Gun
base proplnt manufd by Societ?i Dinamite Nobel Cannone da montagna – Mountain Gun
at Avigliana for use during WWI and WWII. Its Cannone d’assedio – Siege Gun
compn as given in Ref 31, p 210 is NC 70.5, Cannone di grosso calibro – Heavy Gun
NC 23.5, vaseline 5.0 & Na bicarbonate 1% Cannone di piccolo calibro ~ Light Gun
(See also Ref 4, p 179) Cannone di torre corazzata – Turret Gun
Cannone fuori bord – Out-board ‘Gun (Avn)
C-12 (Polvere). Ital solventless proplnt: NC Cannone per fanteria – Infantry Gun
68.0, NC 25.0, Centrrdite 5.0, vaseline 1.0, Cannone ngato – Rifled Gun
Na bicarbonate 0.5 & Amm oxalate 0.5% Cannone seudato – Shielded Gun
(Ref 4, p 183)
CAPSULA (plural Capsule). Capsule or Per-
CG-I3 (Polvere). See Polvere CG-I 3 cussion Cap

CG-14 (Polvere). See Polvere CG-14 Capsula detonante – Blasting Cap or Detonator

Cadinite. A mining expl consisting of Na Capsule incendive ad accensine elettrica - ,

nitrate 56, NG 26, sulfur 10 & carbon (or a Electric Igniter Cap consisted, accdg to Pian-
cellusoic material) 8% (Ref 8, p 321) tanida (Ref 4, p 196), of a mixture of Guncotton
(dry) 50, KC103 25 & Sb2S3 25%, which
Cannel (Polvere). See Polvere Camel surrounded the Pt-Ir wire, connected to two ..4
electrodes
CANNELLO (plural CannelIi). Accdg to Mili-
tary Dictionary (AddnlRef A), it is not a Cannon capsule incendive a percussioe – Percussion
Primer, but it is. rather a F?ojectile I?imer. Caps for igniting propellant charges consisted,
The following types exist: accdg to Piantanida (Ref 4, pp 194–95), of.
Cannello elettrico – Electric Primer mixtures of MF, KC103, Sb2S3, glass powder
Grnnello a frizzione – Friction Primer & gumlac. Less expensive mixture contd KC103,
Cannello fulminate – Igniter Sb2S3 & gumlac or KC103, Pb(SCN)2 & Pb
Cannello fulminate a strappo – Pull Igniter ferrocyanide. Numerical values and other
Cannello fulminate a pressione – Push Igniter compns are listed on pp 195–1 96. These mis-
Cannello a percussion –Percussion Primer tures are probably obsolete
Accdg to AddnlRef C, the cannello is a part
of the colpo compleio (Complete Round of CARICA (plural Cariche) – Charge
Ammunition)
Carica cave o Carica ad effetti concentrate –
CANNONE (plural Cannoni). Accdg to Mili- Hollow or Shaped Charge. In the Catalog of
tary Dictionary’ (AddnlRef A), it can be trans- the Societ~ Mangirotti, Codroipo (Udine),
lated as Cannon, Gun or Piece (of Artillery) published in 1960 are described on p B5 com-
They may be subdivided into: pressed charges of TNT (Tritolo). They are in
~annone ad anima liscti – Smoothbore Cannon the shape of inverse funnels with inside cavity
Cannone ad auancarica – Muzzle-loading Gun to create the Munroe-Neumann Effect action ‘1
Canrrone antiaerea – Antiaircraft Gun on detonation initiated by a cap. The bottom
“;Cannone anticarro – Antitank Gun diameters of chges are 60 & 75mm and their
Cannone a retrocarica – Breech-loading Cannon weights are 80, 100, 120, 160, 230, 300 &
Gmnone a tiro rapido – Rapid-fire Gun 360g. Their intended uses are demolition of
 I 151

large blocks of stone & punching holes thru illustrations, and for this reason we are including
steel plates here two Figs from the article of Col Jarrett,
Abrief, genera.l description of cariche cavi listed here as Ref 5a. The 1st Fig is cartoccio
(including an illustration; Fig 77) is given by a bossolo (Cartridge with Igniter Tube), while
Belgrano (Ref31, pp 267–69) the 2nd Fig is cartoccio a sacchetto (Cartridge
Bag). The illustrations in Jarrett’s article include
Carica d’inflammazione – Igniting Charge cartocci a bossolo for 75mm Shell and also for
105/28, 100/17 and 149/13 Shells
Carica d’innascamento – Priming or Initiating In TM 9-1985-6 (1953), listed here as Ref 16
Charge. Their compositions are listed under are described and illustrated under Cartridge
Composizioni (o Miscele) innescanti Cases,without including Italian names, the cases
for several weapons. Their igniter charges range
Carica di Iancio – Propelling Charge. See under from 10 to 50g of Black Powder
ESPLOSIVI DA GUERRA. Accdg to AddnlRef Cartridge Cases for the following weapons
C; it is a part of the COIPOccwnpleto (qv) are described and illustrated: 75/ 13-mm
Mountain Gun (p 123, Fig 185); 75/18-mm
Carico di polvera nera - Black Powder Charge Mountain Howitzer (p 124, Fig 186); 75/27-mm
Field Gun (pp 124–25, Fig 187); 75/32-mm
Carica posteriore – Base Charge Light Field Gun (p 125, Fig 188); 77/28-rmn
Field Gun (p 126, Fig 189); 100/17-mm Light
Carica praparata – Prepared Charge with Con- Field Howitzer (p 126, Fig 190); 105/14-mm
tainer; Cartridge Light Field Howitzer (p 127, Fig 191); 105/28-mm
(p 127, Fig 192); 149/13-mm Heavy Field
Carica di rinforzo – Booster Charge. See under Howitzer (p 128, Fig 193); 149/13-mm Field
ESPLOSIVI DA GUERRA Howitzer (p 129, Fig 194); 152/37-mm Gun
(p 130, Fig 195); 380/15-mm Heavy Howitzer
Carica di scoppio – Bursting Charge. See under (p 131, Fig 196)
ESPLOSIVI DA GUERRA
CARTOCCI GRANATA. Under the title,
Carlsoniti. Perchlorate based expls, such as “MUNIZIONAMENTO ITALIANO” (Addnl-
a) KC104 85 & vaseline 15% and Ref C) are listed complete rounds (co/pi com-
b) KC104 88 & DNBenzene 12% (Ref31, PP pleti) for weapons caliber 20-mm and larger,
362–63) which for small arms, the corresponding rounds ,
are listed as cartucci under armi portatili
CARTOCCI (singular Cartoccio) (Propellant Con- For example Cartocci Granata per Mitra-
tainers or Cartridge Cases). The description gliera (Machine Gun) da 20-mm Mod 35 con-
given in “MUNIZIONAMENTO ITALIANO” sists of bossolo e cannelo (Cartridge Case with
(AddnlRef C) is incomprehensible without Primer), carica di lancio (Propelling Charge),
bicchiere (Projectile Body), carica di scoppio
(Bursting Charge) and spoletta (Fuze). Bossolo
CARTOCCIO A BOSSOLO is of brass and is filled with polvere FC 4.
SCAL# $,2
Bicchiere is of steel with copper bands and
CARTOCCI
?!,
A SACCHETTO
C.””O”, BA14,/3,
filled with TNT or flegrnatized RDX or PETN
o SCALA t 6
Other cartocci granata described in Addnl-
Ref C are:
Cartocci Granata per Mitragliera da 37/54, Mod 39
Cartocci Granata per Camone da 47/32
Cartocci Granata per Obici (Howitzers) da 75/13,
-...-—- . . ..! .. - .F .- : --J Mod 32
Cartocci Granata da 75/27 per Cannone, Mod 32
Cartridge with Igniter Tube Cartridge Bag Cartocci Granata per Cannone da 76/4045, Mod 36
 I 152

Cartocci Granata per Camone de 90/53 Fig 127); 90-mm AA (p 93, Fig 128); 90/53-mm
Cartocci Gramta per Obice da 100/17, Mod 14-50 AP (p 94, Fig 129); 100-mm HE (p 94, Fig 130);
Cartocci Granata per Obice da 100/22 100/17-mm HE, M32 (p 95, Fig 131); 100-mm
Cartocci Granata per Cannone da 105/28, Mod 32 ADE-HE (p 95, Fig 132); 100/17-mm ADE-HE
Cortocci Granata per Obice da 149/19, Mod 32 (p 96, Fig 133); 100-rnm EP (Hollow Charge)
Cartocci Granata per Cannone da 149/40, Mod 35 (p 96, Fig 134); 100-mm EPS (Hollow Charge)
Colpi completi (Complete Rounds) per Obice da (p 97, Fig 135); 105/28-mm HE (p 97, Fig 136);
210/22 105/28-mm HE, M32 (p 98, Fig 137); 105/28-mm
Colpi completi per Mortaio da 81-mm ADE, M32 (p 98, Fig 138); 105wnrn AP (p
Colpi completi per Mortaio da 120-mm 99, Fig 139); 105/25-mm EP (Hollow Charge)
Cartridges from 6.5mm to 12.7mm, incl, are (p 99, Fig 140); 105-mm Hollow Charge, M43
listed under Armi Portatili, Munizioni (Small- (p 100, Fig 141); 120/21-mm HE (p 100, Fig
Arms Ammunition), while artillery cartridges of 142); 120/2 1-mm HE (Cast Steel) (p 101, Fig
caliber 37mm and higher are listed in MUNI- 143); 120/25-mm HE (Short) (p 101, Fig 144);
ZIONAMENTO ITALIANO as cartocci granata 120/25-mm HE (Long) (p 102, Fig 145); 120/25-
and described, in TM 9-1985-6 (1953) (Ref 16). mm HE (Cast Steel) (p 102, Fig 146); 120/40-mm
From Ref 16, we are listing here: HE (Cast Steel) (p 103, Fig 147); 120/40-mm
37/40-mm HE (p 73, Fig 87); 37/40-mm HE/AP HE (Base Fused) (p 103, Fig 148); 120/45-mm
(p 73, Fig 88); 37/45-mm AP (p 74, Fig 89); HE (p 104, Fig 149); 149/12-mm HE (Short)
37/54-mm AA (p 74, Fig 90); 40/39-mm AA (p 104, Fig 150); 149/12-mm HE (p 105, Fig
(p 75, Fig 91); 47/32-mm HE, M35 (p 75, Fig 151); 149/12-13-mm HE (L@t) (p 105, Fig
92); 47/32-mm AP, M35 (With Cap) (p 76, 152); 149/13-mm HE (p 106, Fig 153); 49/35-mm
Fig 93); 47/32-mm AP, M35 (Without Cap) HE, M32 (p 106, Fig 154); 149/35-mm HE, M32/
(p 76, Fig 94); 47/32-mm AP, M39 (p 77, Fig 38 (p 107, Fig 155); 149/12-13-mm HE (Cast I
95); 47/32-mm EP (Hollow Charge) (p 77, Steel) (p 107, Fig 156); 149/13-35-mm HE
Fig 96); 47/32-mm EPS (Hollow Charge) (p (One-Piece) (p 108, Fig 157); 149/35-mm HE
78, Fig 97); 57/43-mm AP (Without Cap) (p (British) (p 108, Fig 158); 149/35-mm ADE, I
78, Fig 98); 57/43-mm AP (With Cap) (p 79, M32 (p 109, Fig 159); 149/40-mm ADE-HE,
Fig 99); 65/17-mm HE (p 79, Fig 100); 65/17- M35 (p 109, Fig 160); 152-mm HE (p 110,
mm AP (p 80, Fig 101); 65/17-mm EP (Hollow Fig 161); 152/13-mm HE (Short) (p 110, Fig
Charge) (p 80, Fig 102); 65/17-mm EPS 162); 152/1 3-mm HE (Long) (p 111, Fig 163); I
(Hollow Charge) (p 81, Fig 103); 70/17-mm 152/37-mm HE (p 111, Fig 164); 152/45-50-
HE (p 81, Fig 104); 75-mm HE (p 82, Fig 105); mm HE~Base-Fused) (p 112, Fig 165); 152/32- 1
75/13-mm HE (Light Case) (p 82, Fig 106); 45-mm HE (Base-Fuzed) (p 112, Fig 166);
75/13-mm HE, M32 (p 83, Fig 107); 75/27-mm 152/37-mm AP (p 113, Fig 167); 210-mm”HE
HE, M32 (p 83, Fig 108); 75/32.mm HE (p (p 113, Fig 168); 210-mm HE (Cast Steel) (p
84, Fig 109); 75/46-mm HE, M34 (p 84, Fig 114, Fig 169); 210-mm HE (Bombs) (p 114, 1
110); 75/46-mm HE, M36 (p 85, Fig 111); Fig 170); 210/22-mm HE, M35 (p 115, Fig 171);
75/32-mm ADE-HE (p 85, Fig 112); 75-mm AA 260/9-mm HE (p 115, Fig 172); 260/9-mm HE
(p 86, Fig 113); 75-mm AP (p 86, Fig 114); (Cast Steel) (p 116, Fig 173); 305-mm HE (Short)
75/27-mm AP (p 87, Fig 115); 75/32-mm AP (p 116, Fig 174); 305-mm HE (Long) (p 117,
(p 87, Fig 116); 75-mm EP (Hollow Charge) Fig 175); 305-mm HE (Light-Case Long and
(p 88, Fig 117); 75-mm EPS (Hollow Charge) Short) (p 117, Fig 176); 305-mm HE (British)
(p 88, Fig 118); 75/13-mm EP (Hollow Charge) (Long and Short) (p 118, Fig 177); 305/17-mm
(p 89, Fig ‘119); 75-mm EPS, M42 (Hollow HE (p 118, Fig 178); 305/17-mm HE (Heavy)
Charge) (p 89, Fig 120); 75-mm Incendiary (p 119, Fig 179); 305/17-mm HE (Cast-Steel)
(F/C) and (F l/C) (p 90, Fig 121); 76/40-45-mm (p 119, Fig 180); 305/17-mm HE (One-Piece)
HE (p 90, Fig 122); 76/40-45-mm HE, M36 (p 120, Fig 181); 380/15.mm HE (Base-Fuzed) I
(p 91, Fig 123); 77-mm HE (Short) (p 91, Fig (p 120, Fig 182); 420-mm HE (Short and Long)
124); 77-mm HE (Long) (p 92, Fig 125); 77-mm (p 121, Fig 183); 240 and 400-mm HE (Bombs) - \
AA @ 92, Fig 126); 90/42-53-mm HE (p 93, for use in Mortar (p 122, Fig 184) 1
 I 153

Abbreviations: AA – Antiaircraft; ADE-HE – such as Polvere per mitragliatrice FIAT mod 35,
HE Projectile provided with booster system described here under Nitrocellulose a solvente
“Detonator AD Alto Esplosivo”; AP – Armor- volatile and in Ref 31, p 204
Piercing (Perforanti); API – Armor-Piercing-
Incendiary; EP – Hollow Charge with Base Fuze; CG Polvere. See Polvere CG
EPS – Hollow Charge incorporating a nose fuze
with a long flash tube leading to the center of CHEDDITE. Cheddite (plural Chedditi) o
expl charge; HE – High Explosive (Alto esplosivo); Esplosivi Street. Cheddites, invented in 1897
I – Incendiary (Incendario) by E. Street of England, have been patented
since 1898 in many countries. Accdg to Dr
Cartoccio a bossolo. Cartridge Case (for Fixed Omero Vettori of Aulla (Massa Carrara), a sub-
or Semi-Fixed) Rounds (See Illustration under sidiary of the French firm located in Chedde,
CARTOCCIO) Haute Savoie, established in 1901 at Salviano,
near Livorno, Italy, a plant which is likely to
Cartoccio a sacchetto – Cartridge Bag (for Se- be one of those belonging to the Societi2
parate-Loading Rounds) (See Illustration under Italiana Esplosivo Cheddite with the main of-
CARTOCCIO) fice at Torino. This Company, which is now
a subsidiary of the S.A. Suisse d’Explosifs,
Cartridge Case. See CARTOCCIO and under Liestal, near Basel, Switzerland, has also plants
Bossolo located at Torano (Carrara), Borgofranco (Ivr~a)
and Cinzano Torinese. Cheddites are expl compns
CARTUCCIA. Cartridge (plural Cartucce). The based on chlorates or perchlorates of Amm, K
following items are listed in Military Dictionary or Na. Other ingredients are combustibles and
(AddrdRef A): binder. A detailed description of Cheddites is
Cartuccti a capsula centrale. Center Fire Cartridge given in Ref 24, Vol 2, pp C155 to C164
Cartuccia a pallottola perforate. Armor-Piercing Accdg to Dr Omero Vettori (private commu-
Cartridge nications of 1962 & 1963), the plant of Societ5
Cartuccia a pallotola tracciante. Tracer Cartridge Italiana Esplosivo Cheddite at Salviano manufd
Grrtuccia da caccriz. Sporting Cartridge (Ref 31, at that time: Cheddite OS Extra, Cheddite O
pp 595 & 619) Extra, Cheddite O Extra B, Plastigel I and
Curtuccrir di lancia. Propellant Cartridge Plastigel II. Their compns and props are given
in Table 4, p C 159 of Ref 24, Vol 2. There is
Cartuccia “Magnum”’. Cartridge “Magnum”. rdso listed Cheddite gelatina
Several varieties are described in Ref31, pp In the book of Belgrano (Ref 31, pp 355–60)
594–95 are described chlorate and perchlorate Cheddites
Small-arms Cartridges are listed here under Accdg to Ref 28, p 321, Cheddites are too
Armi portatili munizioni, while Artillery Car- sensitive to mechanical action to be used as
tridges, which are actually complete rounds bursting charges in shells, but they can be used
(colpi completi) are listed under CARTOCCI for loading land mines
GRANATA (See also Cremonite, Esplosivo 86/14, Esplo-
sivo P, Esplosivo S, Manlianite, Polvere cannel
Cava D and Romite)
Italian explosives listed in Ref31,
Cava I
p 317 without giving their compns
Cava extra 2} Ciclonite o Ciclotrimetilentrinitroammina. See
T4 and in Belgrano (Ref31, pp 255–59)
Centraliti (Centralizes), invented in 1906 in
Germany, have been used, accdg to Belgrano Ciclotetrametilentetranitroammina. Same as
(Ref 31, p 218), in Italy as stabilizer for NC– Octogene o HMX. It is described in Belgrano
NG proplnts. Description of Centralizes is given (Ref 31, pp 259-60)
in Ref 24, Vol 2, pp Cl 26ff. Centralizes have
also been used in some Italian single-base proplnts, Ciclotol. See Tritolite
 I 154

Cloramite. A mining expl manufd after WWI (195 1) (Also Ref 31, p 640) consisted of Al 17,
by the Dinamificio di Orbetello, Italy, utilizing celluloid 20, susquiossido di ferro (Fe20 ~) 43,
scrap military propellants, consisted of Balistite Ba peroxide (Ba02) 11.5, Na silicate (Na2Si03)
(or Cordite) 64, Amm Perchlorate 20, Na 6.5 and a substance which regulates the dura-
nitrate 15 & K bichromate 1% (Ref 14, Vol 3, tion of combustion (such as bitumen, resin or
p C329-R & Ref 28, p 321) tar) 2%. The mixture could be heated to 100°
and compressed to 5000–6000 atm, w/o danger
Colpo completo (Shot or Complete Round of of expln
Artillery Ammunition). Accdg to “MUNIZION- b) Miscela incendiaria Tonegutti, ItalP 446010
AMENTO ITALIANO” (AddnlRef C), the colpo (1949) of Ministero dells Difesa Marina e M.
completo consists of: il proietto (Projectile); Tonegutti and CA 45, 1770 (1951), consisted
la carica di lancio (Propelling Charge); il cannelo of K chlorate 50, AN 20, Cu sulfate 10 & Mg
[Projectile (or Fuze) Primer] and la spoletta (or Al) powder 20%
(Fuze) Another Italian Patent listed in CA is:
In our opinion, to these must be added il c) Bombrini Parodi-Delfino, ItalP 430931
bossolo (Igniter for Propelling Charge) (1948) &CA 43,8682 (1949): TNT (PETN or
RDX) 15–60, oxidizers (such as chlorates, ni-
Commercial (or Industrial) Explosives of Non- trates, oxides, perchlorates or peroxides) 20–40
permissible Type listed in Ref 24, Vol 3,
are & finely pulverized metals (such as Al, Mg, Zn
pp C438-R to C440-R. Some of them are also or Fe) 20–40%
listed here in alphabetical order
Composizioni (o Miscele) innescanti (Initiating
Commercial (or industrial) Explosives of Per- Compositions) or Composizioni primari (Pri-
missible Type are listed in Ref 24, Vol 3, pp mary Compositions). The following formulations
C45 1-L & C454-L. Some of them are also were found in some Italian ammunition cap-
listed here in alphabetical order tured during WWII and examined at Picatinny
Arsenal: a) KC103 43, Sb2S3 24, MF (Mer-
Complete Round of Ammunition. See Colpo curic Fulminate) 24 & abrasive 9%; used in
completo some cartridge cases, such as the 47-mm APRN
(Armor-piercing Round Nose) shell b) KC103
Composizioni (o Miscele) fumogene (Smoke 44, Sb2S3 48, MF 6 & abrasive 2%; used as a
Compositions). See under PIROTECNIA o primer in fuzes of some bombs and in 47-mm
ARTIFICI DA GUERRA and in Belgrano APRN shell c) LA (Lead Azide) 55, LSt
(Ref 31, p 630) (Lead Styphnate) 44& binder 1%; used as the
upper charge in detonators with base charge of
Composizioni illuminanti (Illuminating Com- T4 (RDX) in some shells (Ref 28, p 322)
positions). See under PIROTECNIA o“ ARTIFICI The following typical Italian military ini-
DA GUERRA and in Belgrano (Ref31, pp 629–30) tiating compns are listed in Belgrano (Ref 31):
a) MF 15–40, KC103 20–50, gelatine 0.5–2,
Composizioni (o Miscele) incendarie (Incendiary Sb2S3 30–35 & Si carbide 10–20% (p 423)
Mixtures). Not found in the books of Molina b) MF 13.7, KC103 41.5, gelatine 0.7, Sb2S3 33.4
(Ref 1), Piantanida (Ref 4), Caprio (Ref 11), & powdered glass 10.7% (p 423)
Belgrano (Ref 13), Giorgio (Ref 26) and Bel- C) MF 38, PETN 15, Sb2S3 39, KC103 7 &
grano (Ref 31), but found in the book of Giua K2Cr207 1% (p 425)
(Ref 19, pp 412-14) d) MF 38, PETN 15, Sb2S3 40, K2Cr207 2
Giua, after giving a general description of & Ba(N03)2 5%. Gave the best results (p 425)
incendiaries (including Napalm) used during e) Miscele innescanti inossidabili a base di stif-
~11 in aerial bombs , lists on p 414 the fol- nato di piombo e tetrazene – LSt 25–55,
lowing incendiaries patented in Italy after WWII: Tetracene 1.2–5, Ba(N03)2 25–45, Pb02
a) Termite, ItalP 448101 (1949) of Ministero 5–10, Sb2S3 0–10, CaSi2 3–15 & glass
dells Difesa Aeronautic and in CA 45, 1770 powdered O–5% (p 484)
 I 155

f) Miscele innescanti inossidabili, found in Composizioni (o Miscele) per traccianti (Tracer

capsule tipo “Sinoxid” Italiane - LSt 35–40, Compositions). See under PIROTECNIA o
Tetracene 1–3, Ba(N03)2 35–40, Sb2S3 ARTIFICI DA GUERRA
10–15, CaSi2 3–5 & Pb02 3–4%. Some mixts
contd ca 2% of Carborundum (p 484) Cordite Italiana. See C2 (Polvere)
g) Miscele inossidabili. Eight formulations
contg Ba nitrate, LSt, Tetracene & Sb sulfide Cotone collodio. (Collodion Cotton, abbrd as
are listed on p 485 CC). See under Nitrocellulose
h) Miscele inossidabili, such as 1) LA 5,
Pb(SCNk 25, KC103 55 & Sb2S3 15% Cotone fulminate. (Guncotton, abbrd as GC).
2) LA 25, KC103 35, Sb2S3 35 & SiC 5% See Fulmicotone under Nitrocellulose
3) LSt 35, Sb2S3 5, Ba(N03)2 40 & CaSi2
20% (Ref 31, p 487) Cremonite. A Cheddite-type expl mixture pro-
i) Miscele di innesco non corrosive contenenti posed in 1902 by U. Alvisi – Amm Perchlorate
fosforo rosso (Noncorrosive Mixtures Con- 48.85 & Amm Picrate 51.15% (Molina, Ref 1,
taining Red Phosphorus) developed betw 1950 p 200)
& 1960 at the Olin Mathieson Chemical Corp
and probably tried in Italy. We are listing two Cresilite. Mixture of TN-m-Cr (Trinitrometa-
examples – Red P 25, PETN 5 & Ba(NO S)2 cresole) 60 & PA (Picric Acid) 40Y0, used in
70% 2) Red P 17, LSt 25, PETN 5 & Ba(N03)2 Italy for loading large-caliber shells. It was de-
53% (Ref 31, p 488) veloped in France under the name of Cr@dite
j) Mixtures contg chlorate or perchlorate of No 2 (Ref 28, p 323 & Ref 31, p 292) (See
thallium developed in 1958–59 by the Manu- also Ecrasite)
facture g6n6rale des munitions, France, were
propably tried in Italy. Three formulations Demolition Charges. Accdg to OrdnSergeant
are listed in Ref 31, p 489 (Ref 4a, p 18), Italian military demolition expls
k) Noncorrosive mixts contg nitrate of thallium of WWH were plastic, such as the one consisting
or/and cesium, developed in 1959 by the Manu- of RDX 67.2, NG 16.3, Al 12.2 & wax 4.170
facture g~ni%ile des munitions. Two formula- (adds to 99.8%). It was of gray color and the
tions are listed in Ref 31, p 489 charge shaped like a pancake, ball or hollow
1) Noncorrosive mixts contg LSt, Tetracene cylinder. Another charge consisted of RDX,
with added 0.1 to 5% “Aerogel”, developed in NG & wax and was of yellow color. The 3rd
1957 by the Olin Mathieson Chemical Corp chge was light-brown in color and consisted of
and probably tried in Italy. Several formulations RDX with a desensitizing agent. Mg shavings
are listed in Ref 31, p 490 (l–3 oz per 1 lb of HE) were added to all
m) Mixtures contg thiocyanate of lead or mercury above demolition chges to increase their in-
developed in France and probably tried in Italy. cendiary effect
Five formulations are listed in Ref31, p 491
Giorgio (Ref 26, p 163) lists several mixtures, Demolition Fuse, Instantaneous is described
among them Cu (Pb or Hg) thiocyanate 30–40, under Fuse (Miccia)
K chlorate 50–55, Sb sulfide O–1 O & powdered
glass O–5% Detonatori. See under INNESCAMENTO

Composizioni (o Miscele) a Iuci colorate (Colored DINAMITI (Dynamites)

Lights Compositions). See under PIROTECNIA Accdg to Giua (Ref 19, pp 338–45), Italian
o ARTIFICI DA GUERRA and in Belgrano Dynamites may be subdivided into: I, Dinamiti
(Ref 31, p 627) a base inerti (Dynamites with inert base) and
II, Dinamiti a base attiua (Dynamites with
Composizioni di scoppio (Bursting Charge Com- Active Base)
positions). See Esplosivi di scoppio ‘ I. Dynamiti a base inerti may be subdivided
into:
 I156

a) Tipo I – Nitroglicerina (NC) 70–75 & AN 20–25, SN and/or KN 30–35 & charcoal
kieselguhr 30–25% 2W0
b) Tipo H – NG 50 & kieselguhr 50%0 Some Dynamites were used by Italians during
C) Dinamite nera (Black Dynamite) – NC WWH as demolition charges
45–55 & coke 55–45% Dynamites and other expls permitted for use
d) Dinamite al carbonic di legno (Charcoal. in gaseous and/or dusty coal mines are “Esplo-
Dynamite) – NG 90 & charcoal 10% sivi antigrisoutosi”, “Esplosivi ammissibili” or
e) Dinamite rossa (Red Dynamite) – NG 68 “Esplosivi di. sicurezza” (Ref 28, p 324)
& tripoli 32% Belgrano (Ref 31, p 170– lists on Table 26
f) Wetterdinamite (Permissible Dynamite) – the, following Dynamites as the principal expls
NC 35–40, kieselguhr 14–1 O & Mg sulfate used in Italy: GDI, GDII, GD2, GDM, GEO,
32–50% Gomma A and Gomma B. All of them are
Il. Dinamiti a base attiva may be subdivided into: listed, including their properties, under ESPLO-
g) Gekrtina gomma o Gelatina esplodente SIVI DA MINA in Table 1. In addition to these,
(Blasting Gelatin) – NG 92–93 &CC Dynamite G EOM is listed there
(Collodion Cotton) 8–7% AddnlRefi L. Avogadro (of Montecatini,
h) Gekrtina esplosiva da guerra (Military Avigliana, Torino), AnnChim(Roma) 49, 352–
Blasting Gelatin) – NG 86.4, CC 9.6 & 57 (1959) & CA 53, 15567 (1959) (Sensiti-
camphor 4.o% (Suitable for use as bursting zation of Dynamite Gelatin by 1–5% of inert
charge) substances of high or moderate hardness such
i) Gelatina dinamite (Gelatin Dynamite or as pumice, quartz, Al 20s, hematite, pyrite,
Gelatin) – NG 67–86; CC 3–5.5, KN (Po- etc can raise deton velocity to as high as 6800
tassium Nitrate) 5–25 & woodflour 2– 10% m/see)
j) Ammon dinamite (Gelatina 65%) – NG
63, CC 2, AN 30 & wood flour 5910 Dinamon. Accdg to Belgrano, 1st Edn (1952)
k) Gelatina diruzmite incongelabile o antigelo (Ref 13, p 163), Dinamon consisted of AN 69,
(Nonfreezing Gelatin Dynamite) - NC 20–55, KC104 8, TNT 20 & Al 3%. It was listed in
CC 1–2, Nitrotoluenes 8–21, SN (Sodium ~ Ref 24, Vol 3, p C440-L
Nitrate) with AN 25–60 & cereal flour 1–8%
1) Gelatina 40% – NG 40, drip ofl [M DNT Dinamon 1B. Accdg.to Belgrano, 2nd Edn
(Dinitrotoluene)] 10, SN 44& cereal flour (1974) (Ref 31, p 171), it is a miningexpl
6% contg NG 3–6910,the rest being AN, TNT,
m) Ammon-gelatina I – NG (gelatinized with woodmeal and some other ingredients
CC) 40, AN 45, SN 5 & woodflour 10%
n) Ammon-gelatina 11- NG (gelatinized with Ethos or Escho. Accdg to Molina (Ref 1, p
CC) 20, AN 75 & wood flour 5% 342), Esplosivo Ethos – AN 75, Si (95% pure)
o) Gelatina Vender o Dinamite inconge~bile, 16, Al pdr 2 & dried horse dung (called “Ippo-
Vender (Gelatin of Vender or Nonfreezing sino”) 7$Z0– was used by the Italians for mili-
Dynamite of Vender). A series of expls in- tary purposes. Silicon can be replaced by ferro-
vented by Venzio Vender and manufd before silicon. Belgrano (Ref 31) lists it as Echo on
WWH at the Dinamitificio di Cengio. They p 316 but erroneously gives AN content as 25
were based on NG mixed with 10–3070 of instead of 75%
Dinitromonoformin or Dinitromonoacetin
and other usual ingredients of Dynamites. Ecrasite. This name is derived from Ekrasit,
It was claimed that these expls remained an Austrian military expl developed in 1892
plastic at temps as low as –20°C and used until 1908 when all of its available
p) Dinamite No 1, Non-gekrtinizzate – NG supply was blown up in Kiev, Russia. Its compn
70–74 & wood flour 30–26% was kept secret and originally was supposed to
q) Dinamite IVO 2, iVon-gelatinizzate - NG be Ammonium Trinitrocresylate. Discussion
35–48, SN and/or PN 52–39 & cereal flour on this subject is given in Ref 24, Vol 5, pp
12–17% E8-R & E9-L
r) Unknown Name Dynamite – NG 20–25,
 I 157

Ecrasite 60/40. Same as Cresilite or Cresylite Esplosivi ammissibile.Permissible Explosives.

No 2 See Esplosivi antigrisutosi

Esanitrodifenilammina, Exil o p-Dipicrilamina. Esplosivi Explosives) o Esplosivi

alti (High
Hexanitrodiphenylamine, dirompenti (Brisant Explosives). To these
(02 N)3C6H2 .NH.C6H2(N02)3, described, under belong Esplosivi da guerra, such as Tritolo
Diphenylamine, in Ref 24, Vol 5, pp D1434-Rff. (TNT), Pentrite (PETN), T4 (RDX), Melinite
Accdg to Ref 28, p 325 it was used as a HE (PA), Tetrile (Tetryl), etc and Esplosivi da
either alone or in mixts with TNT (See also mina, such as listed in Tables I & 111and under
Ref 1, p 399) , DINAMITI, Items a, b, c, d, e, g, h, i, j, k, 1,
Belgrano (Ref 31, pp 375–77) describes it m, p & q. Also Gelignite, Comma A, Gomma
as Exil and states that its mixture with TNT & B, etc ‘
Al has been used in underwater arms (armi sub-
acquee) Esplosivi antigrandini (Antihail Explosives).
See Antigrandini: Esplosivi, Cannone e Razzi
Esanitrosorbite (Hexanitrosorbitol). An expl
compd first prepd and examined during WWII Esplosivi antigrisutosi o Espiosivi ammissibili
in Italy by A. Tetramanzi & N. Arnaldi and ie- (Antifiredamp Explosives or Permissible Explo-
ported in Atti dells Accademia delle Scienze di sives). See under Esplosivi da mina, Tables
Torino, Classe di Scienza Fisiche, Matematiche II & IV and under DINAMITI, Item f. Also
e Naturrdi 77, 278–81 (1942 ).& CA 38, 3841 Grisounite and Grisoutina
(1944). This compd,
02 N.0.CH2 [CH(ON02)]4 .CH2.0.N02, was Esplosivi bassi (Low Explosives). To these belong
obtd by nitrating sorbitol of high purity by weak Esplosivi da mina (such as Esplosivi anti-
means of fuming nitric acid below 0°, followed grisutosi), DINAMITI with low NC content and
by gradual addn of sulfuric acid at below minus Esplosivi di lancio o Esplosivi propellenti
15°. The product obtd, in 9770 yield, was
(after crystn from alcohol) in the form of plate- Esplosivi deflagranti. See Esplosivi di lancio
lets of density 1.58, melting at 55°. Its props
are reported as follows: Heat of combustion ESPLOSIVI DAGUERRA O ESPLOSIVI
1465kcal/kg; Heat of formation 135kcal/mole; Ml LITAR To these belong: Esplosivi innes-
1.
Heat of explosion 1500kcal/kg; Detonation canti o primari (Initiating or Priming Explosives);
Velocity 7230m/sec and Sensitiveness to Impact Esplosivi di lancio o Propellenti (Propellants);
and Stability – similar to NC. It was not con- Esp[osivi di rinforzo (Booster Explosives) and
sidered a satisfactory replacement for NC as a Esplosivi di scoppio (Bursting Explosives). They
gelatinize for NC because of physical changes are described separately below
which occurred in the mixture. Its use for
military purposes was not reported (Ref 28, Esplosivi innescanti o primari. (Initiating or Pri-
p 325) mary Explosives).
Under this title Belgrano (Ref31, pp 405ff)
Escho. See Ethos describes:
a) Innescanti priman (Priming .Explosives),
Esplosivi alla nitroglicerina. See under which include Fulminato di mercurio (MF)
DINAMITI (PP 406-428); Fulminato organico, CHO.CNOH
(p 428); Fuhninato di argento (AgF) (PP 428–
Esplosivi Alvisi. Perchlorate-based, Cheddite 429); Azotidrati (Azides), which includes Acido
type, expls patented by Ugo Alvisi beginqing in azotidrico, HN ~ (Hydrazoic Acid) (p 429);
1899. They were superior to chlorates-based Azotidrato di sodio, NaN3 (SA) (pp 430–38);
expls. The following are described by Molina Azotidrato di piombo, PbN6 (LA) (pp 438–49);
(Ref 1, pp 199-200): Manhirnite, Polvere Azotidrato d’argento, AgNs (PP $49–5 1);
Cannel, Ckemonite and Kratite Azotidrato di amrnonio, NH4N3 (p 451);
 I 158

Acido stifnico or Trinitroresorcina, fumo (pp 201 f~, C2 (Polvere) (p 21 O), and
(HO)2 C ~H(N02)3 (pp 453–55); Dinitroresor- Propellenti per razzi (p 128). They are described
cina, (HO)2 CCHZ(N02)2 (p 456); Stifnato di here separately. To these must be added Filite
piombo (Lead Styphnate) (LSt) (pp 456–63); (qv), which was not described in Belgrano (See
Guanilnitrosoammina o Tetrazene (Tetracene), also POLVERI ITALIANI DA LANCIO SENZA
Cz H8 NI ~O (p 464–67); Solfocianato di piombo FUMO)
(Lead Thiocyanate), Pb(CNS)2 (pp 467-68);
Diazodinitrofenolo o DDNP, C ~H2N405 (pp ESPLOSIVI (o POLVERI) DA MINA. Mining
471 –74); Trinitrofloroglucinato di piombo, Explosives
Pb(C ~HN ~09Pb) (p 475–76); Nitrato di Many Italian Mining Explosives are listed under
diazobenzene, C 6H5.N2 .0N02 (pp 476–77); COMMERCIAL OR INDUSTRIAL EXPLOSIVES
Solfuro di azoto, N ~S~ (pp 477–78); Esametilen- in Ref 24, Vol 3, on pp C438-R to C440-R
triperossidiammina o HMDT, C6HI ~N2 OC (Nonpermissible Explosives) and on pp C451-L
(pp 478-79); Cianurazide, C 3N3(FJ3)3 (PP & R and C454-L (Permissible Explosives). Some
481 –82); Acido diazotriazolcarbonico, of them are listed in this section
NH–N Belgrano (1952) (Ref 13) lists in Tables on
/ pp 280ff 164 formulations, while in the new edn
‘z N–c\N_ C4C02H (pp 482–83)
of Belgrano (1974) (Ref 31) there are listed in
Principal Italian Initiating Compositions (or Tables 53 to 62 incl, 259 Mining Explosives,
Mixtures) are described under Composizioni (o some of them French. The tables give, besides
Miscele) innescanti compns, the following properties: Trauzl (Lead
Block Expansion), Distanza colpo (Gap), and
Esplosivi da Iancio, Esplosivi deflagranti o Pro- Velocit~ detonazione (Detonation Velocity)
pellenti(Propellants). values
To these belong the following items described The tables which follow list expls selected
in Belgrano (Ref 31): Polvere nera da guerra from Belgrano’s books
(p 342), Balistite (p 205), under Polveri senza
TABLE I
ESPLOSIVI DA MINA GELATINOSI CON .NITROGLICERINA
(Mining Explosives with Nitroglycerol)
Composition (%) and 12345678 9 Gomma
Some Properties GDII GD2 GDI GDIM GEOM GEO B A GDM
Nitroglycerin 43.2 48.3 7.0 60.0 38.0 57.0 71.0 40.75 77.5 82.5 92 38.0
Collod Cotton 2.3 2.7 0.8 3.5 2.3 3.5 5.0 1.5 5.0 5.5 8“ 2.3
Am Nitrate —— —— 50.9 29.0 – 17.0 – – – 50.4
Am Perchlorate — — 44.0 – – – – – – – – –
Woodtlour 7.0 5.8 1.0 5.2 – 3.5 5.0 – 5.0 3.0 –, –
Dinitrotoluene — — 10.0 – – – – – – – – –
Trinitrotoluene — — 5.0–––––– –––
Na Nitrate 45.5 42.7 32.2 30.5 6.0 7.0 – – 12.0 8.5 – 6.0
K Nitrate — — — — — — 18.5 – – – – –
Ca Silicide — — — —— —— — —— ——
oil — — — — 2.0 – – – – – – 2.5
PETN — — — — — — — 40.75 – – – –
Ocher, red (Hematite) – – – 0.3 0.5 – 0.5 – – – – 0.5
Ocher, yellow (Limonite) 1.0 – – – – – – – – – – –
Na Carbonate 1.0 0.5 – 0.5 – – – – 0.5 0.5 – –
Ca Carbonate — —— — 0.3 – added – – – – 0.3
0.3
Trauzl Test, cc 340. 355 430 440 475 500 505 525 540 560.630 475
Gap Test, cm 14 15 6 20 21 23 26 25 29 30 35 –
Veloc of deton, m/see 5000 5200 4700 6000 5900 5400 5900 7000 6700 6900 7200 –
 I 159

TABLE II
ESPLOSIVI DA MINA POLVERULENTI CON NITROGLICERINA
(Pulverulent Mining Explosives with Nitroglycerol)
Composition (%) and
Some Properties 12345678 9101112
Nitroglycerin 14.0 110 10.0 4.0 4.0 8.0 12.4 12.76 4.0 12.0 11,.7 9.0
Dinitrotoluene —— . 1.5 – 0.5 0.3 – – – – –
Trinitrotoluene —— __ __ __ 10.0 0.3 – 20.0
Collodion Cotton 0.3 – 0.25 1.5 0.1 0.5 0.3 0.24 – – 0.3 0.3
Woodflour — 6.0– – – – – – – – _ _
Cereal flour —— ___ _ 5.0 – – – 3.0 – -
Am Picrate 65.7 51.0 89.7582.0 89.4 81.0 79.0 83.0 76.0 77.7 76.0 70.7
Na Nitrate —— __ __ __ __ __ $
K Nitrate —— __ __ __ __ __
Dinitronaphthalene – 10.0 – – – – 8.0 4.0 10.0 – 10.0 –
K Perchlorate -— __ __ __ __ __
Na Chloride 20.022.0–11.0–––– ––––
T4 (RDX) —— __ 6.5–––––––
oil —— __ __ __ _ 2.0 2.0 –
Ca Silicide —— __ _ 5.0–––5.0––
Trauzl Test, cc 270 265 300 305 320 375 390 390 400 420 430 450
Gap Test, cm 2520312634 11116
Veloc of deton, rn/sec 2120 23002038 17102500 32002715 32002348 2960 2350 2912
uses C&SMC&SIvlC&SM CM Cl?#MC&SMC&SMC&SM OM CNl OM G&OM
‘ Abbreviations: CM–CoalMines G&OM– Galleries &OpenMines
C&SM – Coal& Sulfur Mines OM – Open Mines Only
Note: Composition No 3 is called Grisoutina

TABLE Ill
ESPLOSIVI DA MINA POLVERULENTI SENZA NITROGLICERINA
(Pulverulent Mining Explosives Without Nitroglycerol)
Composition (%) and
Some Properties 1 2, 3 4 5 6 7 8 9 10 11 12 13 14
Am Nitrate 85.5 77.0 40.0 78.0 82.0 80.0 79.5 70.0 84.5 90.0 – 79.0 70.0 63.0
Dinitronaphthalene – – – – – – – 5.010 .0–––––
Dinitrotoluene —— —— 1.0– – – – – – – – –
Trinitrotoluene 4.5 15.0 – 16.0 14.0 20.0 10.0 10.0 – 8.0 90.0 – – –
h Perchlorate —— 25.0– – – – – – – – – – –
K Perchlorate —— —— —— —— —— —— ——
K Nitrate — — 29.0– – – – – – – – – – –
Wood flour 10.0 6.5 4.0 – 3,0 – 2.5 – – 2.0 – 1.0 – 3.0
oil — — 2.0––––––– ––––
Paraffin — —— —— —— —— —— —— —
Na Nitrate — —— 4.5 – – 8.015 .0––––– 13.0
K Bichromate — —— —— —— — 4.5 – – – – –
Carbon (pulverized) – 1.5 – – – – – – 1.0 – – – – –
Charcoal (pulverized) – – – – – – – – – – – – – –
PETN or RDX — —— —— —— —.— — 10.0 20.0 30.0 21.0
Ca Carbonate — —— 1.0––––––– –––
Ocher (Hematite) —— — 0.5–––– –-– –––
Trauzl Test, cc 330 330 350 400 420 430 450 360 395 375 400 425 450 480
Gap Test, cm 12366772 314536
Veloc of Deton, m/see 1900 2300 2400 3600 37004300 3500 1600 3100 2300 7000 2850 2100 3000
 I 160

TABLE IV
ESPLOSIVI DA MINA CON RESIDUATI DI POLVERI DI LANCIO
(Mining Explosives Containing Surplus Propellants)
Composition (%) and
Some Properties 12345678 9101112
Ballistite 45 12 – 60 10 10 10 – 50 – – –
Polvere B — -— —— —— —— 15 – –
Polvere C — — 54 – – – – 50 – – 54 50
Polvere Dupont — —— —— —— —— 10 20 40
TNT — 10 – – 10 – 4 10 10 10 – 10
Am Nitrate 55 64 – – 70 80 55 – – 60 – –
K Nitrate —— — 40 – – 5 40 40 – – –
Na Nitrate — 9 26, – – – 20 – – – 26 –
Am Chlorate —— 20––––––– ––
K Perchlorate —— —— 5.510 5 – – – – –
Wood flour —— —— 4.5–l–––––
Ca Silicide — 5––––––– 5––
Trauzl Test, cc 430 425 445 315 320 330 350 350 375 410 435 435
Gap Test, cm — 17–44111 134
Veioc of Deton, m/see – – – – 3300 3200 1350 1500 1320 2500 2328 2900
Note: After WIconsiderable mounts ofleft-over propeUmts (botiof berican &Itdimori~n)
were left unused in Italy. Some of thew propellants were used to prepare mining explosives. The
usual procedure was to grind a propellant to pass a sieve with 16 openings per sq cm (US Std Sieve
No 12) and to mix it with an oxidizer and other ingredients ground to pass a sieve with 20 openings
per sq”cm (US Std Sieve No 14)

Black Powder is still used in mining and its 38ps KN03 mixed with 8ps powd S, moistened,
compn: K nitrate 60–72, carbon 14–21 & dried and ground]
sulfur 13–1 8% is listed in Belgrano (Ref 31, C) T. Seguiti, IndMineraria (Roma) 16 (6),
p 342) as Polvere nera da mina 289–98 (1965) & CA ~, 7960 (1966) (Explo-
AddnlRefs from CA: sive mixts contg AN and combustible oil for
A) S. Custodero, ItalP 522944 (1955) & CA general mining uses is described in detail)
53, 3698 (1959) [Synthetic resin-base expls are D) T. Seguiti, IndMineraria (Roma) 16 (8),
prepd by incorporation of oxidizers into a 413–22 (1965) & CA 64, 7960–61 (1966)
liquid polymer which is then solidified by addn (Explosive mixts contg AN and combustible oil
of a suitable catalyst. Thus, to 20% of a mixt for underground uses are described in detail)
contg 100 parts “Araldit D“ and 9–1 Ops “95 1“
(an alipahtic polyamide), 80% NaC103 was added Esplosivi di rinforzo (Booster Explosives).
with slow stirring to obtain a homogeneous paste. The following expls have been used: Acido
After it was shaped into the desired form by picrico (Ref 31, p 281); To (RDX) (Ref 31,
means of a press, it hardened on standing for p 263); Pentrite (PETN) (Ref31, p 176) and
14 hours] Tetrilite o Tetrile (Tetryl) (Ref 31, p 272)
B) A. Simoncini, ItalP 515805 (1955) & CA Illustration of an Italian Booster is given in
52, 15910 (1958) [Tannin contg expl mixts Ref 16, Fig 38 on p 28
and flammable powders are prepd in the fol-
lowing examples: 1) Powdered 76 parts KC1P3, Esplosivi di scoppio (Bursting Explosives or
mixed with 24 parts powd chestnut wood ex- Fillers).
tract (I) (as a paste), dried and ground; 2) Powd Following are the principal High Explosives
38 pts KN03 mixed with 16ps (I) and another (Esplosivi alti) used as fillers of projectiles, by
 I 161

themselves, or in compns: Amatolo (TNT 60 with a NC solvent (acetone). The paste obtd
& AN 40%) (Ref31, p 246); Ammonal (Ref is impregnated in the mold with NG and the
31, p 367); ANS o ASN (Ref 31, p 181); Exil DEtPh in a solvent, centrifuged, and gelled at
(Hexanitrodiphenylarnine) (Ref 31, p 275); 50°]
Octogene o HMX (Ciclotetrametilentetranitro- e) E. Ravelli, ItalP 648270 (1962) & CA 65,
arnmina) (Ref 31, p 259); Pentrite o Tetranitro- 5440 (1965) [Explosives of high density suitable
pentaeritrite (PETN) (Ref 31, pp 176ff); Pen- for loading projs are obtd by mixing T4 (RDX)
trite paraffma, 90/10 (Ref 31, p 182); Pentoliti and/or Pentrite (PETN) with. high density ni-
(PETN 20-80& TNT 80-20%) (Ref 31, p 182); trates. For example, compressed mixt of PETN
T4, Esogene o Trimetilentrinitroarnmina (RDX, 25 with Pb(N03)2 75% gave a loading d 2.5
Cyclonite or Hexogen)(Ref31, pp 255ff); to 2.7; mixt of PETN 29 with Ba(N03)2 71%
Tetritol (Tetryl 75 & TNT 25%)(Ref31, p 246); or PETN 24, Ba(N03)2 74 & Zn stearate 270
Trilite, Tritolo o Trinitrotoluene (Ref 31, p gave d .2.2–2.3
233); Tritolital (TNT 60, RDX 20 & Al 20%)
(Ref 31, p 263); Tritolite (RDX 60, TNT 39 Esplosivi “slurry”, developed after WWII in US,
& beeswax 1%) (Ref 31, p 246) and Xilite o were not manufd, nor used as of 1974 when the
Trinitrometaxilolo (Ref 31, pp 248–49) (See book of Belgrano was published (Ref31, p 320)
also the book of E. Brandimarte, “Cariche di
Scoppio”, Ref 29) Esplosivo 60/40. Amatol contg 60% AN &
The following Bursting Explosives patented 40% TNT. See under Arnatolo
in Italy after WWH are listed in CA:
a) Montecatini Societ~ Generale, ItalP 433633 Esplosivo 86/14. Cheddite-type expl consisting
(1948) &CA 44, 1709 (1950) [Cast explprepd of Amm Perchlorate 86 & paraffin 14% (Ref 4,
by incorporating RDX (or PETN) 75 with Nitro- p 230)
isobut ylglycerol Triacetate 25’ZOat 80°]
b) Polverifici Giovanni Stacchini SA, ItalPats Esplosivo ASN. See ASN o Antisanzionite
433636 (1948); 445206 (1949); 445601,
445602 & 445603 (1949) and CA 44, 1709 Esplosivo FNP. See FNP (Esplosivo)
(1950); 45, 1770 & 3160 (1951) [Compns of
RDX (or PETN) 5–65, TNT 30–90 with pow- Esplosivo MABT. See MABT
dered metal (such as Si, B, Mg, Cu, Fe, Al or
Zn) 5–30%] Esplosivo MAT. See MAT (Picratol)
c) Direzione Superiore del Servizio Tecnico di
Artiglieria a Roma, ItaW 450103 (1949) &CA Esplosivo MBT. See MBT (Esplosivo)
44, 11098 (1950) (RDX 86–92 mixed with
castor oil 8– 14% and pressed in the form of Esplosivo MNDT. See Siperite
beads)
d) Bombrini-Parodi-Delfino S.p.A., FrP 1424216 Esplosivo MST. See Nougat
(1966) (Ital) &CA 65, 10420 (1966) [Plastic
explosives of high power suitable as bursting Esplosivo “P”. Blasting expl consisting of Amm
chges can be prepd as follows: Into molds Perchlorate 61, Na nitrate 30, paraffin 8 &
or bomb bodies are introduced a granulated vaseline 1’%0 (Ref 4, p 230). A similar expl,
mixt of NC and HE’s, followed by the addn of called Esplosivo speciale P consisted of Amm
a solvent contg a nitrate ester, a stabilizer, a Perchlorate 53, Na Nitrate 35 & paraffin 12%
plasticizer and sometimes an accelerating agent. (Ref 28, p 331). It is called in Ref 1, p 202
The compn. of the final expl may be: NC 5–36, Cheddite speciale P
nitrate ester 33-40, HE 20–60, plasticizer 1.5–
2.5, stabilizer 0.5–0.6 and accelerating agent Esplosivo plastico. A plastic expl suitable for
0.4–0.5 part. The granulated compn is prepd military use consists of RDX 85–89, petrolatum
by mixing the NC, the HE, a plasticizer (di- 12–10, plastic binder (Tioplasto molle) 0.5–2
ethylphthalate) and a stabilizer (Centrality) & glycerophthrslic acid 0.5–1%. Its A1-contg
 I 162

modification was: RDX 64–75, petrolatum 10– Fulminato di mercurio. Mercuric Fulminate,
12, Al powder 25–10, plastic binder 0.5–2 & Hg(CNO)2, is described h Belgrano (Ref 31,
glycerophthalic acid 0.5–1% pp 406–27). It was manufd, accdg to Dr
Refi Dinamite Nobel SA, Milano, ItalP 427535 Omero Vettori, during WWH by the Nobel
(1947) & 439931 (1948); CA 43,4768 (1949) Societ2 Generale di Esplosivi e Munizioni at
& 44, 6130 (1950) (See also “T4 plastico”) Tiana and by the Societh Anonirria Bombrini-
Parodi-Delfino at Colloferro-Roma. It has been
Esplosivo “S”. Cheddite-type blasting expl con- used in admixture with KC103 & Sb2S3 with
sisting of NaChlorate 90, paraffin 7 & vaseline or without powdered glass. Some post WWII
3% (Ref 1, p 205 & Ref 28, p 331) formulations are listed here under Composizioni
innescanti and in Belgrano, p 423. See also
Esplosivo S20. Military expl consisting of AN 79, Ref 24, Vol 6, pp F217-L to F230–R and Ref
TNT 20 & woodflour 1%. It was manufd at 28, p 333
Societ~ Stacchini. Its props are similar to those
of French Explosif du type N nOU, which con- Fuochi artificial.See under PIROTECNIA o
sisted of AN 78.7 & TNT 21.370. Their props ARTIFIZI DA GUERRA
are listed on p 332 of Ref 28. See also L.
M6dard & A. LeRoux, MP 34, 201 (1952) Fuse (Miccia). Most important fuses are:
Miccia a lenta combustion – Slow Fuse, such
Esplosivo speciale P. See under Esplosivo P as Safety Fuse. The core of Italian fuse con-
sisted of K nitrate 60, beech charcoal 25, hemp
Exil. See Esanitrodifenilanmina charcoal 5 & Fe oxide 10% (Ref 31, p 523).
Other formulations are BkPdrs, such as K nitrate
Exogene o Trimetilentrinitroammina (RDX) 70 or 77, S 12 or 10 & carbon 18 or 13%
See T4 (Ref 31, p 524)
Miccia detonante – Detonating Cord or Cordeau.
F2. A single-base smokeless proplnt listed by These may have cores of compressed PA (Picric
Belgrano without giving its compn(Ref31, p 581) Acid) - deton vel 5000m/s; core of TNT –
deton vel 4500m/s; fuse of PETN prepd by a
FB (Polvere). See Pdwe FB special method and MF (Mercuric Fulminate)
fuse prepd by a special method(Ref31, p 528)
FC 4 (Polvere). See Polvere FC 4 In OrdnSergeant (Ref 4a, p 18) is described
a WWH Instantaneous Fuse for Initiation of De-
Filite. Brdlistite proplnt consisting of NC 50 & molition Charges which contd a core of MF 79.4
NC 50% with 0.5–1% aniline added as stabilizer. with wax 20.6%. When initiated by a cap, the
It was manufd in the form of cords. Not used fuse functioned at the rate of about 20000ft/s
now because it badly corrodes gun barrels (6100m/s). If initiated by flame it will burn but
(Ref 24, Vol 6, p F24-R). Not listed by Belgrano its use as slow burning fuse was not recommended

FNP (Esplosivo). High Explosive compn consisting GDI, GDII, GD2 and GDIM. Mining Explosives.
of AN 75, PETN 20 & wax 51Z0.Was used during Their compns and props are listed under Esplo-
WWII press-loaded in some projectiles (Ref 28, sivi da Mina in Table I
p 332)
Gelatina 40%: See item 1, under DINAMITI
Fulmicotone (Guncotton). See under Nitro-
cellulose Gelatina 65%. See Ammon dinamite, item j,
under DINAMITI
Fulminato d’argento. Silver Ful.rn@ato, AgCNO,
is described by Belgrano (Ref 31, pp 428–29). Gelatina 92/8. Same as Gomma A
It was used in small quantities by the Marina
Italiana for special detoriators (p 429) (See also Gelatina da guerra. Accdg to Piantanida (Ref
Ref 24, Vol 6, pp F223-R to F224-R and Ref 4, p 257), it consisted of NG 86, CC (ColIo-
28, p 332) dion Cotton) 10 & camphor 4%
 I 163

Gelatina dinamite. See item i, under DINAMIT1 Gomme incongelabili. Accdg to Molina (Ref 1,
p 303), these gelatinous, nonfreezing expls were
Gelatina dinamite incongelabile. See item k, manufd after WWI by the Dinamitificio di
under DINAMITI Orbetello. Their compns were: NG 72 to 65,
CC 6 to 5, TNT 7 to 8 & Arnm nitrate 15 to 22%
Gelatina esplodente o Gelatina gomma. See item
g,under DINAMITI GRANATA (Grenade). Although this term is
also applied by the Italians to a shell (like
Gelatina esplosiva da guerra. See item h, under German Granate), it is preferred to use the term
DINAMITI proietile for shell or projectile, as it is in Muni-
zionamento ITALIANO (AddnlRef C). We
Gelatina gomma. See Gelatina esplodente, item are applying the term granata to Hand Grenade
g, under DINAMITI (Granata a mane) and Mortar Grenade (Granata
a mortaio), but Italians did not use Rifle Grenade
Gelatina PI. Gelatinous expl used during WWH: (Granata da futile) during WWII
DNT 17, CC (Collodion Cotton) 0.5, Amm per- (See also CARTOCCI GRANATA and under
chlorate 36, Na nitrate 25, TNT 3.3 & PETN Hand and Mortar Grenades)
18% (Adds to 99.8%). Trauzl value 460cc &
gap Ocm (Belgrano, Ref 31, p 232) Grisou (Esplosivi ). See Antigrisou (Esplosivi)

Gelatina P2. Gelatinous expl used during WWII: Grisoudinamite. Permissible expl contg AN’88,
DNT 22.5, CC 0.5, Amm perchlorate 36, Na NG 10, CC 0.5 & woodflour 1.5% (Ref 31, p 326)
nitrate 25 & TNT 3.75% (adds to 87.75%);
Trauzl vrdue 400c & gap Ocm (Ref 31, p 232) Grisounite contd 95.5% AN & 4.5% TNN (Tri-
nitronaphthalene ) (Ref 31, p 326)
Gelatina P3. Gelatinous expl used during WWH:
DNT 17, CC 0.5, Amm nitrate 42, K perchlorate Grisounite gomma contd 70% AN, 29.5% ,NG
16.5, Na nitrate 18 & TNT 6%; Trauzl value & 0.5% CC (Ref 31, p 326)
350cc & gap Ocm (Ref 31, p 232)
Grisounite roccia or Rock Grisonite: AN 91.5
Gelatina Vender. See item o, under DINAMITI & TNN 8.5% (Ref 31, p 326)

Gelatinizzanti (Gelatinizes). Belgrano (Ref 31, Grisoutina. See item 3, in Table H, under
pp 2 18–19) lists: Centralizes, phthalides, alkyl- ESPLOSIVI DA MINA
phthalates (such as ethyl & but yl), diphenyl-
urethane and ethylphenylurethane Grisoutina all’ contd 11 .76% NG, 0.24% CC &
88.00% AN (Ref 31, p 324)
Geligniti. Blasting expls originating in England.
The formulation given by Molina (Ref 1, p 291) Grisoutina all: 13.2% NG, 0.52% CC & 86.55%
is NG 59, CC 4, K nitrate 29 & woodflour 8’ZO. AN (adds to fOO.27%) (Ref 31, p 324)
Another weaker formulation called Gelignite
d’ammonio contd NG 29.3, CC 0.7 & Amm Grisoutiti o Dinamiti senza fiamma (Flameless
nitrate 70~0. The stronger formulation was Dynamites). They are described by Molina
used by Italians as a bursting chge in some (Ref 1, pp 296ff). One example is given by
Land Mines (Ref 28, p 334) Belgrano on p 326 of Ref 31: NG 44, NC 12
& MgS04 .7H20 44%. The sulfate served as a
GEO and GEOM. Mining Explosives. Their cooling agent for the gases of expln
compns and props are given in Table I, under
ESPLOSIVI DA GUERRA Guanammon. An experimental castable expl
mixture of AN 85& dicyandiamide 15% (Ref
Gomma A and Gomma B. See Table 1, under 4, p 244) ~
ESPLOSIVI DA GUERRA
 I 164

Hand and Mortar Grenade (Granata a mano e Idrazina o Diammide, H2N.NH2, Hydrazine.
Granata da mortaio). Italian HE–A/P (high- See Belgrano (Ref 31, pp 127–28) and in this
expl-antipersonnel) grenades used during WWII Vol of Encycl, p H190-L
were almost totally of the “offensive” type.
Although the loading factor was usually low, the Idrazina nitrato, N2 H4.HN03. Hydrazine Ni-
grenade bodies were not adapted for maximum trate (Ref31, p 128) and in this Vol of Encycl,
fragmentation. .The antitank (A/T) hand gre- p H 196-R
nades were adaptations of the A/P grenades with
an addnl charge. There was no evidence of the Idroliti. Ammonium nitrate expls contg water,
use of shaped charges in A/T grenades. Like- which serves to lower mp of AN. They were
wise, chemical grenades were made of adapted manufd by the Societ~ Dinamite Nobel at Avi-
A/P grenades. No rifle grenades were used, gliana. The example cited by Piantanida (Ref
but instead there ,was used a small mortar, 4, p 246) contd AN 70, Hexogene (T4) 20,
serving as a grenade projector. The grenades paraffin 3 & water 7%. This expl was insensi-
were of the impact type, being provided with tive to shock (Ref 28, p 334)
an “all-ways” fuze which armed in flight
The following types are described in TM 9- Igniter Composition for Propellants, reported in
1985-6 (1953) (Ref 16): Breda Hand Grenades OrdnSergeant (Ref 4a, p 17), was BkPdr of
M35, M40 & M42 (pp 155–56, Fig 226); compn K nitrate ,74.4, charcoal 16.5 & S 9.1%.
Hand Grenade OTO, M35 (pp 155–157, Fig It was initiated by a primer cap contg MF 28.4,
227); Hand Grenade SRCM, M35 (p 158, Fig KC103 34:4, Sb2S3 35.6 & ground glass 1.6%
228); PCR Grenade (p 158, Fig 229); “L” Type
A/T Hand Grenade (p 160, Fig 230); Breda Igniters, Military. See Accenditori militari
Mortar Grenade (pp 160–61, Fig 231); Incendiary
Bottle Grenade (p 162, Fig 232); Smoke Hand. Imperialite. Blasting expl consisting of AN 85–
Grenades (p 162, no Fig); Breda Drill Grenade 90 & Al scales 15–10%. Its inventor Imperiali
(p 162, Fig 233); and SRCM Practice Grenade was killed in a violent expln during mixing of
(p 163, Fig 234) ingredients (Ref 28, p 334 & Ref 31, p 316)

Hexocire (Esplosivi). RDX-Beeswax Explosives. Incendiarie (Miscele). See Composizioni (o

The following formulations are listed in Belgrano Miscele) Incendiaries
(Ref31, p 264): Hexocire 95/5, Hexocire
grafitata 98/2/1 and 95/5/0.5 INNESCAMENTO (Priming or kdtiating of
Explosion)
Hexocire-Aluminum. RDX 80, beeswax 5 & Under this title, Belgrano (Ref31, p 499ff)
Al 15%; deton vel 8350m/sec (Ref31, p 264) describes the following items:
a) Capsule da mina ordinarie o Detonatori
Hexogene o T4. RDX or Cyclonite. Deton vel normali (Blasting Caps or Ordinary Detonators)
8520m/sec at d 1.71 (Ref 31, p 264) (pp 501-505)
b) Principal prove da eseguirse sui detonatori
Hexogene-Nylon, 95/5. Deton vel 8600m/sec (Principal Tests of Performance of Detonators)
at d 1.73 (Ref 31; p 264) (pp 505-507)
c) Detonatori secondari (Compound Detonators
Hexaliti. RDX/TNT Explosives, such as 30/70, (p 507)
50/50, 60/40, 70/30, 80/20 & 90/10. Their d) Detonatori o Inneschi elettrici (Electric De-
deton vels are betw 7240 & 8200m/sec at d tonators or Primers (pp 508–5 10)
1.6 (Ref 31, p 264) e) Esploditori per I’accensione dei detonatori
elettrici (Exploders for Igniting Electric Deto-
High Explosives (HE’s). See Esplosivi alti nators) (pp 511 –5 14)
 I 165

f) Accenditon elettrici (Electric Igniters) (pp MABT. High Explosive compn consisting of PA,
514–515) TNT & DNPhenol. Can be prepd by mixing
g) Principal Types of Detonators and Their MAT with MBT. Used as bursting charge (Ref
Characteristics are listed in Table 73, pp 516– 11, vo12, p 119)
17. Twelve types are Italian, the rest are W.
German, Austrian, USA and French Manlianite. A Cheddite-type expl consisting of
Giorgio (Ref 26), under the title “Mezzi @m Perchlorate 72, carbon 14.7 & sulfur
d’innesco di uso militare” (Initiating Devices for 13.3%. It was proposed by U. Alvisi (Ref 1,
Military Use), describes the following items: p 199)
Detonatori comuni (Ordinary Detonators) (pp
192–94); Detonatori elettrici instantanei, (In- MAT (Picratol). A castable HE mixture of PA
stant Electric Detonators) (pp 195 –98); Detona- 60 & TNT 40%. It is a yel-buff solid which on
tor elettrici a ritardo ordinario (Electric Deto- heating becomes plastic at 55° and melts at
nators with Ordinary Delay) (pp 198–99); 85°. Its props are: Ballistic Strength 103%
Detonatori elettrici a microritardo (Electric De- TNT; Brisance by Sand Test 44g sand crushed
tonators with Micro Delay) (pp 199–200]; vs 43g for TNT; Explosion Temperature 240–
Miccia a lenta combustion (Slow Fuse) (pp 280° in 5sec; Impact Sensitivity with 2kg Weight
189–92); Miccia detonante (Detonating Fuse) 13 inches vs 14 inches for TNT; Rifle Bullet
(PP 200–202); Miccia a rapida combustion Sensitivity, 10% detonations from impact of a
(p 202); Cordone di accensione, called in US .30 cal bullet fired at a distance of 90 feet;
Igniter Cord and in Italy Pirofis (pp 202–203) Stability, stable in storage; Velocity of Detona-
Accdg to OrdnSergeant (Ref 4a, p 18), tion 7 100m/sec at density 1.62 vs 6900m/sec
Italian Detonators of WWII contd as a primary for TNT. Used for cast-loading’ medium caliber
charge a mixt of LSt (Lead Styphnate), LA shells (Ref 11, Vol 2, p 111 & Ref 28, p 335)
(Lead Azide) and, as a secondary (base) charge,
PETN (Pentaerythritol Trinitrate) MBT (Esplosivo). A castable HE mixture of
Addnl Ref from CA: PA 60 & DNPhenol 40%. It is a yel solid which
E. Brandimarte, RivAeronaut, Astronaut-Missil becomes plastic at 68° and melts at 77°. It is
47 (l), 75–97 (1971) &CA 74, 119 (1971) less brisant and less powerful than TNT and re-
[Discussion on types of detonators, including quires a strong initiator for detonation; used for
metal fdaments, is given. Some detonation loading medium caliber shells. Its mixture with
parameters for T4 (RDX), Tritolo (TNT), NG, MAT is known as MABT (Ref 11, Vol 2, p 119
MeN03 and Tritolite (TDX–TNT mixt) are & Ref 28, p 336) [Comp with French DD (Ex-
included] plosif) and Japanese Cha7Jyaku]

Kratiti e Nitrokratiti. Series of expl mixtures Melinita (Picric Acid), described here as Acido
developed by U. Alvisi, which consisted of Am- picrico
monium Perchlorate with NG and/or NC (Ref
l,p 200&Ref 31, p 363) Metriolo (Nitrometriolo) o Nitropentaglicerina,
H3C.C(CH20N02)3, (Metriol Trinitrate, MtrTN).
Land Mines. See under Mines and Traps A slightly turbid, heavy explosive oil developed
before WWH by the SA Bombrini Parodi-
Luci colorate (Miscele). See Composizioni (o Delfmo (BPD) and manufd at the Colloferro-
Miscele) a luci colorate in Belgrano (Ref 31, Roma Plant. It was obtd in 92% yield by ni-
p 627) and under PIROTECNIA o ARTIFICI trating trimethylolmethylmethane in a batch
DA GUERRA process using mixed nitric-sulfuric acid of zero
water. The process is similar to that used for
M4, M6, M8 Polveri al nitrometriolo. See under prepn of NG, except that high ratios of acids
Polvere al nitrometriolo are used. A detailed description of prepn is
 .

I 166

given in PATR 2510 (1958), p Ger 113-L Fig 239); Wooden Box A/T Mine (p 168, Fig
Metriol Trinitrate has been used in smokeless 240); Four-Igniter A/T Mine (pp 168–69, Fig
proplnt, such as in Polvere BPD described by 241); A/T Mine B-2 (pp 169–70, Fig 242);
Caprio (Ref 11, Vol 2, p 154). By itself, A/T Mines V-3 and V-5 (p 170, Fig 243); ~
MtrTN does not gelatinize NC unless at temps Pignione Type I & II Bakelite A/T Mine (pp
of at least 1100. However, when ca 8% of acetil- 171–72, Fig 244)
metriolo (triacetate of metriol), H 3C.C(CH2 .0 CH3)3, Note: Although the title of the Section includes
is added, gelatinization takes place at 80°. The the word “Traps”, no description of such item
cool Polvere BPD described by Caprio (Ref 11, is given
Vol 1, p 156) contd: MtrTN 59, NC 33, acetyl-
metriol 5.5 & Centrality 2.5% Miscela C o PE. A plastic expl consisting of RDX
Advantages of MtrTN are low volatility, low and a plasticizer; Miscela Cz– RDX, CC &
calorific vahre (which means less erosion of gun plasticizer is water-resistant; MisceLz C~ - RDX,
barrels) and a good degree of flashlessness. The Tetryl, CC & plasticizer; Miscekz C4 – Plastic
Italian Navy was greatly impressed by the con- expl consisting of RDX 91 with Polyisobutylene
siderably reduced !flash in “Metriolo propellenti” & other ingredients(Ref31, p 263)
(Ref 28, p 336)
Miscuglio nitrico-solfurico per nitrazione. (Mixture
Mezze d’innesco (Initiating Devices). See under of nitric-sulfuric Acids for Nitration). As an
INNESCAMENTO example, Belgrano (Ref 31) describes on pp 159–
162, prepn and analysis of acids used in nitra-
Mezze d’innesco, di uso militare (Initiating De- tion of glycerol
vices for Military Use). See under INNESC~ENTO
MNDT. See Siperit
Miccia (Fuse). See under INNESCAMENTO
MST. See Nougat
Mines and Traps. antipersonnel (A/P).
Italian
land mines of WWH ,were operated by pressure MTX. A mixture of French origin: Melinite (PA)
or trip wires. They were often difficult to de- 55, TNT 35 & Xilite (TN-meta-Xylene) 10%
tect, especially those operated by pressure in (Ref 31, p 249)
which only a portion of the lid or igniter ap-
peared above the ground. Bakelite and wood were NAC. See Polvere NAC
used in the construction of some mines to pre-
vent detection by magnetic instruments NA–OC (Nitrato ammonico-olio combustible).
Anti-tank (A/T) mines varied in appearance, See AN–FO
being tubular, rectangular, or circular in shape.
Some were made of bakelite or wood Nitram X. One of the mining expls, listed in
Improvised mines seem to have been the Italian Ref 31, p 171
specialty in. the field. They used the majority
of such mines in Abyssinia, since the supply of Nitramite o Avigliana 3. An Ammonal-type
standard mines was apparently limited. Most of expl mixture consisting of AN 71 –72, Al 22
these mines were of wooden construction and & bitumen pitch (or paraffin) 6–7%. Used as
used blocks of TNT for the bursting chge. a bursting charbe in all types of ammunition
Sometimes shells and shrapnel were used for (Ref 4, p 238; Ref 28, p 337 & Ref 31, p 316)
mines
The following items are described in TM 9- Nitrato ammonico o Nitrato d’ammonio, (Am-
1985-6 (1953) (Ref 16): Picket A/P Mine (p monium Nitrate, abbrd as AN). It is described
165, no Fig); B4 A/P Mine (pp 165–66, Fig in Ref 31, p 306–16. Used in a wide variety of
236); Bakelite and Wooden A/P l-lb Mine (p , military and commercial expls, such as: Afocite,
166 & p 237); Ratchet Mine (Railroad Mine) Albite, Amatolo, Ammonal, Ammonite No 1,
(p 167, Fig 238); Railway Mine (pp 167–68, ANS or ASN, Astralite, Cremonite, Dinamiti,
 I 167

Dinamon, Ethos or Escho, Esplosivi da guerra, Nitrocratiti. See under Kratiti and in Ref 31,
Esplosivi da mina, Esplosivo S20, FNP Esplosivo, p 363
Gelignite, Comma, Idrolita, Imperialite, MST or
Nougat, PAN, PANA, PNP, Polvere “Cannel”, Nitrodiglicole, Nitroeterolo o Dinitrodietilen-
Romite, Sabulite, Schneiderite, Siperite, Solfite, glicoi (Diethyleneglycol Dinitrate, abbrd as,
Umbrite, Vibrite, Virite and others (Ref 28, p DEGDN), 02 N0.CH2 .0.CH2 .0N02, is de-
337) scribed in Belgrano (Ref.31, pp 136–39).
Colorl expl liq used as a component of proplnt,
Nitre X Galleria. One of the mining expls listed and composite expls. The Itahan Army Speci-.
by Belgrano (Ref 31, p 171) without giving its fication Requirements listed in the pamphlet
composition “Capitolato Tecnico Generale per la Fornitura
di Esplosivi Propellenti”, MD Esercito (1 95 1),
NITROCELLULOSE o NITROCOTONE. There CTF 28, are as follows: N content 14.10%,
are three Italian basic types for use in Pofven”. alkalinity (as %Na2C03) .0.0023; and stability
serrzafumo (Smokeless Propellants): by 120° German test, 30 reins for red colora-
A. Cotone collodio (Collodion Cotton), which tion of indicator paper (Ref 28, p 337)
contains 11.2 to 12.3% N Two composite expls contg DEGDN are
B. Pirocollodio (Pyrocotton), which contains listed in Ref 31, pp 139–40: a) Esplosivo da
12.5 to 12.7% N, mina –. DEGDN .36.5”, CC 1.5, PETN 10.0,
C. Fulmicotone o Cotone fulminate. (Gun- AN 28.0 & Na nitrate 24.0% 6) Esplosivo
cotton, abbrd as GC), which contains 13.2 to plastico – DEG.DN 32 & RDX 68%, experiment-
13.4% N(Ref 31, p 188) ~~ ally used by Ital Genio Militare (Corps of En-
All NC’s may be divided into the following gineers)
groups: Two Polveri al nitrodiglicol are listed in
a) Nitrocellulose a solvente volatile (NC used Ref 31, p 208: a) A 860cal/g-DEGDN 68,
with ether-alcohol solvent) is usually Pirocollodio. Nitroacetylcellulose 30 & Centr,alite 2%
As an example of its use is the Polvere per mitrag- b) A 730cal/gDEGDN 27.0, Nitroacetylcellu-
Iiatrice FIAT mod 35 (Propellant for machine lose 63.5, acetylcellulose 5.0 & Centrality 5%
gun FIAT, Mod 35), ‘which consists of NC 97,
Centrality 2 & DPhA (Diphenylamine) 1% (Ref Nitrogelatina. Same as Gelatina dinamite, de.
31, p 203 ~ scribed as item i; under DINAMITI
b) Nitrocellulose a solvente jlsso (NC used with
fixed solvent) is usually Cotone collodio of N NITROGLICERINA, Trinitroglicerina o Olio
content ca 12% and Pirocollodio, As a fixed esplosivo (Nitroglycerol, abbrd as NG),
solvent; NG or its mixture with NGc (Nitro-
glycol) is used. Polveri NAC (qv) is an example (02 NO)H2C.CH(ON02) .CH2(ON02). An oily
of using Cotone collodio and Balistite atten- expl liquid first prepd by Ascanio Sobrero in
nata (qv) is an example of using Pirocollodio Univ of Torino, Italy. A detailed description of.
(Ref31, pp 205–06). Other examples of its prepn, props,. analysis and uses is given by
proplnts using NC with f~ed solvents are Belgrano (Ref31, pp 140ff)
Polveri FB, FC, al nitrodiglicol, al nitrome- The Italian Army Specification Requirements
triolo, and al trinitroanisolo are listed in as of 1951 were as follows: Titolo d’azoto (N
Ref 31, pp 208–10 and also here under content) 18.3670; Reazione (Reaction) neutral
Polveri to phenolphthalein; and Stabilit~ al saggio Abel
c) Nitmcellulose a solvente misto (NC used a 80°C (Stability by Abel Test at 80”C), 14
with mixed solvent) is usually a mixture of minutes (Ref 28, p 338)
Pirocollodio & Fulrnicotone. Mixtures of NG Used in many military and commercial expls
with ether-alcohol or with acetone are used as and proplnts, such as Brdistite & other double-
solvents. Examples of these propellants are” base proplnts, Dinamiti, Esplosivi da mina,
Polvere C2 and Solenite ordinaria(Ref31, p 212) Gelignite, Gomma, Pentrinite & others
 I 168

Nitroglicol o Dinitroglicol [Ethyleneglycol NTP. A military expl mixture consisting of

Dinitrate (EGDN) or Nitroglycol (NGc)] , AN 77, RDX 20 & paraffin 3%; deton vel
02 N0.H2C.CH2 .0N02. An oily expl liquid, 5850m/sec at d 1.62 (Ref 11, Vol 2, p 114 &
fust prepd in 1870 by Henry. Its prepn, props Ref31, p 266)
and anrdysis are described by Belgrano (Ref 31,
-.
pp 133–36) NX. Mixture of AN 77 & Xilite (TN-m-xylene)
Used in many countries as an additive to NG 23% (Ref31, p 249)
to prevent its freezing. Such expls are known
as Dinamiti and Gelatine incongelabili Obice. Howitzer

Nitroguanidina (Nitroguanidine, abbrd as NGu), Olio da combustione. Fuel Oil

H2N.C(:NH).NH.N02, wh ndls, mp 246–47°,
first prepd in 1874 by Jousselin. Its prepn, Olio esplosivo. One of the names for NG
props, uses and analysis are described by Bel- (Nitroglycerol)
grano (Ref 31, pp 251 to 254). NGu has been
used as a component of military and commercial Olio di sgocciolamento (Drip Oil in the USA
expls and as a cooling agent for smokeless pro- and Tropf61 in Germany. A crude, commercial,
pints. Four mining expls contg 15 to 28% are black, oily substance resulting from the two-
listed in Ref 31, p 253 and in Ref 28, p 338. stage nitration of toluene in the man.uf of TNT.
Expl compns Albite and Umprite were used Its main constituents are isomers of .DNT with
during WWII as bursting charges (Ref 28, p 338) small quantities of isomers of TNT and some
other aromatic nitrocompounds. It has been
Nitrometriolo (Metriol Trinitrate). See under used as an antifreeze addn to Dynamites, such
Metriolo as in Dinarniti incongelabili; in some AN expls
and as a gelatinize of NC used in some proplnts.
Nitronaftiti. Accdg to Piantanida (Ref 4, p Due to the fact that its composition is variable,
236), they are mixts of RDX 75–80 with MN- and it contains some sulfuric acid derivatives,
Naphthalene 25–20% manufd by the SA Dina- its use in military expls h not recommended
mite Nobel at Avigliana. The mixt softens at Another way to utilize “drip oil” is to se-
75–80° but does not melt; is press-loaded, while parate it from purified DNT, and nitrate the oil
soft, in ammu~tion (Ref 28, p 339) to TNT, thus making the manuf in three stages.
Accdg to Belgrano (Ref 31, p 26), Nitro- The resulting product is nearly as powerful as
naftiti are ‘plastic rnixts of RDX & DNNaph- TNT but of inferior stability (Ref 28, p 339)
thaline, tirsing ‘at 70–80°. They are moie A typical commercial explosive is given on p
powerful than TNT 340 of Ref 28: Olio di sgocciolamento 16,
TNT 7, AN 45, Na nitrate 15 K perchlorate
Nobelite Galleria. A mining expl consisting’ of 16.5 &CC 0.5%
NC 37, KC104 34, NaN03 24, DNT 3 & mineral
oil 2Yo; temp of expln 2800”C; burns in ajr at Ossonite. A liquid, Sprengel-type expli prepd
ca 130° (Ref 31, p 362) in situ by mixing ca 58 parts of PA (or 28 pts
of MNB) with coned nitric acid, just before use
Nougat o MST (Esplosivo). An Amatol-type (Ref31, p 379). Accdg to Ref 28, p 340, some
expl consisting of AN 49, TNT 44 & DNNaph- liquid N peroxide is also added to PA and nitric
thalene 7%(Ref 11, VOI 2, p93 &Ref 31, p acid
297). It has been used cast-loaded in the fol-
lowing shells: 120/2 lmm HE, 120/2 lmm HE Oxitiquite. It is one of the esplosivi all’aria
(cast steel); 149/35mm HE, 149/35rnm HE (one hi@a (Liquid Air Explosive) prepd in situ by
piece); 210mm HE (bombs), 305/17mm HE pouring, liquid air (or liquid oxygen) into a
(cast steel) and 305/17mm HE (one piece) mixture of 3 parts of carbon, impregnated with
(Ref 28, p 339) . . 2 parts of petroleum, (Ref 31, p 305)
 I 169

Oxilite. A liquid air expl prepd in situ by PANA. HE mixt of PETN 32, PETA 24, AN
pouring liquid air (or liquid oxygen) into a 35 and Al powder 9% developed by BPD for
mixture of fossil flour, previously impregnated pres~loading ammunition. It is more powerful
with petroleum (Ref 31, p 305) than Ammonrd, but also more expensive (Ref
NOTE: Accdg to Belgrano both mixts (Oxi- 4, p 232; Ref 28, p 340& Ref 31, p 182) ‘
liquite & Oxilite) have been used in high
mountains for construction of hydroelectric PE (Amer). Abbrn for Pentaerythritol
plants, for construction of the Sempione tunnel
and for work by Genio Militare (Corps of En- PE (Italian). Designation .of Miscela C (qv).
gineers) (Ref31; p 305) Do not confuse with C (Polvere)

Pl, P2 & P3. See Gelatina PI, Pz & P3 Pentaerythritol Tetranitrate (PETN). See
PENTRITE
PA (American). Abbrn for Picric Acid
Pentolite. See Pentritolo and Pentrol
PA (Italian). Mixtures of Pentrite (PETN) with
Acetato di pentaeritrite (Pentaerythritol Tetra- Pentriniti. Powerful mixts of PETN 80–85 & ‘
nitrate or PETA in proportions of 65/35 & NC 20–15% invented’ in 1929 by the late Dr
75/25. They were developed by BPD (Bombrini- A. Stettbacher of Switzerland. l%ey are de-
Parodi-Delfino SA, Co~oferro-Roma). They scribed by E. Piantanida in MAF 14, 458 (1935).
melt at 85–88°, have the same power as TNT Belgrano (Ref 31) gives on p 182 its compn but
and are fairly insensitive to shock. PA mixts does not list its props
were proposed for cast-loading shells, but were
seldom used because PA is more expensive then PENTRITE o Tetranitrato di Pentaeritrite
TNT. Accdg to Piantanida (Ref 4, p 232), PA (Pentaerythritol Tetranitrate, abbrd as PETN),
was also used in compressed form as a secondary C(CHZ oNo2)4. Its prepn, props, uses and analy-
chge in detonators. See also Ref 28, p 340 & sis are described by Belgrano (Ref 31, p 176–1 83)
Ref 31, p 182) Its props given on p 181 of Ref 31 are as
follows: Density (max) 1.62, Explosion Tem-
Palla – Solid Shot; Ball perature 195°, Flame Temperature on Explo-
sion (Temperature Developed on Explosion)
Palla dum dum – Dumdum Bullet 3600°, Heat of Explosion 1400kcal/kg, Specific
Pressure 10500atm/kg, Volume of Gas at 0° &
Palle – Ball Ammunition 760mm 780 l/kg, Trauzl Test 500cc, Impact
Sensitivity with 2kg Weight 30cm and Detonation
PALLOTTOLA - Bullet; Rifle Bullet; Shot Velocity 8400m/sec. Giua (Ref 19) gave some
slightly different values, such as: Explosion Tem-
Pallottola esplodente – Explosive Bullet; Dumdum perature 190°, Flame Temperature 4050°,
Bulet Trauzl Test 540cc and Impact Sensitivity with
2kg Wt 38cm (listed also on p 258 ofRef31)
Paliottola perforante – Armor-piercing Bullet Straight, compressed, PETN was used during
WWII as a bursting charge in small caliber shells
Pallottola a revestimento d’acciao – Steel- (such as 20mm) and as a booster or base chge
jacketed Bullet in detonators. PETN, phlegmatized by 8–1 O%
wax (or paraffin) and dyed blue,
pallottola tracciante – Tracer Bullet was used as bursting charge in shells larger than
20mm and as demolition charges (Ref 28, p 341)
PAN. Mixture of PETN 42, PETA 23 & AN PETN was also used in composite expls, such
35% developed by BPD for press-loading ammu- as ASN, Esplosivi da guerra, Esplosivi da mina,
nition (Ref 4, p 232; Ref 28, p 340 & Ref 31, FNP Esplosivo, Idrolita, Nitronaftita, PA, PAN,
p 182) PANA, Pentriniti, Pentritolo, Pentrol, PNP Es-
plosivo, Unknown Name Explosives and others
 I 170

Pentritolo o Pentrol (Pentolite). Mixtures of Pirocollodio. See under Nitrocellulose

PETN & TNT in various proportions. Accdg to
Caprio (Ref 11, Vol 2, p 115), mixts of TNT PIROTECNIA O ARTIFIZI DA GUERRA
with PETN 40–6070 were used under the name (Military Pyrotechnics). Colonel and now General
of Pentrol, by the Genio Militare (Corps of Attilio Izzo in “Pirotechnia e Guochi Artificial”
Engineers) in demolition charges. Accdg to (Pyrotechnics and Fireworks), listed as Ref 12,
Ref 28, pp 341–42, mixts of PETN 50–80 describes various Italian milita~ pyrotechnic
and TNT 50–20% were used as early as 1934 devices and gives on pp 204–238 numerous com-
as bursting charges in land mines, demolition positions. More recent book is that of Dr
charges, and in some underwater ammunition, Camillo Belgrano (Ref 31) who on pp 623–35 lists,
such as depth charges. Some Pentritols were under the title “Pirotecnia”, many compns
dyed red and some of them further phlegmatized A. Composizioni a lute gialla per stelle (Compns
by immersing in molten paraffin or by” incorporating for yellow light stars) a) NaN03 74, S 8 &Al
some MNT (Mononitrotoluene) in the mixture. 18% b) KN03 14, NaHC03 5, pulverin (meal
Accdg to Belgrano (Ref 31, p 182), mixts with powder) 23 & shellac 6% (Izzo, p 204)
40–60% PETN, called Pentrol, have been used B. Comp a lute gialla per segnalazioni (Compns
in granate (shells or grenades), razzi (rockets), for yellow light signals) a) NaN03 55.5 &
proietili anticarro (A/T projectiles) or for cariche polyvinyl chloride 44.5% b) KN03 62.5,
cave (shaped charges) NaN03 10.5, S 23 & charcoal 4% (IzzO, p 204)
C. Comp a lute gialla per torre (Yel light compn
Pertite. See ACIDO PICRICO for torches) KC104 18, Na oxalate 9, Ba(N03)2
60, S 4 & shellac 9% (Izzo, p 205)
PETN. See Pentrite D. Comp a lute rossa per stelle (Compns for
red light stars) a) KC103 40, Sr(N03)2 40,
Picramide. See Trinitroanilino charcoal 6, lampblack 6 & tar 8% b) KC103
60, Sr(N03)2 25 & shellac 15% (Izzo, p 207)
Picrato ammonico o Picrato di ammonio (Am- E. Comp a lute rossa per segnalazioni (Compns
monium Picrate or AP), (02 N)3C6H2 .0NH4. for red light signals) a) KC103 30, Sr(N03)2
Its prepn and props are in Belgrano (Ref 31, pp 44, S 18, charcoal 2 & Sb2~ 6% b) KC104
288–89). Straight AP has been used in the 54, Sr(N03)2 36 & shellac 10% (Izzo, p 207)
US, under the name Explosive D, while in Italy F. Composizioni per tracianti (Tracer Compns).
it was used in composite expls Cremonite (qv) & In the book of Izzo (Ref 12, pp 210, 213 &
Prkratol 235) are listed a) Red (rosso) -colored tracer –
Sr02 40, Mg (powder) 40 & Sr oxalate 20%
Picratol. Mixture of Ammonium .Picrate 52 & b) Green (verde) tracer – Ba02 72.5, Mg 15;
TNT 48% listed in Belgrano (Ref31, p 246) Ba oxalate 5 & gumlac 7.5% c) Yellow (giallo)
as for use in semi-armor piercing projectiles. tracer – KN03 50, red arsenic 30 & sulfur 20%
Its power by Trauzl test is 380cc vs 285cc for In the book of Belgrano (Ref 31, p 633) are
TNT listed under the title traccianti a) Red tracer –
Sr nitrate 69, Mg 25 & binder 6%; b) Green
Piombite. Accdg to Caprio (Ref 11, Vol 2, ‘ tracer – Ba nitrate 55, Mg 35 & binder 10%; (

p 96) and Belgrano (Ref 31, p 35 1), it is an expl c) Tracer – KC103 58, SrC03 22 & shellac 20%
mixture consisting of Lead nitrate 76,. Tri- A typicrd Italian tracer compn examined during I
nitronaphthalene ,1.6,Calcium silicide 5 & vase- WWII at’ Picatinny Arsenal contd Ba nitrate 63.0,
Iine 3%. Trauzl Test value 155CCvs 285cc for Mg pdr 34.3 & binder-fuel 2.7%. It was used in
TNT. It was used in mining expls 47-mm AP (Armor-piercing) Shell (Ref 28, p 322)
Accdg to Molina (Ref 1, p 358), the follow- G. Comp a lute verde per stelle (Compns for
ing Piombite was used during WWI as a bursting green light stars) a) KC103, 30, Ba(N03)2 53,
charge in cast-iron shells of medium caliber: Pb shellac 15 & lampblack 2%; b) Ba(N03)2 70,
nitrate 75, Ca silicide 16, Pb carbonate (basic) shellac 17 & milk sugar 13% (Izzo, p 211)
6.5, TNNaphthrdene 1.5 & vaseline oil 1% (See H. Comp a lute verde per segnalazioni (Compn
also Ref 28, p 342) ~~
 I 171

for green light signals) KC103 31, Ba(N03)2 52, fossil meal 5%
S, 10& charcoal 6% (Izzo, p 211) R. Miscele all’esacloroetano (Mixtures with hexa-
I. Comp a lute verde per traccianti (Green light chloroethane). There are two mixts proposed
tracer compn) Ba02 72.5, Ba oxalate 5, Mg 15 by lzzo and three mixts by the Societ?i ACNA.
& gumlac 7.5% (Izzo, p 213) They contd 45 to 52.5 hexachloroethane, 25
J. Comp a lute azzurra per stelle (Compn for to 31.5 Zn dust, O to 2.0%0ZnO and some other
blue light star) a) KC103 70, ammoniacal Cu ingredients (Izzo, p 234). Belgrano, p 631, gives
sulfate 15 & shellac 1570; b) KC103 50, Paris HCIEt 50, Zn 25, ZnO 20 & fossil meal 5%
green 20, Ba(N03 h 17, shellac 10 & gum arabic S. Cbmposizione a tetracloroetano (Compn with
or dextrin 3% (Izzo, p 213) tetrachloroethane): TeCIEt 40, ZnO 20, Zn dust
K. Comp a lute azzurra per segnalazioni (Compns 15, Ca silicide 15 & NaC103 10% (Izzo, p 234)
for blue light signals) a) KC103 54.5, ammoniacal T. Composizioni per miscele fumogene colorate
Cu sulfate 27.5 & charcoal 18%; b) KC103 53, (Compns for colored smoke mixts). Good results
ammoniacal Cu nitrate 26, S 5 & charcord 16% were claimed to be obtd with the following:
(1220, p 214) Coloring substance (dye) 36, KC103 28, milk
L. Comp a lute violetta per stelle (Compn for sugar 28, sulfur 4 & Amm chloride 4% (Izzo,
violet light star) KC103 58.5, Sr(C103)2 14.5, p 231)
CUC03 10, gurnlac 7 & S 10% (Izzo, p 215) U. Composizioni a fimo giallo (Compns for yel-
M. Comp a lute bianche per stelle (Compns for low colored smoke) a) KN03 27, AS2S2 27,
white light star) a) KN03 65, S 19 & Sb2S3 S 27 & Sb2S3 19%; b) Realgar (As2S2) 30, S
16%; b) KN03 59, S 30 & pulverin (meal pow- 20 & KN03 50%o;used in traces for rockets;
der) 11%; c) KN03 60, charcoal 8, pulverin 8, c) Chrysoidine 30, Auramine (yellow) 10, KC103
iron fdings (paraffined) 16 & gum arabic or 35 & milk sugar 25% (Izzo, p 235). Belgrano,
dextrin 8%(P 216) and d) KC104 61, Al 31 & p 632, gave Chrysoidine 9–30, Auramine yel-
lycopodium powder 8% (p 218) low 34–1 O, KC103 33–35 & lattosio (milk
M1. Comp per stelle (Star compns). Belgrano, sugar) 24–25%
pp 632–33 lists the following compns: a) V. Composizione a fumo arancione (Compn for
NaN03 74, S 8 & Al 18%; b) NaN03 56, S 21, orange-colored smoke) Chrysoidine 45, KC103
charcoal 14, Na bicarbonate 4.5 & SrS04 4.5% 25, milk sugar 30 & mineral coal flour 5%
and c) Ba nitrate 50, KC103 35 & gumlac 1570 (Izzo, p 235). Belgrano,, p 632, gives HCIE
N. Comp a lute bianche per segnakrzioni (Compn 20, Auramine 14, Red of p-Nitroaniline 23,
for white light signals) a) KN03 52, S 22, pul- KC103 25, MgC03 4 & lattosio (milk sugar) 14%
verin 22 & Sb2S3 4%; b) KN03 61, S 19, pul- W. Composizioni a fumo rosso (Red smoke
verin 5 & Sb2S3 15% (Izzo, p 218) compns) a) Red of para-Nitroaniline 60,
O. Comp per miscele sibilanti (Compns for KC103 20 & milk sugar 20%; b) Red of p-
whistling mixtures) a) K picrate 70 & NaN03 Nitroaniline 26, Rhodamine B 53 & KC1Os 21%
30%; b) Gallic acid 50 & KC103 50% (Izzo, p 226) (Izzo, p 236). Belgrano, p 631, gives Rhodamine
P. Composizwne per fumata grigia (Compn for 70, KC103 15 & milk sugar 25%; also HCIE 30,
gray smoke) KN03 50, lampblack 12.5, charcord Rhodamine 34, KC103 18, milk sugar 14 &
12.5, colophony 12.5 & AS2S2 12.5%. The mixt MgC03 4%
is packed in cylinders 10cm in diam and 25cm X. Composizioni a fumo verde (Green smoke
long. For its initiation, a mixture of KN03 66, compns) a) Auramine yellow O 15, Indigo 26,
S 13, pulverin 11 & Sb2S3 11% is used (Izzo, KC103 33 & milk sugar 26%; b) Auramine yel-
p 231) low O 10, Indigo 20, KC103 30, milk sugar 20
Q. Composizioni per miscele fumogene a fumo & malachite green oxalate 20%0(Izzo, p 236).
brirnco (Compn for mixt producing white smoke). Belgrano, p 632, gives HCIE 31, Green of Mala-
Formula used by Italians duiing WWI: NaN03 chite 35, KC103 16, milk sugar 14 & MgC03 4~0
25, mineral oil 15, sawdust 50 & water 10%. It Y. Composizione a fumo azzurro (Blue smoke
was initiated by a mixture of NaN03 47.5, compn). Formulation of Izzo: Indigo 50, KC103
KN03 5 & sawdust 47.5% (Izzo, p 233). Belgrano, 30 & milk sugar 207. (Izzo, p 236). Belgrano,
p 631 gave CC14 50, Zn dust 25, ZnO 20 & p 632, gives Indigo 40–50, KC103 25–30, milk
 I 172

sugar 15–20 & Methylene Blue 20 or O% mixture with 25 pts of Black Powder. When
Z. Composizioni a fumo nero (Black smoke compressed at 150 atm, its luminosity is 600000
compns) a) Hexachloroethane 50, anthracene candles
15, naphthalene 15 & Mg powder 20% (Izzo, b) Mg 55, Na nitrate 33, Laminac 6 & Ba stearate
p 236 & Belgrano, p 631); b) HCIE 65, anthra- 6%; luminosity 600000 candles
cene 6, o!-naphthol 17 & Al powder 12%. They c) Mg 35, Al 5, Ba nitrate 52, Na oxalate 5.5
were used in Italian smoke bombs (bombs fumo- & oil 2.5%; luminosity 540000 candles
gena) initiated by a mixture of KN03 61, S 17.5, II 1. Miscela innescante per fumogeni (Initiating
AS2S2 17.5 & gum arabic or dextrin 4% (Izzo, mixture for smoke compns) KN03 61, red arsenic
p 236) and c) KC103 31, naphthalene 11, red P 17.5, S 17.5 & gum arabic 4% (Ref 31, p 632)
11 & tar 47%; d) KC1O 45, naphthalene 40 &
charcoal 15% (Izzo, p 237) PNP Esplosivo. A HE consisting of PETN 20,
Z1. Composizione a fumo viola (Violet smoke AN 77, & wax 3% has been used press-loaded
compn) 1-methylaminonitroquinone 18, 1,4- as a bursting charge in various projectiles (Ref
diamino-2,3-dihydroanthraquinone 26, KC103 26, p 160& Ref 31, p 182)
30.2, S 11.8 & Na bicarbonate 14% (Belgrano,
p 632) PNT. Belgrano (Ref 31) lists it on p 267 with-
Accdg to Gen Izzo (Ref 12, p 200), the prin- out giving its compn
cipal Italian factories manufg pyrotechnic compns
and items were, as of 1950, as follows: Polveri- Polvere alla ftalide - centrality. See Polvere FC
fichi Stacchini di Roma, la ditta Camocini di
Como, la Mugnaioni, la Societ2 ACNA, etc Polvere alla nitrocellulose. See Polvere NAC
The following Italian Military Pyrotechnic
smoke compns used in colored smoke signal de- Polvere BPD (Belgrano-Parodi-Delfmo Powder).
vices for air-to-air liaison were described by J. See under Metriolo (Nitrometriolo)
Goldenson & C.E. Danner in Chem & Engrg
News 26, 1976–78 (1948): Pohrere bruna o Polvere cioccolata (Brown Powder
Red – KC1O 26, lactose 27, Sudan IV 27, or Chocolate Powder) contd KN03 79, incom-
Rhodamine B 14, Auramine 5 & sucrose 1% pletely carbonized wood as po”wder 18 & sulfur
Yellow – KC103 30, “Auramine O“ 65 & 3%; used in some cannons prior to the invention
kieselguhr 5% of smokeless proplnts (Ref 1, p 147–8 & Ref
Green - KC103 27, lactose 25, dimethylamino- 28, p 345)
azobenzene 21 & 1,4-di-p-tohridinoanthraquinone
27% Polvere C. Same as Cordite Italiana
Black – KC103 60, naphthalene 20 & cY-MN-
Naphthalene 20% (Ref 28, pp 342–43) Polvere C2. See C2 (Polvere)
Following is addnl information given in the
book of Belgrano (Ref 31) Polvere C-12. See C-12 (Polvere)
1. Mhcele a Iuci colorate (p 627), calcd in
parts: a) White – KN03 70, pulverin 30, S 30 Polvere “Cannel”. A Cheddite-type expl contg I

& Sb2S3 5 pts; b) Red – Sr nitrate 45, KC103 Amm Perchlorate 80 & Cannel coal from Scot-
30, S 18, Sb$ ~ 6 & carbon 2 pts; c) Green – land 20% was proposed in 1900 by U. Alvisi
KN03 50, KC103 30 & S 10 pts; d) Yellow – as a blasting expl (Ref 1, p 200) .
KN03 60, NaN03 10, S 22 & carbon 4 pts;
e) Violet – KC103 42, Sr nitrate 18, S 30, Polvere CG-I 3. A Ballistite-type expl contg
calomel 5 & CUC03 5 pts and f) Blue – KC103 NG 25, NC (N 12.5%) 60 & DNT (solid) 15%
50, Cu nitrate 25, carbon 15 & S 5 pts (Ref 11, Vol 2, p 139 and Ref 31, p 210)
II. Miscele illuminanti compresse (Ref31, pp
629–30) Polvere CG-14. A Ballistite-type expl contg
a) Mg 43, Na nitrate 47 & ‘binder (Iaminac) NG 25, NC (N 12.5%) 60, DNT (solid) 10 &
10%. For its initiation use 75 pts of above Centrality 5% (Ref 4, p 183 and Ref 31, p 210)
 I 173

Polvere FB o Polvere allo ftalato di butilo. The principal Italian uses of Military BkPdrs
There are 860and 960 calorie-types, which contd, are as igniters in percussion primers. For example,
respectively: NC 32 & 31, NC (12% N) 57 & 61, the Igniter of the 105/28mm cartridge case contd
butyl phthalate 9 & 5.5 and Centrality 2 & 2.5%; 25-30g of BkPdr & ca 5g of lead foil, serving
used in rapid-fire cannons (Ref 11, Vol 2, p 148 as a decoppering agent (Ref 28, p 345)
& Ref 31, pp 206 & 208)
Polvere al nitrodiglicol (Propellant with DEGcDN).
Polvere FC o Polvere alla ftalide-centralite. Two types are described in Belgrano (Ref 31, p
There are 860 & 960 calorie-types, which contd, 208), 860 cal & 730 cal of compns, respectively:
respectively: NC 28 & 32, NC (12% N) 64 & DEGcDN 68 & 27, Nitroacetylcellulose 30 &
62.5, phthrdide, C6H4.CH2.0.C0 4 & 3.5, Cen- 63.5, acetylcellulose O & 5 and Centrality 2 &
trality 3 & 1.5 and vaseline 1 & 0.5%; used in 4.5%
rapid-fire cannons (Ref 11, Vol 2, p 148 & Ref
31, p 206) Polvere al nitrometriolo (Metriol Trinitrate Pro-
pellant). Three types are described in Belgrano
Polvere per mitragliatrice FIAT mod 35 e cal 8 (Ref31, p 210), ikf4, M6 & M8 with compns,
(Propellant for Machinegun FIAT, Mod 35, Cal 8). respectively: Metriol Trinitrate 55.5, 57.5 &
See “Polvere italiana per cartucce cal 8, per 59%; NC 40, 36 & 33%; acetylmetriol 2.5,
mitragliatrici”, under POLVERI DA LANCIO 4.5 & 5.9%; and Centrrdite 2, 2 & 2.5%
SENZA FUMO, item A. Polveri alla sola
nitrocellulosa o Polveri a una base Polvere al trinitroanisolo–Stabilite. Two formu-
lations are listed in Belgrano (Ref31, p 210):
Polvere NAC o Polvere alla nitroacetilcellulosa a) TNAns (Trinitroanisole) 40 & NC 60%0
(Propellant with Nitroacetylcellulose). There are b) TNAns 34, NC 60, NC 5 & water 1%
860 & 960 calorie-types, which contd, respectively:
NC 27 & 32, Nitroacetylcellulose (N 11.2%) 66 Polvere verde (Green Powder). A Cheddite-type
& 63, Centrality 7 & 4 and DPhA O & 1%; used expl: KN03 66.7, PA 19.0 & hFe(CN)6 14.3%;
in cal 20 & 37mrn cannons (Ref 11, p 147 & was used in blasting operations (Ref 28, p 346).
Ref31, p 206) Belgrapo (Ref 31, p 356) lists this expl, but
gives for KN03 39%, which is evidently in error
POLVERE NERA (Black Powder) o Polvere da
fuom (Fire Powder) (Abbreviated as BkPdr) POLVERI DA LANCIO SENZA FUMO (Smoke-
The latest Italian book describing Black Pow- less Propellants) o Polveri colloidal (See also
der is that of Belgrano (Ref 31, pp 341–50). Esplosivi da lancio o Deflagranti).
Black Powders are subdivided into three types: Giorgio (Ref 26, pp 204–08) subdivides them
1) Polvere da guerra (Military Type) KN03 as follows:
74–75, carbon 15–1 6 & sulfur 10%O A. Polveri alla sola nitrocellulosa a solvente
2) Polvere da caccia (Hunting or Sporting Type) volatile o Polveri Base Pro-
a una base (Single
KN03 75–78, carbon 12–15 & sulfur 9–12% pellants with Volatile Solvent). .,To these belong
3) Polvere da mina (Mining or Blasting Type) a proplnt listed by Giorgio, p 205 as Polvere
KN03 60--72, carbon 14–21 & sulfur 13–18% italiana per cartucce cal 8 per mitragliatrice,
The following average props of BkPdr are which contd: NC (12.8% N) 97, Centrality 2
listed by Belgrano on p 349: Density (max) & DPhA (Diphenylarnine) 1910.It is in the form
1.7; Temperature of Explosive Decomposition of tubes 0.75–.01 x 2mm, graphited. The same
300°; Temperature of Explosion 2700°; Heat proplnt is listed by Belgrano (Ref 31, p 204) as
of Explosion 740cal/g, Specific Pressure 3250 “Polvere per mitragliatrice FIAT mod 35 e cal
atm/kg; Volume of Gas Developed on Explosion, 8“ (Propellant for Machinegun FIAT Mod 35,
calcd at STP 325 liters/kg; Trauzl Test value Caliber 8)
30–40cc; Impact Sensitivity with 2kg Weight B. Polveri a doppia base (con NGL) [Double-
70cm; and Velocity of Detonation 1400m/sec Base Propellants with NG (Nitroglycerol)] are
(See also Ref 28, p 345) divided into:
 I 174

a) Polveri a doppia base senza solvente volah”le similar to British, French and Japanese. Most
(Double-Base Propellants Without Volatile Sol- field equipment was semi-f~ed, with the smaller
vent), called by Belgrano Polveri a solvente jhso caliber and AA (Antiaircraft) guns using fixed
(Propellants with Fixed Solvent). To these be- ammunition. When the semi-fmed type of am-
long Balistite normale o ordinaria (with 50% munition was used, the propellant charge was
NG); Brdistite a basso titolo (with 42% NG) divided into a number of parts which were en-
(Ref 26, p 205); Polvere FB, Polvere FC & closed in silk bags. Igniters of BkPdr were also
Polvere NAC (Ref 31, p 206) included. The complete charge was ~nclosed in
b) Polveri a doppia base con solvente volatile the cartridge case and closed by means of a
(Double-Base Propellants With Volatile Solvent), cardboard cup. In the base of the cases were
called by Belgrano (Ref 31, p 211) Polveri a fitted percussion primers of standard design
solvente misto (Propellants with Mixed Solvent). In guns using bag ammunition, an igniter
To these belong Polvere Cz [described here as which had an extension piece was fitted into
Cz (Polvere)], also known as Cordite italiana the vent hole. For initiation of propellant
and Solenite (qv) (Ref 26, p 206) charges, the types of tubes used were friction,
C. Polveri a piu’ componenti (Propellants with percussion, and electric percussion
Several Components). Giorgio (Ref 26) lists The Italians designated their projectiles by
on p 207 among them some propellants which the caliber, the specific equipment in whcih they
are listed by Belgrano on p 206 under Polveri were used and the model numbers of the pro-
a solvente fisso. One of them, Polvere alla jectiles. In most casesthe model number in-
Centrality, lsited by Giorgio on p 207, was not dicated the year in which the item was designed
found in Belgrano. Its compn is NG 24, NC Accdg to MUNIZIONAMENTO ITALIANO
69 & Centrality I 7% (Addnl Ref C), Proiettili Italiani may be divided
Under the title “La preparazione delle polveri into: Proietti”li di piccoli calibn” (Small caliber
colloidal”, Giorgio described on pp 209– 10 projectiles, inclusive to 100-mm); Proiettili di
the prepn of single-base and double-base proplnts medi calibn” (Medium caliber projectile, from 102
Under the title “Fabricazione delle polveri to 210-mm) and Proiettili di grosso calibri (Large
a solvente fisso”, Belgrano described on pp 206– caliber projectiles, above 210-mm)
07 methods of prepn of double-base proplnts Projectiles may be classified also accdg to
with fixed solvent their effect on the target (bersaglio), as follows:
Under the title “Analisi sulle polveri di lancio”, a) Proiettili ad azione esp[osiva. Projs fdled
, Belgrano described on pp 2 13– 14 analytical pro- with HE’s, which when initiated by the fuze
cedures used for single-base and double-base blow up either during flight or on reaching the
proplnts contg as stabilizers DPhA, Centrality, target (Granate mine, Granate bombe, Granate
etc torpedini and Granate scoppianti) (Mine-, Bomb-,
Torpedo- and Explosive Shells)
Polveri senza fumo. See POLVERI DA LANCIO b) Z+oiettili ad azione proiettiva (Antipersomel
SENZA FUMO or Projecting Shells), which on bursting scatter
splinters or pellets over more or less wide range
PRIOETTO o PROIETTILE (Projectile) and are designed to hit personnel or equipment.
Accdg to “MUNIZIONAMENTO ITALIANO” They may be called antipersonnel or fragmenta-
(Addnl Ref C), the terms proietto o proiettile tion (Granate ordinarie, Granate di ghisa acciai-
are used referring to any heavy object which is osa, Granate dirompenti o a tempo e Granate
fired from a gun and produces a destructive a fratura prestabilita) (Ordinary-, Steel-pig-,
effect at a distance. This object may be solid Demolition-, Time- or Predetermined Time Burst
(like an AP Bullet) or hollow (like HE Projectile) Shells)
loaded with a bursting charge expl (carica di c) Proiettili speciali (Special Shells). These in-
scoppio) which is detonated by an initiation clude incendiary (Incendiary), fumogeni (Smoke),
train nebbiogeni (fog), illuminanti (Illuminating) e
Accdg to TM 9-1985-6 (1953) (Ref 16, p proiettili carichi di aggresivi chimici (CW Shells)
61), Italian projs used during WWH were very d) Proiettili perforanti (Armor-Piercing Pro-
 I 175

jectiles, abbrd AP). They contain a small expl (p 134, Fig 201); Percussion Nose Fuzes M1O
charge encased in specially treated steel. Used (Guerritore) PC and M (Guerritore) MEGC (p
against tanks, ships and fortifications 135, Fig 202); Percussion Nose Fuze 1, M35
e) Proiettili semiperforanti (Semi-penetrating (p 136, Fig 203); Percussion Nose Fuze 1,
Shells) contain a larger expl chge and, in addn M38 (p 137, Fig 204); Percussion Nose Fuze 1,
to penetrating effect,’ they have an expl effect M32/38 (p 137, Fig 205); Percussion Nose Fuze
f) Scatola a mitraglia (Case Shot or Canister) M40 with Detonator M40-Ordinary (p 138, Fig
consists of sheetmetal cylinders contg pellets 206); Ditto – Instantaneous (p 138, Fig 207);
cemented by resinous or similar binder. Used Percussion Nose Fuze for 37/40 AP (p 139,
in close-range combat Fig 208); Percussion Nose Fuze M39 (p 140,
g) Hollow (Shaped) Charge Projectiles (Cariche Fig 209); Percussion Nose Fuze OK BO SC 41
cava) are not described in AddrdRef C (p 141, Fig 210); Percussion Nose Fuze M16
There were also inert projectiles used for (OK 259 12) (p 141, Fig 21 1); Percussion Nose
training purposes Fuze O BO 34/37 (p 142, Fig 212); Percussion
Italian WWII projectiles are described and Nose Fuze for 37/54 HE Shell (p 143, Fig 213);
illustrated under “ITALIAN PROJECTILES Nose Time Fuze M900/14 (p 144, Fig 214);
AND CASES” in TM 9-1985-6 (1953) (Ref 16) Nose Time Fuze OT 32 (p 145, Fig 21 5); Time
and in “MUNIZIONAMENTO ITALIANO and Percussion Nose Fuze ADE M99 (p 146,
(AddnlRef C), ako as complete rounds. We are Fig 216); Nose Time Fuze M06/17 (p 147, Fig
describing rounds for small arms under Armi 217); Time and Percussion Nose Fuzes ADE
portatili, munizioni, while artillery ammunition M06 (p 147, Fig 218); Time and Percussion
is described and illustrated under CARTOCCI Nose Fuze ADE M12 (p 148, Fig 219(; Time
GRANATA, where many Hollow Charge and Percussion Nose Fuze ADE M36 (p 149,
(Catica cava) Shells are listed Fig 220); Time and Percussion Nose Fuze ADE
M32 (p 150, Fig 221); Nose Time Fuze OT 33
PROJECTILE FUZES (Spolette per proiettili). (p 151, Fig 222); Mechanical Time Nose Fuze
Accdg to MUNIZIONAMENTO ITALIANO M36 (p 152, Fig 223); Base Fuze for 47/32
(AddnlRef C), projectile fuzes may be divided AP (p 153, Fig 224); Base Fuze for 100/17
by their location into spolette anteriori (Nose Hollow Charge (Carica cava) (PP 153–54, Fig
Fuzes) and spolette posteriori (Base Fuzes); 225)
and in terms of operation into instantenee
(Instantaneous), ordinarie (Regular) and Propellenti (Propellants). See Esplosivi da lancio
rr”tardate (Delay)
A number of fuzes used before WWII are Propellenti per razzi (Rocket Propellants). A
known, but it is preferable to list here fuzes of brief description is given by Belgrano (Ref 31,
WWII, which are described and illustrated in pp 128–29). They are divided into liquidi e
TM 9-1985-6 (1953) (Ref 16). The fuzes are solidi. Liquids are divided into monopropellenti
divided into: and bipropellenti, and monopropellenti are sub-
a) Nose Percussion Fuzes (Field Equipment), divided into three groups:
spolette percusswni 1) Those contg in its molecule both combustible
b) Nose Percussion Fuzes (Naval and Coastal and oxidizer, such as nitromethane, nitroethane,
Defense) ethyl nitrate, NG, etc
c) Time Fuzes (Field Equipment), spoletta a 2) Compounds which easily undergo exothermic
tempo – Combustion Type and spoletta me- decompn, such as hydrazine, acetylene, ethylene,
canica a tempo – Mechanical Type etc
d) Time Fuze (Naval and Coastal Defense). 3) Synthetic mixtures of oxidizers with com-
OT – Nose Time Combustion Type and OMT - bustibles
Nose Mechanical Time Type PropeUants used during WWI1 were usually ,
e) Time and Percussion Fuze ADE liquid bipr,opellants, consisting of gasoline,
FolIowing are the fuzes described in Ref 5a: aromatic amines and alcohol as combustibles
Percussion Nose Fuze for 65/17 HE Projectile with oxidants, such as liquid oxygen, hydrogen
 I 176

peroxide or fuming nitric acid The free-radical group of fuels offers specific
Among solid rocket propellants, Belgrano impulses much higher than conventional proplnts,
mentions the mixtures of Na Nitrate & Amm but handling problems appear to be insurmount-
Picrate with thermoplastic resin of urea-aldehyde able]
type C) G. Partel, Riving 15 (10), 969–76 (1965) &
Belgrano ~so mentions liquid proplnt mix- CA 64, 14015 (1966) (Nitric oxide, NO, tested
tures of hydrogen with light substances such as in 28 expts as an oxidant in rocket proplnts
boranes of lithium or beryllium appeared to be unsuitable for that purpose, be-
It is not shown by Belgrano which of the cause it required a long reaction time inside the
above propellants were used by Italians rocket engine. However, it could be used as
Addnl Refs from CA: regulator, when nitric acid is the oxidant)
A. M. Pallotta of Bombrini-Parodi-Delfino S.p.A. D) D. Perfumo (of Bombrini-Parodi-Delfino
(Societ2 per Azioni), ItalP 640004 (1962) & S.p.A.), ItalP 696714 (1965) &CA 65, 16784
CA 58, 11163 (1963) [Inhibition of Solid NC– (1966) [In the manuf of solid rocket proplnts
NC base Rocket Propellants and/or sticking of the extruded type, the action of plasticizers
them to their container can be achieved by a on the primary proplnt is accelerated by the addn
mixt compatible with the ingredients of the of small amts of N-alkylformrunides (such as
proplnt, eg, 2-Nitrodiphenylamine – it consists HCONMe2). Processing temps can be low and
of a substance having ~ 1 reactive HS groups, primary plasticizers (such as alkylphthalates)
another having L 1 unsatd monomers with 1 can be omitted. In a typical prepn a proplnt
or 2 double bonds, and a substance or a com- contg NC 61.5, NC 4, Nitroglycol 3, Amm
bination of substances which promotes the co- Perchlorate 30.5 & Ethylcentralite 1%, was
polymerization. The adhesion is stable betw treated with a Iiq contg NC 62, NGc 34,
–30° & +50°. For example, a NC–NC based Ethylcentralite 1, and HCONMe2 3%]
proplnt contg 2-NDPhA and plasticizers was E) Mario Giaccio (Univ of Pescara) Quad
cent ered in a container of steel or Al. In the Merceol 7 (l), 63–87 (1968) & CA 71, 146
empty space, a mixt of 100 parts by wt of a (1969) [Historical notes on solid proplnts for
polysulfide, HS(C2H40CH20C2 H4)2s (C2 H4- rockets, from Chinese craftsmen to large-scale
0CH20C2H4SH), 64 ps Me methacrylate, 20 ps industry are given. Modern proplnts (fuels and
Ti02, 1 p vinyl acetate, and 2 ps acrylonitrile oxidizers)are included and future developments
was introduced. To this, 6 ps cumenehydro- are discussed]
peroxide and 0.4 p diphenylguanidine were F) G.B. Guarise & G.A. Menin (Univ of Padova),
added. In< 3 hours at RT, complete polymeriza- AttiMemAccadPatarinaSciLettArti 1967–1968
tion followed resulting in perfect inhibition and (Pub 1969) 80 (I% 2), 399-415 [Chem &
sticking of the grains] mech characteristics of oxygen gas-JP4 propInt
B) R.M. Corelli (Univ Roma), Missili 4 (4), mixts were detd in an exptl rocket engine. De-
13–24 (1962) &CA 60, 15672 (1964) [De- tails of expts and results, such as specific im-
velopment of high-energy chemicrd propellants pulse & thrust limit are given]
which were classified into two groups: 1st
group, consisting” of liquid, solid, and hybrid Randite. A Cheddite-type expl contg KC103
(liquid, solid or lithergolic) proplnts, is based on 42, MNBenzene 15 & Mn02 43% (Ref 31, p 356)
oxidn-redn reactions; 2nd group, based on the
metastability of the substance, is the so-called Razzi (Rockets). No description is given by
free-radical group of high-energy fuels, primarily Belgrano except for razzo antigradino (Antihail
H, O, N, NH3, Me and Et. The liq proplnts Rocket). Its outside view is on p 626
include 02, 03, F, boranes, dimethylhydrazine,
and derivs of F & B. The solid proplnts include RDX. See T4
thermoplastics (such as polyvinyl chloride), &
polyethylene; the thermosetting compds (such as Romite. A Cheddite-type expl used for loading
polyurethane, epoxy & polyester resins); and land mines: KC103 39, AN 49 & naphthalene
elastometers (such as polyisobutylene & Thiokol). or paraffin 12% (Ref 28, p 346 & Ref 31, p
356)
 I 177

Sabuliti. Originally Sabulite, developed in Seismic Explosives. See under Tutamite

Belgium and used as permissible (SPG) Dynamite,
contd AN 54, K nitrate 22, TNT 6, Amm chloride Selenite Italiana. NC 36.0, Guncotton 30.5,
13 & Ca silicide 5%. The Italians modified it Collodion Cotton 30.5 & mineral oil 3.0%
to AN 78, TNT 8 & Ca silicide 14% for use (Ref 4, p 180)
during WWI as a bursting charge in some ammu-
nition (Ref 1, p 342). Then they replaced TNT Sevranite A. An expl mixt of French origin
(probably due to its shortage) by TNN (Trinitro- consisting of Amm Perchlorate 31, PETN 48,
mphthalene) and developed, accdg to Piantanida DNT 18 & Al 3%; density 1.55 & deton vel
?,3 5000m/sec (Ref 31, p 363)
(Ref 4, p 246), the following compns for use as
bursting charges: a) Sabulite norrnale – AN 60,
Na nitrate 18, TNN 8 & Ca silicide 14% and Sevranite B. Amm Perchlorate 42, PETN 42
b) Sabulite extra – AN 65, TNN 10 & Ca sili- & DNT 16%; density 1.50 & deton vel 4500
cide 25’%o m/see (Ref 31, p 363)
All these compns are listed in Ref 28, p 346
and, in addition, there is Sabzdite 18 which contd Siperite o MNDT (Esplosivo). Accdg to Molina
AN 42, Na nitrate 40 & TNN 18% (Ref 1, p 342), Siperite was an expl compn con-
Belgrano (Ref 31) stated on p 329 that Sabu- sisting of AN 82–87 & DNN 18–13 parts, to
lite is a Belgian expl type SPG (s6curiti$grisou- which 20ps of TNN was added. Piantanida
poussi~re), while on p 316 he stated that Sabulite (Ref 4, p 242) gives: AN 72.8, TNT 16.7 &
consists of AN, Ca silicide & TNT with a Trauzl DNN 10.5%. Belgrano (Ref 31, p 297) gives
value of 255cc its compn as AN 73, DNN 10 & TNT 17%.
(See also Piantanida, Ref 4, p 246) Accdg to Ref 28, p 347, it was used as a burst-
ing charge for some projectiles
Saggio (Test), plural Seggi. The following
stability tests are described in Belgrano (Ref 31): Small-Arms Ammunition. See ARMI PORTA-
Saggio Abel (pp 64–7); Saggio Angeli (p 67) TILI MUNIZIONI
and Saggio di Bergmann-Junk o Saggio Tedesco
(p 199) Solenite italiana o ordinaria. Accdg to Pianta-
nida (Ref 4, p 180), it consisted of NG 36.0,
Schneiderite. An expl mixture of AN 87.4 & fuhnicotone 30.5, cotone collodio 30.5 & olio
DNN (Di@tronaphthalene) which originated in minerale 3Y0. Same compn is given by Belgrano
France and used during W(WIas + bursting charge. (Ref 31, p 212) except that he lists pirocollodio
It was adopted in Italy and in Russia. It was instead of cotone collodio. It was used as a
also used as a demolition charge. Its mixture rifle proplnt for Futile Mod 91 & Manrdicher
with TNT is known as Esplosivo MST, described (See also in this Vol of Encycl, p H152-R)
here as Nougat (Ref 4, p 241; Ref 28, p 346 &
Ref 31, p 316) Solfite. Mixture of AN 83–88 & sulfur 17–12%
“proposed in 1930 by Dr Parrnoncini. It is listed
Sebomite. A Cheddite-type expl: KC103 90, in Ref 28, p 347 and in Ref 31, p 317. Its
MNT 5 & tallow (sego) 5% (Ref 1, p 194) use is not indicated

Securite. A Dynamite which used to be manufd Solfocianato di piombo’ (Lead Thiocyanate),

at Dinamitificio di Segni: NC 52 & 30 and NC Pb(CNS)2, is described by Belgrano (Ref 31, pp
48 & 70%. (Ref 1, p 298). Belgrano (Ref 3,1, 467–68). It was used in some initiating mix-
p 317) lists another Securite consisting of AN tures such as KC103 50–55, Pb(CNS)2 ca 25,
& m-DNBz (meta-Dinitrobenzene) Sb2S3 15–18 & Pb(N3)2 ca 5%

Sedulite. A Cheddite-type expl: KC103 85, Solfuro di antimonio (Antimony Sulfide), Sb2S3,
Mn02 5 & vaseline or paraffin 10% (Ref 1, p 198) has been used in many initiating mixtures contg
 I 178

MF (Mercuric Fulminate) with KC103, such as and synthetic resins

listed in two tables on p 423 of Belgrano (Ref31) Mixtures of RDX with TNT, called Tntoliti o
Hexoliti (qv), and with TNT & Al; called Tri-
Spoletta (plural Spolette). Fuze (Fuzes). See tolital (qv), are used as bursting charges. Other
under Bomb Fuzes and under PROJECTILE mixts contg RDX are Hexocire, Hexocire-
FUZES Aluminum, Hexogene-Nylon and Idroliti are
listed here
Stifnato di piombo (Lead Styphnate, abbrd as A mixture consisting of AN 73.4, RDX 22 &
LSt) o Trinitroresorcinato di piombo), wax 4.6% was used, accdg”to Ref 28, p 348,
C6H(N02)302Pb is described in Belgrano (Ref during WWII, as a bursting chge for some armor-’
31, pp 456–64). It has been manufd by the piercing long-nose shells. A similar mixture
Societ2 Nobel and used as an igniting charge called NTP (qv) is listed in Ref 31, p 266, as
for LA (Lead Azide) in detonators and as an one of the Miscele belliche polverulente a base
ingredient in priming compns (Ref 28, p 350) di T4
Addnl Refs from CA:
T4, Esogene o Ciclotrimetilentrinitroamina A) Firm Rag. G. Mangiarotti, ItalP 528927
(RDX, Cyclotrimethylenetrinitramine, Hexogene (1955) &CA 53, 3598 (1959) [Purification of
or Cyclonite). Its prepn, props and analytical a mixture of T4 (RDX) and Tritolo (TNT) can
procedures are described by Belgrano (Ref 31, pp be achieved by dissolving it at 45° in acetone,
255–59) cooling to 25° and, after recantation, fdtration,’
Its props listed in Ref 31, p 259 are Density centrifugation and treatment with C or decolon-
(max) 1.69, Explosion Temperature 230°, Flame izing earth, crystallizing in a vertical crystallizer.
Temperature at Explosion (Temperature of Ex- The trysts of T4 which separate are continuously
plosion) 3380°, Heat of Explosion 1390kcal/kg, filtered out and TNT is separated from the mother
Volume of gas at 0° & 760mm 890 l/kg, Impact liquor by pouring it into water or by evaporating
Sensitivity with 2kg Weight 30cm, Detonation the solvent]
Velocity 8400m/see, and Trauzl Test Value B), G. Dini’ & G. Manfredi, ItalP 558782 (1957)
470cc. Giua (Ref 19) gave some dightly dif- & CA 53, 22956 (1959) [Details of conventional
ferent values, such as Density (max) 1.70, method of prepn of T4 (Cyclonite or RDX) from
Explosion Temperature 290°, Volume of ‘Gas hexamethylenetetramine (treatment with excess
at 0° & 760mm 908 l/kg, Impact Sensitivity nitric acid), are claimed which make it possible
with 2kg Wt 42cm, Detonation Velocity 8380 to recover this excess directly in him concn]
m/see and Trauzl Test 520cc (listed also on p
258 of Ref 31) T4 plastico (Plastic RDX). One such is RDX
T4 by itself is too sensitive to be used as a 89 & vaseline 11%. By adding 10–20% of Al
bursting charge in projectiles, birt “it is suitable powder, the T4 plastico con aluminio is obtd
for use in detonators & in blasting caps. When Ref 31, p 262) .,
so used, T4 is dissolved in cold acetone and pre- In Ref 28, p 348, is listed a mixture contg
cipitated by adding cold water to the soln., After RDX 78.5, DEGDN (with 0.3–0.4% of Collo-
filtering, the T4 is dried in an aluminum- dion Cotton) 17.5 & vaseline 3%. This mixt is :
jacketed rotating drum thru which air preheated known as “Italian” and supersedes the so-called
to 125° is driven. Then the dry particles are “American” mixture consisting of RDX 89 &
coated with lfZOgraphite to facilitate their petrolatum 11%, which is listed under Esplosivo
press-loading in detonators plastico. The Italian mixt was used in land mines
In a“slightly desensitized form, as for example and in antitank bombs
95/5–T4/wax or paraffin, it is used as a booster Other RDX plastic expls are Miscela C, Mis-
charge in ammunition (Ref 28, p 348). Belgrano cela CB and Misceb C4. They are listed here
(Ref31, p 261) calls such expl T4 ji’emmatizzato and in Ref 31, p 263
and says that it is colored pink (rosa) in Italy.
Other flemmatizzanti listed by Belgrano are NGu, T-Ammonal or Toluolammonal. See under ,A’mmonal
DNT, mineral oil, castor oil, acetanilide, MNN
 I 179

Termite (Thermite). See under Composizioni AN, Na nitrate, TNT, with or w/o Al and ca
(o Miscele) Incendarie andinBelgrano(Ref31, 15% of water were developed in the USA after
p 640) and Giua (Ref 19, p 414) WWII. Four formulations of Tovex are listed
by Belgrano (Ref 31, p 322), who states on p
Tetralite. See TETRILE 320 that slurry expls are not yet manufd, nor
used in Italy
Tetranitroanilina (Tetranitroaniline or TeNA).
It is described in Belgrano (Ref31, pp 271 –72). Tracianti (Tracers). See under PIROTECNIA
Used in tryst form in some detonators and in
mixts with TNT, TNN & DNBz Trialen 105. An expl mixture similar to Torpex
and Tritolital. It contd TNT 50, RDX 25 & Al
Tetranitropentaeritrite. See PENTRITE 25~0. Used in torpedoes and other underwater
ordnance (Ref 28, p 349)
Tetrazene o Guanilnitrosoammina (Tetracene or
Guanylnitrosoammine) is described by Belgrano Trilite. See TRITOLO
(Ref31, pp 464–67). Used in Composizioni
(o Miscele) innescanti, items e, f, g and 1 Trinitroanilina o Picramide (TNA) is an explosive
equal in power to PA (Picric Acid). Its props
TETRILE, Tetranitrometilanilina, Trinitrofenil- are described in Belgrano (Ref 31, pp 270–71)
metilnitroammine (Tetryl, Amer
o Tetralite but uses are not indicated
and CE, British). It is described in Belgrano
(Ref31, pp 272–75). He lists its uses in Gt- Trinitroanisolo (TNAns) is described in Belgrano
Britain and the USA but says nothing about its (Ref 31, pp 300–02). It was not produced in
uses in Italy. In Ref 28, p 349 it is stated that Italy industrially but studies were made in regard
it is used as a component of some expl mixtures, to its use for mining purposes. One of such mixts
as with TNT, such as Tetritol consisted of AN 80 & TNAns 20%0. incorporation
of TNT in this mixt increased its brisance. It was
Tetritol (Tetrytol). Accdg to Belgrano (Ref 31, used during WWII for military purposes by Japan,
p 246), the mixture used in Italy consisted of Germany & France (Ref 28, p 350)
Tetryl 75 & TNT 25% and was colored yellow.
It was used for. cast-loading in demolition charges Trinitrocresolo (TNCrs). Its isomer, Trinitro-
metacresolo (Trinitro-m-methylphenol) is de-
Tipo I and II Dinamite. See under DINAMITE scribed in Belgrano (Ref 31, pp 291 –92). Was
used in Italy in mixture: TNCrs 60 & PA 40%,
Titan. One of Ital mining expls. It is listed under the name ~esilite (qv), for military pur-
without giving its compn by Belgrano (Ref 31, poses
p 317)
Trinitrofenilmetilnitroammina. See Tetrile
TNT. See TRITOLO
Trinitrofenolo. See ACIDO PICRICO
Tolite. See Tritolo
Trinitrofloroglucinato di piombo (Trinitrophloro-
Tolulammonal. See under Ammonal ghrcinate of Lead or Trinitro-1 ,3,5 -trihydroxynate
of Lead) is described in Belgrano (Ref 31, pp
Torpex. Accdg to Belgrano (Ref 31, p 265), it 475–76). Used in initiating compns and is con-
is a mixt consisting of RDX 44, TNT 38 & Al sidered by Belgrano to be better than LSt (Lead
powder 18%. Trauzl Test value is 490cc. lt Styphnate)
was used for loading warheads of torpedoes,
depth bombs & sea mines Trinitroglicerina. See NITROGLICERINA

Tovex (Esplosivi “slurry”). Expl mixts contg Trinitrometacresolo. See under Trinitrocresolo
 I 180

Trinitrometaxilolo. See Xilite 1% paraffin (instead of wax). Its props are

Trauzl test value 470cc and deton vel 6950rn/sec.
Trinitronaftalina (TNN) is described in Belgrano Was used in aerial bombs, armor-piercing shells,
(Ref 31, pp 298–99). It was used during WWI torpedoes and mines (Ref31, p265)
in mixture with TNT called Tritrinal (qv); also Accdg to Ref 28, p 351, the following mixts
in some “esplosivi di sicurezza” (Safety Explo- were used during WWH for loading shaped
sives) such as TNN 27, AN 27 & Na nitrate 58% charge shells and mines:
(See also Sabrditi) a) 50/50 –RDX/TNT; b) 60/38 /2–RDX/TNT/Wax
The higher deriv, Tetranitronaftalina (TeNN) (dyed red); c) 25/50/25 –RDX/TNT/Al (Trialen
has not been used on account of difficulty of 105) and d) 20/60/20–RDX/TNT/Al
manuf (Ref 31, p 299) The simplest method to prepare blends of
RDX & TNT is to dissolve them in “acetone and
Trinitroresorcina. See Acido stifnico precipitate the powder by adding cold water

Trinitroresorcinato di piombo. See Stifnato di TRITOLO (Trotile, Trilite, Tolite, Trinolo o

piombo (Lead Styphnate, abbrd LSt) Trinitrotoluolo) (TNT 01 Trinitrotohrene]. lt
is described in Belgrano (Ref 31, pp 233–47).
Trinitrotolueno. See Tritolo TNT is manufd in Italy in two grades: 1) A.P.
(alto punto) with solidification (setting) point
Triperossido di esametilentetramina o Esametilen- above 80° and 2) B.P. (basso punto) solidifying
triperossidiammina. Italian names for Hexa- between 77 & 78°
methylenetriperoxidediamine (HMTD) which is The following values for props of TNT are
described in this Vol of Encycl, p H83-L. Bel- listed in Ref31, p 241: Density (max) 1.58,
grano (Ref 31) describes it on pp 478–79 with- Explosion Temperature 240°, Flame Tempera-
out indicating its uses in Italy ture at Explosion 2800°, Heat of Explosion
980kcal/kg, Detonation Velocity at d 1.5
Tritolital. Accdg to Ref 28, p 351 & Ref 31, 6700m/see, Volume of Gas at 0° & 760mm
p 263, it is a castable explosive used during WWH 6801iters/kg, Specific Pressure 8100atm/kg,
by Italians and Germans for loading underwater Trauzl Test Value 285cc and Impact Sensitivity
weapons, such as torpedoes, depth charges & with 2kg Weight 90cm. Giua (Ref 19) gave
sea mines. It consisted of TNT 60, RDX 20 & ‘ some slightly different vahres such as density
Al 20%. Its Trauzl test value is 400cc, deton (max) 1.59, Explosion Temperature 295°,
vel 7400m/sec and brisance by Ital steel plate Volume of Gas 6901iters/kg, Trauzl Test 310CC
test (prova dells piastra di accaio) 2 lmm & Imapct Sensitivity at 2kg Wt 60cm (listed
also on p 258 of Ref 31)
Tritolite o Ciclotol. Accdg to Ref 28, p 351, Accdg to Ref31, p 236, the grade of TNT
it is a castable mixt of TNT 50 & RDX 50%0pro- solidifying above 80° was used straight in de-
posed in 1930 by M. Tonegutti for loading tonators and in some projectiles, while the lower
underwater weapons, such as torpedoes, sea grade (77–78°) was used in mixtures such as
mines & depth charges. Its props are accdg to Arnatol
Ref 31, p 265: cast density 1.65, Trauzl value Accdg to Ref 28, p 352, straight TNT has
460cc, deton vel 6900m/sec and brisance by been used by the Italians to a much lesser ex-
Ital steel plate test 23mm. The compn was tent than by the Americans or British. Pressed
changed during WWH to TNT 60 & RDX 40%. TNT is used as a booster in some bombs and as
Its props are cast density 1.62, Trauzl value a main ffler for some demolition charges.
440cc, deton vel 6600m/sec and brisance 21mm, Granular TNT is used as the bursting chge of
but the 50/50 formulation, being stronger, was hand grenades, mortar shells and in mines. Cast
used for loading aerial bombs and antitank TNT is used as a bursting charge in some bombs,
shells (Ref 31, p 265) 2 to 1000kg in weight, and for artillery shells,
The formulation RDX 60, TNT 39 & wax 1% 57 to 420mm
is similar to Amer Composih”on B, which contd TNT has also been used extensively in compo-
 I 181

site expls, such as Amatol, Ammonrd, Dinamon, 41.4 & ferrosilicon 13.5%; Trauzl value 340cc.
Esplosivi da guerra, Esplosivi da mina, .Esplosivo Accdg to Ref 28, p 352 they were used as
S20, Gomma incongelabile, MABT, MAT, MST bursting chges in some projectiles
o Nougat, Pentritolo, Pentrol, Picrat ol, Siperite
or MNDT, Tetritol, Trialen 105, Tritolital, Universal Italiana. Accdg to Belgrano (Ref 31,
Tritolite, Tritonal and Tritrinal p 580), it is one of the polven da caccia
Analytical procedures and tests used in Italy [Hunting (Sporting) Propellants], which was
are described in Ref 31, pp 243–45 based on completely gelatinized NC. Molina
(Ref 1, p 412) gives its compn as NC 80–82,
Tritonal. Composite explosive consisting of DNT 12–10, DEDPhU (Diethyldiphenylurea)
TNT 80 & Al powder 20%; Trauzl Test Value 4–4, vaseline 3–3 & volatiles 1–1%
350cc; used for cast-loading light case under-
water ammunition (Ref 31, p .246)
UNKNOWN NAME EXPLOSIVES.
The following expls are extracted from
Tritrinal of WWI. Composite expl of 1 part TNN
Chemical Abstracts, A.M. Tonegutti, FrP
(Trinitronaphthalene) and 2 parts TNT; used 833720 (1938) &CA 33, 3590 (1939):
during WWI for cast-loading some ammunition a) A castable bursting type expl – AN 70,
(Ref 31, p 299)
PETN 20 & cyanoguanidine 10%0
b) A press-loaded expl for use as a bursting chge
Trotil. See Tritolo for 47mm AP Shells – AN 73.4, R.DX 22 &
wax 4.6$Z0
Tutamite. One of the Italian “Esplosivi per
c) A press-loaded expl for use as a booster in
prospezioni geosismiche” (Explosives for Geo-
ammunition – RDX 95 & wax (dyed red) 5%
seismic Prospecting) is listed by Belgrano (Ref
d) A castable expl for use as a bursting chge in
31, p 334) together with other Italian seismic
500-kg bomb – PETN 65 & PETA (Penta-
expls Sismite and Geo-Mon A, without giving
erythritol Tetraacetate) 35%. It is comparable
their compositions
to TNT in sensitivity to shock, but is about 25%
Tutamite is also listed in Catalog of Monte-
less brisant
catimi ~SGIMC, Milano (1959), p 30. Its props
are given but no compn
VE4. One of the mining expls manufd by
Geo-Mon A is listed in the same catalog, p 19
with props but no compn. Other Esplosivi per Vulcania SPA, Brescia, which is based on aro-
prospezini geosismiche listed in Montecati matic nitroderivatives and AN. Its Trauzl test
catalog are Gee-Din A and Gee-Din B (p 17) value is 335cc & Deton Vel 3550m/sec at d
In catalog of Vulcania SPA, Brescia, are listed 1.02. Suitable for use in quarries with rock
three seismic expls: 1) Vzdcania DB, based on not too hard (Vulcania Catalog of 1960, p
TNT & nitric salts; Trauzl value 320cc, Deton not indicated)
Vel 2600m/sec at d 1.1 and Impact Test with Belgrano (Ref31) lists VE4 on p 317 with-
2kg Wt > 90cm; 2) Vulcania DBS, based on out giving its composition
TNT, RDX & AN; Trauzl value 370cc, Deton
Vel 5600m/sec at d 1.25 and Impact with 2kg Vibrite. Blasting expl contg AN 78, TNNaph-
Wt > 90cm; 3) Sismite A, based on TNT, Tetril thalene 8 & Ca silicide 14% (Ref 1, p 342 &
and nitrates; Trauzl value 400cc, Deton Vel Ref 28, p 353) (Compare with Sabulite)
5000m/sec at d 1.4 & Impact Test
70cm Vietorite. Cheddite-type expl consisting of
[Italian catalogs were obtd thru the courtesy KC103 40.0, PA 53.2, K (Na or Ba) nitrate
of Dr Omero Vettori of Ar.dla (Massa Carrara)] 4.8 & carbon 2% (Ref 28, p 353)

I Umbrite. Two formulations are listed by Bel-

grano (Ref31, p 254): Umbrite A – NGu
48.4. AN 37.3 & ferrosilicon 14.3%: Trauzl
value 260cc and Umbrite B – NGu 45.1, AN
Virite. Black Powder-type expl consisting of K
nitrate 33—38, AN 35-40, sulfur 4—5, carbon
10–12 & Amm oxalate 9–12% (Ref 28, p 353
& Ref 31, p 340)

I
 I 182

Vulcania DB and DBS. Seismic prospecting expls Navy Dept Bur Ordn OPNAV 1668 (1946),
listed here under Tutamite pp 1–27 9) A. Mangini, “Quaderni di Chi-
mica Industrial 14; Esplosivi”, Patron, Bologna
Vulcanite P. A mining expl suitable for blasting (1947), pp 147-235 10) Col A.D. Merrirnan,
tunnels thru hard, rock. It is based on inorg “Itrdian Bombs and Fuzes”, British Ministry of,
nitrates, nitroaromatic compds and nitric di- Supply Monograph 17-805 (1948) 11) c.
ethers. Its Trauzl test value is 5 15CC,Deton Vel Caprio, “Corso di Esplosivi”, Scuolo Salesiana
5100m/sec at d 1.15 & Impact with 2kg Wt Libro, Roma, Vol 1 (1948) & Vol 2 (1949)
80cm [Catalog of Vulcania SPA, Brescia (1960)] 12) A. Izzo, “Pirotecnia e Fuochi Artificial”,
Hoepli, Milano (1950) 13) C. Belgrano, “Gli
Vulcanite PR. A mining expl suitable for tunnel Esplosivi”,, Hoepli, Milano (1952) 14) Minis-
work thru hard rock. It is based on inorg tero, de la Difesa Marina, Editore, “Guida por
nitrates & nitroaromatic compds. Its Trauzl l’Esecuzione delle Prove Pratiche o dells Analisi
value is 5 10cc, Deton Vel 5600m/sec at d 1.15 sugli Esplosivi”, Roma (1952) 15) A. IZZO,
& Impact 70cm [Catrdog of Vulcania SPA, “Manuale del Minatore Esplosivista” (Fochino),
Brescia (1960)] Hoepli, Milano (1953) 16) Anon, “ltalian
and French Explosive Ordnance”, US Dept of
Vulcan Powder. It is listed in Belgrano (Ref31, the Army TechManual TM 9-1985-6 (1953), pp
p 339) as contg NC 30.0, Na nitrate 52.5, 1 to 176 17) G. Castelfranchi & P. Malatesta,
carbon 10.5 & S 7 .O$ZO without indicating which “Lezioni di Chimica di Guerra”, Part 1: “Esplo-
country used it sivi”, Pt 2: “Aggressive Chimice”, Edit Studium,
Roma (1954), 640pp 18) B.T. Fedoroff et
Xilite o Trinitrometaxilolo (TNX or Trinitro- al, “Italian Explosives and Ammunition”, Pica-
m-dimethylbenzene). It is very briefly described tinny Arsenal Mnauscript, Unpublished (1 955)
in Belgrano (Ref 31, pp 248–49). It was used 19) Michele Giua & Maria Luisa Marchino,
during WWI in mixtures with AN, such as in “Esplosivi”, pp 1–497 in “Trattato di Chirnica
NX, contg AN 77, & xilite 23%. Another mix- Industrial”, 6 (1° ) UTET, Torino (1959) I
ture was MTX which contd PA 55, TNT 35 & 20) Major T.H. Reynolds, “The Munitions In-
xilite 1O% dustry, Bombrini-Parodi-Deltino”, US Military
References for Italian Explosives, Ammunition Intelligence Report R-720-59 (1959)
and Weapons: 21) P.B. Tweed, “Report on Trip to Europe
1) R. Molina, “Esplodenti e Modo di Fabricarli, During May 1960”, Picatinny Arsenal Technical
Hoepli, Milano (1930) 2) M. Giua, “Lezioni Memorandum Report OR DE B-TE9-28 (1960
di Esplosivi”, 2 Vols, Rattero, Torino (1932– 22) R.P. Antonelli, “Encyclopedia of Explo-
33) 3) General Carlo Montu, “Storia dell’ sives”, OTIA,”Ordnance Liaison Group, Durham,
Artiglieria Italiana”, Vol 1 (1935) [Reviewed in North Carolina (1960), pp 150–51 (Italian I
MAF 14, 557 (1935)] 4) E. Piantanida, Terms) 23) W.H.B. Smith & J.E. Smith,
“Chimica degli Esplosivi e dei Gas de Guerra”, “Small Arms of the World”, Stackpole, Harris-
Regia, Accademia Navale, Livorno (1940) burg, Pennsylvania (1960), pp 476–97 (Italy)
4a) Lt Col G.B. Jarrett, OrdnanceSergeant, 24) B.T. Fedoroff & O.E. Sheffield, “Encyclo-
Aug 1943, p 18 5) Anon, “Data on Foreign pedia of Explosives and Related Items, “Pica-
Explosives”, US Chemical Warfare Service Field tinny Arsenal Technical Report PATR 2700,
Lab Memo 4-6-2 (1944), US Office of Techni- Vol 1 (1960); Vol 2 (1962); Vol 3 (1966);
cal Services PB Report 11544 5a) Lt Col Vol 4 (1969);V01 5 (1972) and Vol 6 (1974)
G.B. Jarrett, “Italian Artillery”, Field Artillery (Pages indicated under each item) 25) L. di
Journal 35, 663–7 1 (1945) 6) J.D. Parsons, G. Pirola, “Esplosivi”, Collezione Legale Pirola
“Visit to Italian Explosives Factories”, PB No 1187, Milano (1962) 26) C. Giorgio,
Rept 12663 (1945) 7) Anon, “Explosives “Tecnica degli Esplosivi”, Vol 1, Del Blanco,
and Demolitions”, US War Department Manual Udine (1964) 27) E. Brandimarte, “Teoria
FM 5-25 (1945), pp 136ff (Italian Explosives) dell’Esplosione ed Esplosivi di Scoppio”, Acca-
8) Anon, “Italian and Erench Explosives”, US demia Navale, Livorno (1965) 28) O.E.
 I 183

Sheffield, “Handbook of Foreign Explosives”, m) A.B. Schilling, 1539 (1945) (Offensive Hand
US Army Materiel Command Intelligence Docu- Grenade)
ment FSTC 381-5042 (1965), pp 318 to 359 n) F.G. Haverlack, 1549 (1945) (149/13-mm
29) E. Brandimarte, Editor, “Le Cariche di HE Shell)
Scoppio” (Bursting Charges), Accademia Navale, o) A.B. Schilling, PAMR 105 (1956) (Hand
Livorno (1966) (Theoretical discussion dealing and Smoke Grenades with Friction Type Igniter)
with shapes of bursting charges) 30) M. E) J.D. Parsons, “Visit to Italian Explosives
Busco, “Ottica Geometric degli Esplosivi”,’ Factories” (1945) (US Office of Technical Ser-
Vol 1 (1973) (Obtainable from author at Via vices, PB Rept 12663)
Quatro Venti 247, Roma) 31) Camillo F) Anon, “Allied and Enemy Explosives”,
Belgrano, “Gli Esplosivi”, 2nd End, Arti Gra- Aberdeen Proving Ground, Maryland (1946)
fiche Fiulane, Udine (1974). Introduction by G) R. Denti, “Dizionario Tecnico, Italiano-
General Attilio Izzo 32) Dr Omero Vettore, Inglese, Inglese-Italiano”, Hoepli, Milano (1958)
Aulla (Massa Carrara); private communications
on Italian explosives during the years 1972–75 Abbreviations: CRA – Complete Round of
Additional References: Ammunition; AP, HE, LN – Armor-Piercing,
A) US War Department “Military Dictionary”, High Explosive, Long Nose; MB – Monoblock;
TM 30-2569, English-Italian and Italian-English, HC – High Capacity; LE – Low Explosive
Washington, DC (19.43)
B) “Military Italian-Russian Dictionary”, Italrim Catalogs, furnished thru the courtesy
GosIzdatInostr i NazionSlovarey, Moscow (1953) of Dr Omero Vettori of Aulla (Massa Carrara):
C) “MUNIZIONAMENTO ITALIANO” (1941) 1) Catalog of “Esplosivi ed Accessori da Mire”,
Sent by Dr Omero Vettori, Aulla (MC) in May, Montecatinni SGIMC, Milano (1959). Described
1973 are the properties and uses of mining expls de-
D) Picatinny Arsemd Technical Reports (PATR) signated as Gomma A, Gomma Agel, Gomma
on examination of Italian Ammunition picked B.M., G.E.O.M., G.D. 1°M.T., G.D. 1°M.B.,
up at the front or captured: G. D. S., Gelignite S.A., Semigel A, Dinamon 1°,
a) C.G. Scheibner, PATR 903 (1938) (Cal .50 Dinamon S, Cava M, Grisoutina 13.20%, Gri-
Expl Shell) soutina 10%, Tionite, Gee-Din A, Gee-Din B,
b) A.B. Schilling, 1241 (1943) [47-mm AP, Geo-Mon A and Tutamite. No compositions
HE (LN) CRA] are given. Also are described initiating devices,
c) Ibid, 1258 (1943) [47-mm AP, HE (MB) nonelectric and electric
CRA] II) Catalog of “Esplosivi Mangiarotti”, Codroipo
d) R.M. Dennis, 1315 (1943) [47-mm HE (Udine) (1960). Described are the properties,
(Tritolo) CRA] uses and testing of mining explosives designated
e) A.B. Schilling, 1327 (1943) (Stick-Type as BM.1, BM.as, BM.ac, BM.57, Super BM,
BM.a2, Super BM.Cava, BM.2 per Galleria.
Land Mine)
f) R.M. Dennis, 1332 (1944) (37-mm LE Compns are given without numerical values
Shell CRA) 111) Catalog of “Vulcania SPA. Polveri per Mina,
g) Ibid, 1344 (1944) (81-mm HE Mortar Shell Caccia, Agricultural, Difesa”, Brescia (1960).
CRA) Described are the properties and uses of mining
h) A.B. Schilling, 1348 (1944) (Variable Pres- expls: Antonites, Alger C, Alger D, Alger E,
sure Land Mine) VE4, Vulcania D. B., Vulcania D. B.S., Vulcanite

i) Ibid, 1349 (1944) (20-mm AP, HE Shell P, Vulcanite Compns are

PR and Sismite A.
Complete Round) given without numerical values
j) Ibid, 1362 (1944) (81-mm HC, HE Mortar IV) Catalog of “Sorlini Esplosivi SPA, Brescia
Shell CRA) (1961). Described are properties and uses of
k) Ibid, 1381 (1944) (Pressure Igniter and mining expls: Martia Alpha, Martia Beta,
Demolition Block) Martia Gamma, Martia Delta 45, Martia Eta S.
1) F.G. Haverlack, 1515 (1945) (120/45-mm No compositions are given
HE Shell)
 I 184

V) Catalog of SMI (Societ3 Metallurgic for the fine and 25% for the coarse. Densities
Italiana) SpA “Catalogo Munizionamento are 0.80 to 0.90 for No 1 and 0.5 to 0.7 for
Militare”. At their plant near Campo Tizzoro No 2. Oxygen balance to C02 is about -115%
(Province of Pistoia) the Co manufs Small for the dried material
Arms Cartridges, while at Fornaci di Barga Refs: 1) J. Patterson, JCS 1923, 1139 & CA
(Prov of Lucca) Artillery Cartridges are manufd. 17, 2566 (1923) 2) Marshall 3 (1932), p
The Co also manufs steel cartridges for Re- 230 3) Hackh’s (1944), pp 256 & 460;
coilless Rifles (Bossoli Acciaio per Cannoni (1972), 178 & 364
Senza Rinculo), Percussion & Electric Primers
(Cannelli a Percussion ed Elettrici) and other
metallic items Ivory Nut, Nitrated. No specs or procedures for
VI) Professor L. Musciarelli, “Storia delle Armi” nitration were found. Its use in the following
(History of Weapons) which includes History of Dynamite compn is claimed by Stine (Ref 1):
Beretta Factory and Catalog of Pistols, Rifles NC 35, NC 1, Nitrated ivory nut 5, NaN’03
& Shotguns. Published by Fabbrica d’Armi 52 and Woodmead 7 parts. The nitrated ivory
Pietro Beretta, Milano nut is insol in NC and its use as a substitute
for an equal amt of NC produces an explosive
which is more easily detonated
Ivory Nut (Corajo, Coroso or Vegetable Ivory). Nitrated Ivory Nut is also claimed (Ref 2)
A hard white substance obtained from the as an explosive by itself or a constituent of
tagud nut, such as Phytelephas Macrocarpa or primary or secondary charges containing other
negrito palm, which grows in Ecuador explosives, such as MF, LA, TNT etc
It is composed of cellulosic bodies and Refs: 1) C.M. Stine, USP 1143330 (1915) &
other hydrocarbons CA 9, 2313 (1915) 2) E. Marks, BritP
In powdered form, it is used as a “fuel” 124303 (1919) & CA 14, 2713 (1920)
component of dynamites and other blasting
explosives. According to Marshall (Ref,1 ), such
material should not contain more than 570 of
moisture and 37. ash; its volubility in 95~0 Izod Test. See Charpy and Izod Tests in Vol
alcohol should not exceed 3% 2, p C154-L
Ivory nut meal used in US dynamites is
usually either fine (No 1), which has about ‘S70
remaining on No 20 sieve and 30% passing No
100 sieve, or coarse (No 2) with 5% remaining IZZO, A. Author of Manual del minatore
on No 10 and 5% passing No 60. The per- explosivista. Milan: u Hoepli (1953) 189pp.
centage of ash in both cases is below 5$Z0 and Reviewed in Chem & Ind 71, 1173 (1954)
moisture below 10YO.Absorption value: 30-35% & CA 48, 11062 (1954)
.-.

,. .’
 J1

J (Poudre de chasse); A French smokeless Jacket, Coolant. The metal enclosure that con-
sporting proplnt invented by Bruneau and manufd sists of an inner ‘wall (liner) and an outer metal
before WWI. It contained NC 83 & ammonium wall (outer case), with a coolant passagebe-
bichromate 17%. It replaced poudre pyroxy16 type S tween them, occasionally held apart by spacers
Refs: 1) Daniel (1902), p 385 2) Pascal or coolant helices. Term also applied to the
(1930), p 228 double metal walls of a regeneratively-cooled
thrust-chamber assembly
The main component of a modem liquid-
Jablonsky’s Propellant. Two samples of proplnt propellant rocket thrust-chamber assembly is
powder were submitted by Dr Frans Jablons@ called the coolant jacket. There are many
for tests as to suitability for use in small arms jacket designs but, in nearly rdl cases, the jacket
ammo. The powder was stated to contain NC structure extends thru the throat region as well
recovered from scrap moving picture fdm & as the combustion chamber
other chemicals intended to increase the oxygen Refi J.W. Herrick & E. Burgess, “Rocket En-
content. Chem analysis showed the samples to cyclopedia Illustrated”, Aero Publ, Los Angeles,
have the following compn: Calif (1959), p 240
Composition, % Sample No 1 Sample No 2
Nitrocellulose 76.26 74.08
Jacketed Projectile. In order to take advantage
Ammonium Picrate 13.82 10.89
of the increased striking energy made possible
Potassium Chlorate 5.40 7.75
by the use of a smaller caliber, higher vel, per-
Camphor 3.46 3.54
forating missile, designers have made use of the
Ethyl Acetate 0.86 3.74
— principle of the subprojectile as shown in the
Red org material 0.20
Fig. Here the jacket around the smaller tungsten
Tests showed the proplnts to be.of relatively
low stability, unduly volatile & hydroscopic.
IDEALIZED PROJECTILE TYPES
Ballistic tests gave results indicating the proplnts
to have less ballistic potential than Pyrocellulose,
and to deposit unburned residue in the rifle # Caf3 Ja
barrel. The proplnts, represented by the two
samples, were considered to be of little promise
for use in milita~ ammo
f’
Refi A.J. Phillips, “Study of Propellant Powder Core
Submitted by Dr Frans Jablonsky”, PATR 796
(Jan 1937) ?
n B’
MONOBLOC CAPPED JACKETED
. PROJECTILE PROJECTILE PROJECTILE
Jacket. A cylinder of steel covering & strength-
ening the breech end of a gun or howitzer tube. carbide core, or subprojectile enables the missile
It also refers to the water jacket on some ma- to derive full benefit of the proplnt powder
chine guns gases. Further, since the jacket or carrier is
Ref OrdTechTerm (1962), p 168-L made of Al, the lighter over-all wt of the com-
plete projectile coupled with the use of high
potential proplnts reWlts in a higher muzzle
Jacket, Bullet. A metal shell surrounding a vel. Unfortunately, the decrease in over-all
metal core, the combination comprising a bullet wt, while helping to give greater muzzle vel,
for small arms. The jacket is either composed also results in a lower ballistic coefficient and,
of, or coated with, a relatively soft metal, such therefore, a higher rate of 10SSof the muzzle vel.
as gilding metal, which engagesthe rifling in Since the jacket is rigidly attached to the core
the bore, causing rotation of the bullet and does not fall off until contact with the
Refi OrdTechTerm (1962), p 168-L target, the HVAP (hypervelocity armor-piercing)
 J2

is also known. as the composite rigid or compo- Janite. A large grain, black blasting powder
rigid type impregnated with NG. It was used to a limited
Rej ArmamentEngrg (1954), pp 208–09 extent for excavation work on the Isthmus of
Corinth in Greece
Refi Daniel (1902), p 386
Jacque Stability Test. Jacqu6, director of the
Spanish plant Cantabrica at Guld5cano, near
Bilbao, proposed a test for NC which was simple, JANNAF. Abbr for Joint Army-Navy-NASA-
rapid, and did not requk’e complicated apparatus. Air Force (often pronounced as one word)
It is not advisable to use this test when it is established in 1969. Its activities are described
known in advance that the NC is of low stability in Ref
Procedure. A NC sample of 2-3g, previously Refi Expls & Pyrots 6 (2), 1973
dried in a loosely covered weighing dish or
crystallizer to constant wt, is transferred to an
oven maintained at 130–40° and left there for Jannopoulos Test. A stability test for expls which
2 hrs. It is cooled in a vacuum desiccator and is a modification of Abel’s Test (See Vol 1
reweighed. The sample is again heated at 140° of Encycl, p A2-L) and of Guttmann’s Test
and weighed at intervals of %–2 hrs until it (See Vol 6 of Encycl, p G196-L). The freely
decomposes, as indicated by an abnormal loss ground sample is previously warmed to 35–38°
of wt. After termination of the test, it is ad- for four days before testing. The test is not
visable to wash the NC with distilled water, applicable to double-base proplnts contg NC
add a few drops of O.lN KMn04 soln and de- Refi Reilly (1938), p 78
termine the amt of HN03, either by the nitron
or diphenylamine method
A somewhat analogous test is described by Janovsky Test. Color reactions produced by
Sy [(JACS 25, 549 (1903)] and by Berkhout treating aromatic nitro compds with hot&
[SS 17, 33 (1922)]. See also Heat Tests in cold alcoholic NaOH or KOH and acetonic
Vol 1 of Encycl, p XV NaOH solns. A table of color reactions of
Refs: 1) M. Jacqu6, SS 1, 395 (1906) & CA some nitro compds is given’ in Ref 2. See
2, 1346 (1908) 2) Reilly (1938), p 85 Janovshy ’s Reagent under COLOR REAC-
TIONS and COLOR REAGENTS in Vol 3 of
Encycl, p C405-R
Jahnite Powders. Austrian mining expls patented Refs: 1) J.V. Janovsky, Ber 24,971 (1891)
by Jahn many years ago. They contained NaN03 2) G.D. Parks & A.C. Farthing, JChemSoc
70–75, sulfur 12–10, lignite 17–10, KC103 1948, 1278
0.4–2, Na Picrate O–3, PA 0.3–0 & NaC03
0.3–0% .
Refs: 1) Cundill (1889) in MP 6, 19 (1893) JAPANESE EXPLOSIVES, AMMUNITION
2) Daniel (1902), 387–88 AND WEAPONS
Accdg to Ref 5, p 360, the Japanese used during
WWII a greater variety of HE’s (High Expls) and
Jalnias Powders. The following compns for ammunition than other nations at the time (except
Cannon Powder – KN03 75, Na Picrate 3, probably the Germans and Italians). This was due
sulfur 10, coal 10 & KC103 270 and to a shortage of raw materials necessary for the
Rifle Powder – KNO~ 15, Na Picrate 8, sulfur manuf of the best expls. Although they used many
10, coal 15 & KC103 2% are found in Ref standard HE’s (such as TNT, Picric Acid, PETN,
Refi P6rez Ara (1945), p 223 RDX and Tetryl), every other available expl sub-
stance was also used as an ingredient of expl compns.
Among these substances may be mentioned the fol-
JANAF. Abbr for Joint Army-Navy-Air Force lowing: TNAns (Trinitroanisole), TNPht (Trinitro-
(often pronounced as one word) phenetole), HNDPhA (Hexanitrodiphenylamine),
Refi OrdTechTerm (1962), p 168-L GuN (Guanidine Nitrate), DNN (Dinitronaphtha-
 J3

lene), DNBz (Dinitrobenzene), AP (Ammonium and the year of the era. Type 11(Taisho)= 1922;
Picrate), as well as a number of commercial expls, Type 41 (Meiji)=1908
p~ticularly Dymmites. As nonexplosive ingre- 4. The term Model usually indicated a change
dients, the materials used included: inorganic in basic design, while the term Modification re-
nitrates, chlorates & perchlorates; aluminum, sili- presented minor changes in design or a change in
con carbide, ferrosilicon, petroleum, woodpulp, the expl ffling
powdered coal & charcoal, tars, waxes, oils and Addrd explanation is given in the intro-
their mixtures duction to each Section, such as Bombs, Land
The Japanese Initiating Agents were similar Mines, Grenades, Projectiles, Rockets, Mortars,
to those used by the Germans, except that Fuzes, Firing Devices and Sabotage Devices
Tetracene was not used and fewer mixts were The Japanese explosives and related items
employed in ammunition. MF (Mercuric Ful- are listed alphabetically in the pages which foIlow
minate) was used in many primary mixts, while
LA (Lead Azide) was used in fewer mixts. It Alphabetical List of Japanese Explosives
does not appeti that LSt (Lead Styphnate) was and Related Items
used in compns contg nonexpl ingredients. As Aerial Torpedo. Kurai
a base ingredient of detonators, PETN was
mainly used and to a lesser extent, Tetryl Akatsuki. An Ammonium Nitrate expl contg:
As to Japanese ammunition itself, one can AN 73–75, NC gel 5–6, cellulose 3–5 & other
point out the great variety of improvised devices, ingredients 14–9%. Detonation Velocity 3490m/s
such as Mines & Depth Charges made from wood- at density 1.0; Detonation Pressure (experimental)
en boxes, burlap bags with rubber lining, & oil 42.3kbar, while the calculated value is 33kbar
drums; Grenades made of pottery, glass & gas Ref K. Sassa& I. Ito, “Studies of Detonation
pipes; Booby Traps made of tin cans; and Pressure Using Aquarium Technique”, K6gyI$
Bangalore Torpedoes made of bamboo tubes KayakuKy8kaishi 32, No 6 (Nov–Dec 1971).
Accdg to Refs 2 & 3, the Japanese Explosive Engl translation by Mrs Geti Saad of the US-
Ordnance used during WWII was subdivided into BurMines (1972)
,those used for the Army (Rikugun) and those
for the Navy (Kaigun) A[ko) or Type A (Explosive). See Otsu-B
System of Designation
1. Type Number. Item of Ordnance, as well Aluminum. See Aruminyumu
as most other items of military equipment, were
given a type number indicating the year the ar- Ammonaru Ammonal. Compn and specific
–
ticle was finally adopted for service use. Until uses are not known (Ref 5, p 361)
the reign of the present Emperor (Showa era,
started in 1926), items were designated by the Ammonium Chlorate, used in “Brown Powder”
year of the era. Now, however, the year of the of compn: Amm chlorate 51.5, Ba nitrate 34.5,
Japanese Empire (Japanese year 2600 corresponds TNNaphthalene with oil 8.2 & woodpulp 5.0%
to our 1940) could be used. For items intro- (adds to 99.2%). Found as a booster in bombs
duced up to the year 2600, the last two numbers for demolition (Ref 1, p 32)
are used in the designation. Thus Type 99 means
that the item was adopted in 2599 (our 1939). Ammonium Nitrate. See Ammon Shosanen
The year 2600 may be represented as Type 100
or Type O, while the years 2601, 2602, etc are Ammonium Perchlorate was used in Karito
represented as Type 1, Type 2, etc (Army Expl), Kaishikuyaku (Army Expl) and
2. Exptl Ordn items were marked with the .in Type 88 (Navy Expl) & Type 4 (Navy Expl)
year of the Showa era during which the experi-
ment was authorized Ammonium Picrate. See picurinsan Ammonia.
3. Ordn items authorized in the eras preceding Used in Type 1 Explosives (Navy Expls)
the Showa era: namely, Taisho (19 12–1 926) and
Meiji (1 867–19 12), were designated by the era Ammon Shosanen. Ammonium Nitrate (AN)
 J4

Used in a number of commercial and military They contd larger HE charges than AP and
expl compns, such as: Akatsuki, Ammon7iru, smaller than standard HE projs
Ammonyaku, Anbeyaku, Angayaku, “E” (Ex- There were “old” and “new” color systems
plosive), Keyaki, Kiri Nos 1, 2 & 3, Ko-Shoan for marking the Army projectiles, and they are
Bakuyaku, Shin-Kiri, Shinkyro~oku, Shin- briefly explained on pp 266–69 of Ref 3
Toku-Shoan, Shoan-Bakuyaku, Shoan Bakuyaku The following abbrns are used in this Section
Nos ] 04 & 201, Shoanyaku, Shobenyaku, Shona on AMMUNITION:
yaku, Shotoyaku, Type 4 Mk 2, and others (Ref AAMG – Antiaircraft Machine Gun
5, p 361) AC – Aircraft Cannon
There have also been conducted research on ACMG – Aircraft Machine
the use of AN in Composite Propellants for Ammo – Ammunition
Rocket Engines (Ref 5, p 361) AP – Armor-Piercing
AP-HE – Armor-Piercing-High Explosive
Ammonyaku. Army expl compn consisting of API – Armor-Piercing Incendiary
AN & charcoal. Japanese documents cite it as – Armor-Piercing Tracer
“substitute powder”. It was never recovered by ATk – Anti-Tank
Americans (Ref 1, p 29; Ref 5, p 361 and Ref BkPdr – Black Powder
6, p 8-3) HE – High Explosive
HEAT – High-Explosive Antitank (Shaped
AMMUNITION (Danyaku) Charge)
HEI – High-Explosive Incendiary
Introduction
HE IT – High-Explosive Incendiary Tracer
Ammunition and Weapons used by the Army
HET – High-Explosive Tracer
(Rikugun) were in most cases different from
HMG – Heavy Machine Gun
those used by the Navy (Kaigun). For this rea-
How – Howitzer
son it is necessary to indicate whether the item
I or Intend – Incendiary
was used by the Army or the Navy
Accdg to OPNAV 30-3M (1945) (Ref 1, p IT – Incendiary Tracer
LMG – Light Machine Gun
123), Japanese Army Ammunition of WWII
MG – Machine Gun
was divided into the following groups:
a) Small Arms Ammunition — items smaller MK – Mark
Mod – Modification (or Modified)
than caliber 20-mm
b) Aircraft Cannon Ammunition – items of Proj – Projectile
Proplnt – Propellant
caliber 20-mm and over
c) Medium and Large Caliber Gun Ammuni- SD – Self-Destroying
Tk – Tank
tion – items of 20-mm and over
w – White Phosphorus
d) Mortar Ammunition
e) Fuzes
Ammunition, Army (Danyaku Rikugun)
Under the title “Japanese Ammunition– Accdg to TM 9-1985-5 (1953) (Ref 3, p
Explanatory Notes”, TM 9-1985-5 (1953) 265), such ammunition and weapons were
(Ref 3, p IV), the following information is generally copies of German and French designs
given: or were developed following their customs. In
The Japanese Army Terminology of WWH comparison with items used by other countries
for projectiles conformed fairly well with US in the years preceding WWII, the Japanese ammo
custom. The abbrn AP indicated a projectile and weapons appear to be outmoded. This is
intended for piercing heavy armor, such as particularly true in considering Small Arms
armor plate of thickness equal to or greater (ShtXuhei) because there is little evidence that
than the caliber of the projectile. These projs they were standardized. The weapon used
had a small HE bursting charge. Abbrn AP-HE prior to 1930 was 6.5mm, but shortly there-
indicated a solid-nosed proj in general similar to after it was superseded by cal 7.7mm, but the
AP but designed for much lighter penetration. change was not complete and many 6.5mm
 J5

items were used during WWII – 12.7-mm AC Cannon Proj contd PETN &
The foreign influence in design was particu- Intend chge (pp 278–79)
larly evident after 1939 when Aircraft Cannons –Type 97 & Type 98 20-mm Ammo contd
(K75kiiki taih~) of German and Italian design single-base propht; no info about filling of
were copied. The largest Aircraft Cannon de- proj. Used in A/Tk and AA-A/Tk Guns (p 280)
vised was 120mm, but nothing larger than 57mm –20-mm HE Tracer, Type 98 HET and Type
was ever put in service use 100 HET Projectiles contd RDX and Tracer
Most Infantry Artillery Weapons (Hiiheih6) compn (pp 281 –82)
were characterized by their immobility, as very –20-mm HE Incendiary and 20-mm HEI (Ma
few of them were designed for rapid motor 201) Projs contd RDX or PETN and Incendiary
transport. The standard Field Piece (Yah~) (pp 282-84)
was 75mm, although 105mm and 150mm were –20-mm HEIT Ammo for use in Ho-1 & Ho-3
frequently encountered AC Cannons. Its proj contd RDX, Incendiary
One outstanding characteristic of Japanese & Tracer (p 284)
armament was the large variety of type and –Type 100 Mod 2 20-mm IT, SD Ammo for
sizes of Mortars (Kyilh6) in use. They were use in Type 98 AC-A/Tk Gun. Its proj contd
used not only as Infantry (Hohei) support wea- Intend and Tracer compns but there is no HE
pons but also as Artillery Pieces (Hi7). They except in Booster (p 285)
ranged in size from the 50-mm Grenade Dis- –20-mm APT Ammo for Type 97 A/Tk, Type
charger (Tekidanti5) to the 320-mm “Spigot” 98 AA-A/Tk, Ho-1 & Ho-3 Guns. Its proj contd
——
Mortar (“Spigot” Kyuho) 7.Og of Tracer compn (pp 285–86)
The standard Antiaircraft Gun (K6shahZi) was –Ho-5 20-mm AP Ammo for use in Army AC
a 75-mm Gun, but there was also an 88-mm AA Machine Gun. Its proj was solid steel shot and
Gun which was one of their most effective wea- proplnt consisted of graphited cylindrical grains
pons and a 105-mm AA Gun. The Japanese of single-base pdr (p 286)
also designed a 150-mm AA Gun for the de- –Type 2 and Type 2 Mod 20-mm HEI Ammo.
fense of the home islands, but this was used The projs contd Cyclonite and Intend compn
only in the last few months of WWII (p 287)
The newest trend in research and develop- –Type 4 20-mm HEI (Ma 202) Ammo. Its
ment in ammunition was along the line of proj contd PETN and Intend compn contg Ba
Rockets (Roketto). Very few types were used nitrate, Al pdr, Mg pdr & wax (pp 287–88)
during the war, but there were many experi- –Type 2 20-mm APT “Ammo. Its proj contd
mental models of Antitank (Taisensha) and 7.Og of Tracer compn (pp 288–89) “
Artillery (Ht7hei) Rockets, ranging in size –37-mm HEI Ammo for use in Ho-203 AC
from 75mm to 60cm Cannon. Its proj contd Cyclonite & Intend
Research was rdso conducted on Smooth- compn; proplnt consists of 59.8g of flat 4-mm
bore (KakkG no) and Recoilless (Hihand5) squares poured loosely into brass case and sealed
Weapons (Mu-Hand8), but none of them was in with cardboard disc (pp 289–90)
developed during the war beyond the experi- –37-mm HEI Ammo for use in Ho-204 AC
mental stage Cannon. Its proj contd Cyclonite/Wax and In-
The following Items of Japanese Army, Am- tend compn; proplnt – 75. lg of the same type
munition are described, including illustrations, as above (pp 290–91)
in TM 9-1985-5 (1953) (Ref 3, pages indicated –37-mm Army Ammunition for eight A/Tk
under each item): and Tk Guns listed on pp 293—97 used the same
-Type 38 6.5-mm Ammo for Rifle, Carbine and type of projs filled with PA (Picric Acid), but
Light MG; used single-base graphited proplnt different cartridge cases. They were for the
(pp 270-71) following guns:
-Type 99 7.7-mm (Rimless) and Type 92 Type 11th Year Infantry Gun – 1.850z of
7.7-mm (Semi-rimmed) for MG’s (pp 274–75) graphited proplnt in the form of flakes; they
–7.92-mm Aircraft MG Ammo (p 277) were poured into the case and sealed with a
–8-mm Pistol and 9.mm Pistol Ammo (pp 277–78) cardboard disc (pp 293–95)
 J6

Type 94 Tank Gun – 2.70z of graphited proplnt with Black Powder and its proplnt was the same
in the form’ of rectangular flakes (pp 293 & 295) as in above HE Ammo (p 301)
Type 94 A/Tk, Type 98 Tank and Type 100 –Type 92 5.7-cm (57-mm) AP Ammo was used
Tank Guns – 4.30z of graphited proplnt in the in Type 90 & Type 97 Tank Guns. Its proj
form of unitubular grains contd in a silk bag contd two sections of expl, individually wrapped
(pp 293& 295) in paper; upper section was pressed PA/Wax,
Type 97 A/Tk Gun – 5.00z of graphited proplnt while lower section was cast TNT. Proplnt was
in the form of short, cylindrical grains contd Mk 1 square grain (reed) (p 302)
in a silk bag (p 293) –Ho-401 5.7.cm (57-mm) Ammo for use in
–Type 94 37-mm HE Ammo had the proplnt Ho-401 AC Cannon; no data are given for its
as above and the forward 1/3 of the proj proplnt and for ftiing of proj (p 303)
cavity filled with PA, while the after 2/3 of –Type 92 7-cm’ (70-mm) HE Ammo for use in
the cavity filled with cast TNT. Used in all Type 92 Infantry Gun (Howitzer). Its proj
37-mm Guns (p 295) contd 590g of cast TNT (or pressed RDX/AN
–Type 94 37-mm AP-HE Ammo had the pro- mixture). Proplnt (50g) was in square flakes
plnt as above and the proj fdled with PA; used contd in four pads made by sewing portions of
in many A/Tk & Tank Guns (p 295) the proplnt betw two dark blue silk discs. The
–Type 1 37-mm HE Ammo had the proplnt sections were not uniform in size, holding 5.4,
as above and the proj ffled with PA; used in 8.9, 16.8 & 18.7g of proplnt each. The 5th
Type 1 Tank & A/Tk Guns and also in Type disc, light blue in color, contd 3.lg of BkPdr
94 A/T Gun (p 296) serving as an ignition chge. The cartridge cases
–Ho 301 40-mm HE Ammo for use in Ho-301 were of two designs; the newer type designated
40-mm AC Camon; had proj filled with TNT, “B” (OTSU) was one-piece and slipped off the
contg in forward part a pellet of PA. The proj to change the proplnt chge; an older de-
proplnt chge (0.40z) consisted of small greenish- sign, presumably “A” had a threaded base which
gray, square flakes (ca lmm in size) enclosed could be unscrewed to vary the chge (PP 304–05)
in a silk bag (pp 296–97) Note: Its variety for use in Type 94 Tank Gun
–Type 1 47-mm HE Ammo for use in Type 1 is shown on p 308
A/Tk and Type 1 Tank Guns. The filling –Type 92 7-cm (70-mm) Ammo with Substitute
(87g) of its proj consisted of two preformed Projectile for use in Type 92 Infantry Gun
paper-wrapped blocks taped together and wrapped. (Howitzer). Its proj was filled with BkPdr and
The forward block consisted of two pellets of its proplnt arrangement was the same as in 7-cm
PA – a ring pellet around the gaine and a solid HE Ammo (p 305)
pellet behind the gaine. The after block was –Type 3 7-cm (70-mm) Hollow Charge Ammo for
one cast piece of TNT. Its proplnt chge (398g) use in Type 92 Infantry Gun (Howitzer) as an
consisted of single-perforated cylindrical grains A/Tk weapon. Its proj contd a Ho chge of cast
of a graphited double-base smokeless proplnt TNT/RDX mixture wrapped in varnished paper;
contg NC 60.0, NG 34.5, EtCentralite 3.0 & proplnt – same as in Type 92 7-cm HE Ammo
Diphenylformamide 2.5% (pp 297–98) (pp 305-06)
–Type 1 47-mm AP Ammo for use in Type 1 –Type 95 7-cm (70-mm) Illuminating Ammo for
A/Tk and Tank Guns. Its proj contd 18g of use in Type 92 Infantry Gun (Howitzer). Filling
90/ 10–RDX/paraffin and a Tracer compn. of proj consisted of ejection chge (BkPdr) and
Used 398g of the same double-base proplnt Illuminating chge, probably consisting of mixt of
as in HE Ammo (p 299) Mg & Al pdrs with Ba”nitrate; proplnt – same as
–Type 90 5.7-cm (57-mm) HE Ammo for Type in Type 92 7-cm HE Ammo (pp 306–07)
90 and Type 97 Tank Guns. Its steel proj was Type 95 7-cm (70-mm) AP Ammo for use in
filled with 250g of TNT and its proplnt was Type 94 Tank Gun contains proj filled with 170g
113g of Mk 1 square grain (reed) (p 300) of preformed, paper wrapped HE’s: dshiyaku (qv)
–Type 90 5.7-cm (57-mm) Ammo with Sub- in forward portion and TNT in rear portion;
stitute Cast Iron Projectile was used in Type 90 proplnt was 120g of 5-mm square grain (medium)
~d Type 97 Tank Guns. The proj was filled (p 309)
 J7

7-cm (75-mm) Army Ammunition. There were Field Gun Group (p 323)
ten or more 75-mm (designated as 7-cm) guns in 7-cm (75-mm) Design “B” HE Proj contd
use. Although the weapons varied considerably ~nayaku filling and was used in the same guns
in design, length of bore, and “employment, the as above (p 324)
bore diam was held constant to 75-mm and the Type 98 Modified 7-cm (75-mm) HE Proj was
projs were designed to be interchangeable for ffled with cast TNT and used in Type 41
numerous guns. In this case identical projs Mountain Gun and Type 38 Field Gun Group
could be assembled with different sizes of cart- (pp 325–26) .
ridge cases and proplnt charges to fit the various Type 90 7-cm (75-mm) HE Semisteel Proj was
weapons filled with cast TNT; was used in Types 41, 94,
Ammunition for Navy guns designated 38 & 90 Guns (pp 326–27)
“8-cm” have a bore diam” 3 inches (76.2mm) Type 97 7-cm (75-mm) HE Semisteel Proj was
and are not interchangeable with Army ammuni- filled with cast TNT; used in Type 41 Mountain
tion Gun (pp 327–28)
Following are the 75-mm Army guns belong- Type 90 “A” 7-cm (75-mm) Substitute Proj was
ing to this group, as listed on p 311: filled with BkPdr; used in Types 41, 94, 38
Type 41 Mountain (Regimental) &90 Guns (p 328)
Type 94 Mountain Gun Type 2 7-cm (75-mm) Hollow-Charge Proj
Type 38 Field Gun contd 500g of cast 60/40–TNT/RDX wrapped
Type 41 Cavalry Gun in varnished paper; used in Type 94 and Type
Type 38 Improved Field Gun 41 Mountain Guns (pp 328–29)
Type 95 Field Gun Type 95 7-cm (75-mm) AP-HE Proj contd 460g
Type 11 Year Field or AA Gun of ~nayaku; used in Types 41, 38, 90, 94 &
Type 90 Field Gun 88 Guns (pp 330–31)
Type 1 Self-Propelled Gun Type 1 7-cm (75-mm) AP Proj contd 53g of
Type 88 Field Gun 90/ 10–RDX/Paraffm, coated with graphite and
Type 88 Field or AA (Specird) Gun packed in an Al foil wrapper; used in Types
Propellant cases for these guns are illustrated on 94,41, 90& 38 Guns (pp 331–32)
pp 3 12–15 and complete rounds are listed in Type 38 7-cm (75-mm) Shrapnel Proj contd
Table on pp 3 16–17 100g of BkPdr as bursting chge together with
Following projectiles were used in the above lead balls; used in Types 41, 98, 38 & 90 Guns
guns: (pp 332-33)
7-cm (75-mm) HE-AA Proj fdled with ~nayaku Type 90 7-cm (75-mm) Shrapnel Proj contd
(qv) was used in Type 1l-Year Field AA Gun 100g of BkPdr as bursting chge and ca 272
(p 318) lead balls; used in the same Guns as above (PP
Type 90 7-cm (75-mm) HE-AA Long-Pointed 333–34)
Proj was filled with cast TNT (standard) and as 7-cm (75-mm) Smoke (WP) Proj contd BkPdr as
alternate, PA. Used in Type 1 l-Year & Type 88 bursting chge and WP as chemical agent; no
Guns (pp 3 19–20) data for weapons (p 335)
Type 90 7-cm (75-mm) HE, Long Pointed Pro- Type 90 7-cm (75-mm) “Smoke (WP) Proj contd
jectile was ffled with cast TNT (standard) or 100g of ~nayaku as bursting chge and 700g WP;
Heineiyaku (qv) as alternate. Used in Type 38 used in Types 41, 94, 38 & 90 Guns. Its
Field Gun Group (four weapons), Type 88 screening capacity was 20 meters high & wide”
Field AA (Special) Gun, Type 90 Field Gun and and duration 1–2 minutes (pp 336–37)
Type 94 Mountain Gun (p 321) Type 90 7-cm (75-mm) Incendiary Proj contd’
Type 94 7-cm (75-mm) HE Proj was filled with 20g of BkPdr as expelling chge and 530g as
TNT, while Angayaku and Heineiyaku were incendiary chge; used in the same guns as above
used as alternates; used in the same guns as (p 337)
above (pp 321 –22) Type 90 7-cm (75-mm) Illuminating Proj contd
7-cm (75-mm) Design “A” HE Proj contd BkPdr as expelling chge and 250g of illuminating
625g of ~nayaku (qv); was used in Type 41 chge (probably a mixture of Al, Mg & Ba nitrate);
and Type 94 Mountain Guns and in Type 38 used in the same guns as above (PP 338–39)
 J8

Type 1l-Year 7-cm (75-mm) Target Proj contd Type 38 Gun – 1740g in 1 increment of Mk 2
folded parachute and shrouds in cardboard strip
cylinder. After propelling the proj, the para- Type 14-Year AA Gun – 3075g in 1 increment
chute became ejected bya small chge of expl, of Mk 3 strip
located in Time Fuze. Then the descending ~ Illustrations for “cartridge cases used in the above
parachute andshrotids served astargetsfor AA weapons are on pp 347 to 350 and foflo wing
practice; used in Type 11-Year AA Gun andin are the projectiles used in 105-mm weapons:
Type 88 Field AA Gun (p 339) Type 91 10-cm (105-mm) HE Proj is ftied with
7-cm (7$-mm) Liquid Incendiary Proj contd 2300g of cast TNT; used in Type 91 How and
40g of granular PA in paper container as burst- Types 38, 92 & 14-Year Field Guns (p 351)
ing chge and soln of WP iri CS2 (300g) with Type 91 1O-cm (105-mm) HE, Long-Pointed. Nose
rubber pelIets (320g); used in Types 41, 94, 38 Proj was filled with cast TNT and “White Com-
&’90 Guns (pp 339–40) position” of AN, RDX & GuN; used in Type 91
7-cm (75-mm) Vomit-Gas Proj contd 460g of How, Types 38, 92 & 14-Year Field Guns and
70/30–TNT/Naphthalene as bursting chge and 14-Year AA Gun (with freed Ammo) (pp 352–53)
170g of Diphenylcyanarsine as liquid chemical 12-cm (120-mm) Shrapnel Ammo with Proj contg
agent; used in Type 41 Regimental or Mountain BkPdr as ejecting chge and 539 lead balls packed
Gun (p 34i) in a rosin matrix. The proplnt was in two in-
Type 100 8-cm (88-mm) HE-AA Ammo with crements each encased in a silk bag with a small
Long-Pointed Proj which was ffled with 900g igniter chge sewed to the bottom of each; the
of TNT; was propelled by 2330g of No 16 1st increment was NC in 5/16” square flakes,
cylindrical proplnt; used in Type 99 AA Gun while the 2nd was NC in l/ 16“ square flakes; ~
(pp 342-43) used in Type 38 How (pp 353–54)
9-cm (90-rnm) HE Ammo with PIOJ filled with 12-cm (120-mm) AP-HE Ammo with Proj filled
590g of crude TNT; used in an antiquated wea’ with PA; used the same proplnt and in the same
pon classified as mortar; no info about proplnt weapon as for shrapnel ammo (pp 354-55)
used (p 343) 15-cm (lSO-mm) Army Ammunition
9-cm (90-mm) HE Ammo with Se’fisteel Proj There were three 150-mm Howitzers and four
which is ffled with 650g of TNT; used in the 150-mm Guns, which varied greatly in design
same type of weapon as hove; no info about from a very short-range How to long-range
proplnt used (pp 343–44) Field Guns. The projs were not as interchange-
Army 10-cm (105-mm) Ammunition able as in 75-mm & 105-mm weapons. Usually
There were three 105-mm Howitzers and four there was one type of proj for use in Hews
105-rnm Guns, which are designated 10-cm by ~ and another type for the Guns. All the weapons
the Japanese. The projs were in most cases used semifmed arnrno with the exception of Type
interchangeable. All weapons used semif~ed 88 Gun which used a bag charge
ammo except’ the Type 14-Year AA Gun which Following list (extracted from p 35,7) gives
used freed ammo (p 344) types and weights of proplnt chges used in 150-mm
Following list (extracted from p 346) gives Weapons:
types and weights of propellant charges used in Type 4-Year How – 2260g in 5 increments of
105-mrn Weapons: Mk 2 square grain
Type 14-Year Howitzer – 430g ih 3 increments Type 38 How - 825g in 2 increments of Mk 1
of Mk 1 square grain or Mk 3 strip square grains
Type 91 Howitzer – 1135g in 4 increments of Type 96 How – 2930g in 5 increments of Mk 2
Mk 2 square grain square grains
Type 14-Year Improved Howitzer – 692g in 3 Type 45 Gun
Type 7-Year Gun 16650g in 3 “increments
increments of Mk 2 square grain
Type 90 Gun of Mk 5 strip
Type 92 Gun – 4000g in 2 increments of Mark }
3 strip Type 89 Gun – 9700g in 2 increments of Mk 4
Type 14-Year Gun – 2535g in 2 increments strip
of Mark 3 strip Illustrations of cartridge cases used 150-mm wea-
,,
 J9

pens are given on pp 358–61 and the following (Ref 3, p IV), the following information is
projectiles used in these weapons: given:
Type 92 15-cm (150-mm) HE Proj was filled The Japanese Navy Terminology of WWII
with Angayaku (qv); used in Type 4-Year, Type for projectiles was highly irregular and cumber-
96& Type 38 Hews (p 362) some. Complete and accurate identification of
Type 93 15-cm (150-mm) HE Proj was ffled proj required identification of the gun, de-
with cast TNT; used in Type 89, Type 45, Type scriptive nomenclature of the proj, and mark
7-Year and Type 90 Guns (p 363) (or type) and modification number. For this
Type 92 15-cm (150-mm) HE, Long-Pointed Proj reason an arbitrary system of nomenclature is
was ftied with cast TNT; used in Type 4-Year, used in TM 9-1985-5 (Ref 3). All Navy projs
Type 96 & Type 38 Hews (p 364) with a relatively heavy HE charge (including
Type 93 15-cm (150-rnm) HE, Long-Pointed Proj light AP types) are designated TSUJODAN,
was filled with cast TNT; used in Type 89, Type which may be translated either “Ordinary Pro-
45, Type 7-Year & Type 90 Guns (p 365) ject~e” or “Common Projectile”. In TM 9-
Type 95 15-cm (150-mrn) AP-HE Proj was filled 1985:5; ‘the term “Common” is reserved for
with two preformed blocks of high grade TNT; light penetrating type of projectile (solid nose,
used in Type 4-Year, Type 38 & Type 96 Hews base fuzed), while for projs having point-
and in Type 45, Type 7-Year, Type 90 & Type detonating fuzes, the US designation HE is
89 (bag chge) Guns (p 366) used
15-cm (150-mm) AP-HE Proj was filled with PA Color system of marking projectiles for all
in two preformed, paper-wrapped bags; used in sizes over 40-mm is explained on pp 427–31
the same guns and Hews as above (p 367) of Ref 3, and projs of 40-mm and below on
Type 13 15-cm(150-mrn) Smoke (WP) Proj pp 432–33
contd PA as bursting chge and WP cast in a The following Items of Japanese Navy Am-
brass cylinder which, surrounded by wax, was munition are described, including the illustra-
fitted below PA chge; used in Type 4-Year, tions, in TM 9-1985-5 (1953) (Ref 3, pages in-
Type 96 & Type 38 Hews (pp 367–68) dicated under each Item):
30-cm (305-mm) AP-HE Proj; no data for its 7.7-mm Aircraft Machine Gun Ammunition with
filling (p 369) Ball AP, Intend, Tracer & HE Projectiles; no
3CLcm(305-mm) AP-HE Proj; no data for its data for proplnt; used in Type 92 & Type 97
ffling (p 370) ACMG’S and in Type 92 AAMG (pp 434–35)
Army Rockets (Ref 3, pp 371 –72) – See under , 13-mm ACMG Ammunition with Tracer, HE
ROCKETS (PETN)T and Intend (WP) Projs; no data for
Army Mortars (Ref”3, pp 372–90) – See under proplnt; used in Type 2 ACMG (pp 436–37)
MORTARS 13.2-mm AC and AAMG Ammo with Tracer,
Army Projectile Fuzes (Ref 3, pp 391–426) – AP & HE(PETN) Intend @P) Projs; no data
See under FUZES for proplnt; used in Type 3 ACMG & Type 93
Ammunition, Navy (Danyaku Kaigun) AAMG (pp 438-39)
Accdg to Ref 1, p 170, Japanese Navy Am- Naval 20-mm Ammunition was divided into
munition of WWII was divided into the following the foliowing:
groups: Type 99 20-mm Ammo (p 440) existed as Mk I
a) Small Arms Ammunition – items caliber and Mk H and was copied from the Swiss
7.7-mm, 7.9-mm, 13-mm and 13.2-mm Oerlikon design. The proplnt consisted of
b) Aircraft Cannon Ammunition – items caliber graphited single-base, single-perforated cylindri-
20-mm and 30-mm cal grains, 13.6g for Mk I and 2 1.4g for Mk II.
c) Antiaircraft “Automatic Weapons” Ammuni- Both Mk’s used the same types of projectiles,
tion – items caliber 25-mm and 40-mm which were as follows:
d) Large Caliber Ammunition – items of caliber 20-mm HE Proj contd as ffling 50/50–Pentolite
5-cm (50-mm) and over (p 441)
Under the title “Japanese Ammunition– 20-mm HEIncend Proj contd as ftiing TNT and
Explanatory Notes”, TM 9-1985-5 (1953) WP (p 442)
 J 10

20-mm HETracer Proj contd Pentolite and 30-mm Type 2 & Type 5 HEIncend Projs
tracer compn (p 443) contd 3.56g of Pentolite and 19.94g of WP
20-inm HET, Self-Destroying Proj contd Pento- (p 452)
lite and Tracer compn. The proj was similar to 30-mm Type 5 HETracer Proj contd in upper
the HET type except for its self-destroying fea- cavity Pentolite, while Tracer was in lower
ture. This was accomplished by ignition of cavity (p 453)
BkPdr train leading from the tracer thru the 30-mm Type 5 Tracer Proj contd nothing but
hole drilled, thru the septum of the proj and HE Tracer (p 454)
ffing to the base of the gaine (p 444) 30-mm Practice Proj contd no filling; was used
L
20-mm APIncend Proj contd Intend consisting as the first round to clear the gun bore (p 455)
of NC 77.5, Na nitrate 11.3 & Al pdr 11.2% 40-mm Naval Ammunition was used in 40-mm
which was loaded at the base. Upon impact the Navy’s Vickers-Armstrong Guns. Its proplnt
rear end of proj ruptured and the heat generated consisted of 95 .9g cylindrical length of smoke-
ignited the Intend compn. There was no fuze less pdr (p 455) and the following projectiles
(p444) were used:
20-mm Tracer Proj was loaded with Tracer 40-mm AP Proj contd 23g of cast TNT (p 456)
compn; the proj was called “bag buster” be- 40-mm HE. AA Proj contd 70g of cast TNT
cause it was usually the f~st round to be fired (p 457)
to break the muzzle cover of the gun (p 445) 40-mm Tracer Proj contd nothing but Tracer
20-mm Practice Proj contd no filling (p 445) compn (p 458)
25-mm Naval Ammunition 5-cm (47-mm) Complete Round and Common
The only 25-mm Gun used by the Japanese Projectile. Its proplnt consisted of 67g unper-
was Type 96 Model 2 AA-A/Tk Gun. It was forated, cylindricrd, amber-colored sticks of
multiple-barreled, air-cooled, magazine-fed, double-base proplnt (5C2 Type 5-Year) enclosed
automatic weapon. Used different projectiles, in a compartmented bag of heavy brownish
but the same propellant which consisted of 120g silk, placed in brass or steel cartridge. Its proj
of single-perforated graphited cylindrical grains was 50g of loose granular BkPdr. Used in
of NC (p 446) Short 5-cm Gun, mounted on wooden-spoked ,
The following 25-mm Projectiles were used: wheels as a field piece (pp 458–59)
25-mm HE Proj contd 66/34–TNT/Al as std 8-cm (76.2-mm) (3-inch) Ammunition for use
ffling or cast TNT .or Tetryl as alternates in various 8-cm/40 Guns included:
(p 447) 8-cm (’76.2-mm) Complete Round (Semifixed)
25-mm HEIncend Proj was ffled with TNT/Al used 900g of 203C (Type 89) proplnt which
and WP (p 447) consisted of unperforated 1/1 6–1/32 by 12.75
25-mm HETracer Proj was filled with TNT/Al inches cylindrical sticks of double-base pdr
pellets and Tracer element. As alternate HE enclosed in heavy paper and placed in brass
pressed or cast Tetryl was used (p 448) cartridge (p 460); used one of the following
25-mm HET (Self-Destroying) Proj contd TNT/Al projectiles:
pellets with BkPdr core in the lower pellet (p 448) 8-cm (Ordinary Mk 2 Mod 2) HE Proj contd
25-mm APT Proj contd 8.64g Tracer compn (Na 0.71 lb of Shimose (cast PA) in single block
nitrate, Mg & Ba peroxide) and 3.52g inert ma- sealed in a waxed paper (p 461)
terial (dry clay) (p 449) 8-cm Shrapnel Proj contd BkPdr as ejecting chge
30-mm Naval Ammunition and shrapnel balls (p 462)
Two 30-mm Aircraft Cannons, the Type 2 8-cm (Ordinary Mk 3 Mod 1) HE Proj contd
and Type 5 were used during WWII. They were 0.9 lb of Shimose (cast PA) (p 464)
of Swiss (Oerlikon Co) design. Same proplnt 8-cm AP Type 1 Special Common Proj contd
was used in ammo of these guns. It consisted 0.41 lb Type 91 Expl (Trinitroanisole) (p 465)
of graphited, single-perforated cylindrical grains 8-cm Time Practice Proj filled with either smoke
of NC. The projectiles used were as follows: compd or spotting dye (p 466)
30-mm Type 5 HE Proj was filled with cast 10-cm (100-mm) (3. 9-inch) Complete Round
Pentolite (p 451) (Fixed) contd 12.7 lb of double-base proplnt
 J 11

(Type 91 Mk 2) in the form of flat strips (pp 13 Double-Base Propellant consisting of graphited
467–68). It was used with: unperforated cylindrical sticks 0.079 by 15.75
10-cm (100-mm) HE Proj which contd 3.13 lb inches packed in a compartmented bag of heavy
of Type 92 Expl (cast TNT). Used in Type silk. Used in Type 88 & Type 89 12.7-cm/40
98 10-cm/65 & 10-cm/50 Dual Purpose Guns Dual Purpose Guns with the following projectiles:
(p 468) 12.7-cm HE Proj was ffled with 3.94 lb of
12-cm (120-mm) (4. 7-inch) Complete Round Shimose (p 485)
(Fixed) contd 1.1 lb Type 89 Proplnt consisting 12.7-cm Incendiary Shrapnel (Type 3 Ordinary)
of unperforated cylindrical stick 1/32 by 6-7 inches Proj contd 162g Shimose, 2.3g Tetryl, 0.13g
of double-base pdr. Used in Short 12-cm Gun, LA, 35g BkPdr and Incendiary charge, which
12 Calibers Long (p 469). Its projectile was: consisted of 43 steel pellets ftied with the
12-cm/Short HE Proj contd 5.5 lb of Type 91 following compn: Mg pdr S4, Ba dioxide 26,
Expl (Trinitroanisole) (p 470) rubber 15, Fe oxide 1.5 & sulfur 3% (adds to
12-cm (12@mm) (4. 7-inch) Complete Round 99.5%) (p 486)
(Semiftied) contd in brass cartridge 11,88 lb 14-cm (14&mm) (5.5-inch) Propellant and
of Type ,13 Propellant consisting of unperforated Powder Tanks.
cylindricrd sticks of double-base pdr. Used in Under the term “powder tanks” sealed water-
Type 1l-Year 12-cm/45 Gun (Low Angle) proof cylinders were used for storing propellant
with the following projs: charges. Two types were recovered by Americans:
12-cm HE (Ordimry Mk 3) Proj contd 3.61 lb one was a heavy tank (26;4 lbs) made of cast
of cast PA (Shimose) (pp 472–73) steel and bronze; the other was of sheet steel
12-cm HE (Ordinary Mk 3 Mod 1) Proj contd and Al (15.4 Ibs). Both tanks were well lacquered
3.61 lb of Shimose (p 474) inside and had the same internal dimensions –
12-cm HE (Ordinary Mk 4) Proj contd Shimose 6.2 by 33.4 inches
(p 475) Propellant chge of 14-cm Bag Ammo consisted
12-cm Common Projectile contd Shimose (p 476) of 24.51 lbs of double-base proplnt 37C which
12-cm Illuminating Proj contd 0.5 oz of BkPdr consisted of graphited unperforated cylindrical
as expelling chge and illuminant consisting of Ba sticks 0.15 by 28 inches, enclosed in a heavy
nitrate 35.6, K nitrate 10.4, Mg 38.0, wax 13.9, silk bag. Used in’ 3-Year 40-cm/50 Gun (Low
carbon 0.8 & sulfur 1.q~o. Compn of first fue Angle) with the following projectiles:
compd was: K nitrate 63.2, wax 5.5, glass 6.1 14-cm HE Proj contd 7.9 lb Shimose (p 489)
& carbon 13.1%. Illuminant was located in 10 14-cm HE (Type O, Ordinary) Proj contd 6.60
cardboard cylinders arranged in two layers of lb Shimose (p 490)
5 cylinders, each contg 5.4 oz of illuminant. 14-cm (Ordinary Mk 1) Common Proj contd
The proj was used in Type 11-Year and Type 5,94 lb Shimose (p 491)
3-Year 12-cm/45 Guns (pp 477–78) 14-cm (Ordinary Mod 1) Common Capped
12-cm (120-mm) (4, 7-inch) Complete Round Proj contd 4.80 lb Shimose (p 492)
(Fixed) contd in brass cartridge 12.0 lb of Type 14-cm Illuminating Proj contd: primary ejection
13 double-base proplnt in the form of cylindr- chge (100g BkPdr), secondary ejection chge
ical sticks. Used in Type 10-Year 12-cm/45 (41g BkPdr); initiating pellet, relay train and
Durd Purpose Gun with the following projs: delay were BkPdr; ignition compd for the il-
12-cm HE (Ordinary Mod 1) Proj contd 3.96 luminant (mixt of K nitrate, Fe oxide, Al, S
lb Type 91 Expl (pp 481–82) & wax); illuminant (mixt of Ba nitrate, Mg &
12-cm HE (Ordinary Mod 2) Proj contd 3.46 wax). Total weight of ffling 31 lbs (p 493)
lb of Shimose (p 482) 14-cm Smoke Proj was ffled presumably with
12-cm Incendiary Shrapnel contd 1.19 lb of WP (p 494)
Shimose and Incendiary charge consisting of 14-cm (140-mm) (5.5-inch) Cartridge Case
WP & 48 steel pellets, total wt, 8.55 lbs (pp (Sem#ied) was of brass and contd 6860g of
482–83) Type 13 double-base proplnt consisting of
12. 7-cm (127-mm) (5-inch) Complete Round graphited unperforated cylindrical sticks 1/8
(Fixed) contd in brass cartridge 8.87 lb of Type by 19% inches enclosed in a heavy silk bag. No
 J 12

projs used with this case are listed (p 495) but they are described here separately under
15-cm (152-mm) (6-inch) Complete Round corresponding letters in alphabetical order
(Semifmed) used 18.94 lb 37DC Double-Base Refs for AMMUNITION:
Proplnt which consisted of graphited unperforated 1) Anon, “Handbook of Japanese Explosive
cylindrical sticks 1/8 by 26 inches enclosed in Ordnance”, OPNAV 30-3M (1945), pp 123–57
heavy silk bag packed in a brass cartridge. Used (Army Ammo) & 170–91 (Navy Ammo)
in Type 41 (Meiji) 15-cm/40 Gun (Low Angle) 2) Anon, “Japanese Explosive Ordnance”.,
with the following projectiles: TM 9-1985-5 (1953) 4) W.H. Tantum IV
15-cm Common (Ordinary Mod 1) Proj contd & E.J. Hoffschmidt, Edts, “Japanese Combat
Shimose (p 497) Weapons of World War H“, WE Inc, Old Green-
15-cm HE (Ordinary Type O) Proj contd 6.8 lb wich, Corn, Vol 2 (1968)
Shimose (p 498)
15-cm Common (Ordinary Mk 4) Proj contd Amphibian (Water) Mines. See under MINES
5.9 lb Shimose (p 499)
15-cm Incendiary Shrapnel Proj – no data for Anbenyaku or Shobenyaku. HE mixture con-
filling (p 500) sisting of AN 55 & Dinitrobenzene 45’%0 used
15.5-cm (155-mm) (6.1-inch) Ammunition was during WWII as bursting chge of some projectiles.
used in 15.5-cm Gun (Bag). No data for proplnt The name Sh6benyaku was used at Nanman Ar-
used but the following projectiles are listed: senal, Manchuria. An exptl mixt by the same
15.5-cm HE (Ordinary Type O) Proj contd name consisted of AN, TNBz & Tetryl
7.5 lb Shimose (p 502) A blasting expl, also called Anbenyaku, con-
15.5-cm AP (Type 91) Proj contd 6.84 lb Tri- sisting of AN 71.7, NG 8.0, Collod Cotton 0.3
nitroanisole (p 503) and powdered seaweed 20% was proposed in
15.5-cm Illuminating Proj was ffled with the 1948 by T. Watanabe, JapanP 176113 (1948)
same substance as 14-cm Illuminating Proj (p &CA 45,4930 (1951) (Ref 5, p 361)
504)
20-cm/Short (202-mm) (8-inch) Complete Angayaku. Several HE compns were known.
Round (Semiftied) was used in 20-cm Short One of them listed in Ref 1, p 27 consisted of
Gun. Its proplnt was double-base 10C3 (Type AN 75 & RDX 25%. It was cast in TNT sur-
89) consisting of unperforated cylindrical sticks round for ftiing bombs. The compn listed in
1/32 by 8*%–9 inches, enclosed in two com- Ref 6, p 8-3: RDX 85 & wax 15% was used in
partmented heavy silk bags packed in brass ~ Projectiles while compn: RDX 41, PETN
cartridge. The inner bag contd 2.1 lb of proplnt, 50 & wax 8% was used in Machinegun Bullets
while the outer bag had 2.3 lb. The following In addn to these, the following compns are
projs were used: , listed in Ref 5, p 362: a) AN 84 & RDX 16%;
20-cm/Short HE (Ordinary Mk 1) Proj contd b) AN 51, RDX 15 & GuN (Guanidine Nitrate)
28.50 lbs Trinitroanisole in three cast blocks 34% and c) AN 48, RDX 20 & GuN 32%
(p 506) All of the above compns were white in color,
20-cm AP, Type 91 Proj contd 17.38 lb TNAns nontoxic and comparable in performance to
in a preformed block (p 507) Amatols. It was claimed that compns contg
20-cm HE (Ordinary Type O) Proj contd 21.34 GuN had low coefficients of shrinkage and,
lb of TNAns (p 508) therefore, could be poured in large casts in a
36-cm (365-mm) (14-inch) AP I%oj used in single pour
36-cm/45 Gun (Bag); probable filling of proj – Another Angayaku compn considered to be
TNAns (p 510) similar to Brit & US Torpex consisted of AN
40-cm (406-mm) (16-inch) Mk 5 AP Proj was 43.2, GuN 28.8, RDX 8.0 & Al powder 20%
used in 40-cm/45 Gun (Bag); probable filling – was manufd at the Sankanoichi Factory of the
Trinitroanisole (p 5.11) Tokyo Army Arsenal No 2. It was used to a
Note: Under Navy Ammunition are also de- limited extent in various types of underwater
scribed Rockets (Ref 3, pp 5 12–1 4); Mortars expls (Ref 5, pp 361–62)
(pp 515–17) and Projectile Fuzes (PP 514–43), As an example of use of Angayaku as a
 J 13

ffler may be cited Type 94 7-cm (75-mm) 75-mm Field Gun, Mod 90 (1930) (p 96)
HE Proj described and illustrated in Ref 3, p 321 75-mm Mountain (Pack) Gun, Mod 94 (1934)
(pp 97-8)
Armored Cars. See under Combat Vehicles 75-mm Field Gun, Mod 95 (1935) (pp 99–1 00)
8-cm (7.62) High Angle Gun, Type 3 (p 101)
Armor-Piercing High-Explosive (AP-HE) Pro- 88-mm Antiaircraft Gun, Type 99 (Year ?)
jectile. Hakoryudan Te~odan (p 104)
105-mm Howitzer, Mod 91 (1931) (pp 103–04)
Armor-Piercing (AP) Projectile. Hakodan or 105-mm Gun, Mod 92 (1932) (pp 105–06)
Tekkodan 120-mm, 45 Calibers, Naval Dual Purpose Gun,
Type 10 (p 107)
Arsenals (Koshoor Z6neisho) and Powder 120-mm, 45 Calibers, 1 l-Year Type Gun (p 108)
Factories (Kayaku seiztisho) 140-mm Seacoast Gun, Type 3 (Year ?) (p 109)
The following Arsenals are listed in Ref 1, Note: Table on p 110 lists “Characteristics
p 6: Tokyo, Osaka, Kure, Toyokawa, Yok6- of Principal Japanew Weapons”:
suka, Maizuro and Sasebo. Tokyo and Osaka 150-rnm Howitzer, Mod 4 (1915) (pp 11 1–12)
were the Army Arsenals, while the other five 150-mm Howitzer, Mod 96 (1936) (pp 113–14)
were the Navy Arsenals 300-mm Short Howitzer, Type 7 (Year ?) (p 115)
The following Arsenals are listed in the 105-mm Field Gun, Type 14 (Year ?) (p 115a)
book of Tantum & Hoffschmidt, listed here as (See also Mortar and Rocket)
Ref 7, p 38: Kokura, Tokyo, Nagoya, Heijo,
Osaka, Chioda and South Arsenrd. In the same Artillery Ammunition. See under ~MUNITION
book the Tokyo Explosives Plant is listed
Aruminyumu. Aluminum. It was used in
ARTILLERY (Hohei) AND ITS WEAPONS (Ho) powdered form in many Japanese Navy compns,
In the book of Tantum and Hoffschmidt such as Otsu B, Type 2,’ Type 4 & Type 92,
(Ref 7), Section 3, pp 80–1 16, the following listed in Ref 1, pp 32–33. It was also contd in
weapons are described and illustrated: one of the Army expls – Angayaku (qv)
37-mm Infantry Gun, Mod 11 (1922) (pp 80–1)
37-mm Gun, Mod 94 (1934) (PP 84–5) B4 (Incendiary) or Type 2 Navy Explosive.
47-mm Antitank Gun, Mod 1 (1941) (pp 84–5) A light-gray castable mixture of Trinitroanisole
70-mm Battalion Howitzer, Mod 92 (1932) (pp 60 to 70 & Al 40 to 30%. The props of the
86–7) 60/40 mixture were: density 1.90; Brisance by
75-mm Field Gun, Mod 38 (1905) (Improved) Cu cylinder crusher test 82% (PA= 1OO%);
(pp 88-9) Expln Temp 300°; Impact Sensitivity with 5kg
75-mm Regimental Gun, Mod 41 (1908) (pp wt 17cm maximum with no explns; Friction
90–1) Sensitivity with 60kg pressure – no explns;
75-mm Antiaircraft ‘Gun, Mod 88 (1928) (p 92) and Power by Ballistic Mortar 64% of PA. It
75-mm Mobile Field AA Gun, Mod 88 (1928) was used in Submarine Gun Incendiary Shells
(p 93) (Ref 5, p 362)
Note: On p 94 are given illustrations of the
following Japanese Antiaircraft Cannons: “Baka” Piloted Rocket Bomb. See under
75-mm Heavy AA Cannon, M88 (1928) – the BOMBS and in Ref 2, pp 116–18
Standard Army; 76-mm AA Cannon, M3 (1914);
105-mm Amy AA Cannon M14 (1925) and Bakkan Blasting Cap
127-mm Twin Mount, Dual-Purpose Cannon,
M98 (1929) Bakubo. Detonator
Table on p 95 lists “Japanese 75-mm Artillery
Ammunition”. This includes Models of Pro- Bakuchiku. Squib ‘
jectiles, Their Bursting Charges, Standard Fuzes
and Models of Guns: Bakudan. See BOMB
 J 14

Bakufun. Detonating Explosive or Exploding ing items: a) Army 20-mm Ammo as a tempo-
Powder. A light-gray to tan pdr consisting of ra~ measure; b) Army ejector charges for 70-mm
MF (Mercuric Fulminate) 28.8, K chlorate Barrage Mortar, Shrapnel Shells & Pyrotechnics;
37.7, Antimony trisulfide 31.5 & abrasive 2%. c) Army Delays & Relays in Bomb & Projectile
Accdg to documents, Mks I & III are used in Fuzes; d) Army Delays and Igniters in Pyro-
ammunition primers while Mk 2 is used in fuze technics; e) Navy ejector charges for Illuminating
primers (Ref 1, p 25 & Ref 5, pp 362–63). Shells & Pyrotechnics; ~ Navy Delays & Relays
See also Raibun in Bomb & Projectile Fuzes and g) Navy Delays
& Igniters for Pyrotechnics (Ref 1, pp 27, 30
Bakuhaki. Exploder; Blasting Machine & 33)

Bakuhatsu. Explosion, Blast or Detonation Blast. Bakuhatsu

Bakuhatsu Blast Effect

koryoku. Blasting Cap. Bakkan
,..
Bakuhatsu sei. Blasting Gelatin Bogyo Sabotage

Bakuhayaku. Detonating Explosive; Brisant Bogyo Defense

Explosive
Bogyo jirai. Antitank Mine
Bakuhuyo bakudan. General Purpose Bombs;
Demolition Bomb Bokuyo kaki. Antiaircraft Weapon

Bakurai. Depth Charge BOMBS (Bakudan) (Excluding Flares and Rocket

Bombs)
Bakurai toshaho Mine Thrower; Y-Gun Introduction
Accdg to TM 9-19854 (1953) (Ref 2, p 1),
Bakuretsu judan. Explosive Bullet the Japanese Army (Rikugun) and Navy (Kaigun)
had during WWII separate Air Forces (Kiigun),
Bakuyaku. Explosive Charge; Powder Charge each of which employed its own distinct bombs
and fuzes (Shinkan). For the most part the
Bakuyakyto. Bangalore Torpedo Army and ‘Navy bombs and fuzes camot be
used interchangeably. Special adapters have
Balloons, Paper. Ingenious paper balloons been developed, however, which allowed, some
were launched in 1944 against the West’ Coast flexibility of this rule
of the US and Canada.. This is described in Until the reign of the present Emperor (Shows
Vol 2 of Encycl on p B1 l-L, under “Brdloons era, which started in 1926), items were designated
and Airships and Their “Application in War” by the year era. Now, however, the year of the,
Japanese Empire-2600, which corresponds to
Bangalore Torpedo. Bakuyakuto or Hakaito See our 1940, may be used. For items introduced
under Demolition Tubes up to the year 2600, the last two numbers are
used in the designation. Thus, Type 99 means
Barisutaito. Ballistite the item was adopted in 2599 or our 1939.
The year 2600 may be represented as Type 100
Biransei gasu. Blister Gas or Type O, and the years 2601, 2602, etc as
Types 1, 2, etc
Black Powder. Kokushokuyaku (Black Color Exptl ordnance items are assigned the type
Explosive) or Yuerzyaku (Nonsmokeless Powder); numbers indicating the year of Showa era during
Gunpowder – Kayaku. Black, loose-powdery which the experiment was standardized
material consisting of K nitrate, sulfur & char- Ordmnce items standardized in the eras pre-
coal. It was used during WWII for the follow- ceding the Showa era; namely, Taiaho (19 12–
 J 15

1926) and Meiji (1 867–1912) are designated by was surrounded by steel pellets set in concrete
the era and the year. Type H (Taisho) = 1922 (p 27);
and Type 41 (Meiji) = 1908 Type 1 30-kg Substitute Bomb consisted of a
Some items developed for a special purpose light sheet steel cylinder surrounding a central
were designated by a Mark number. The term steel burster tube contg in forward part BkPdr
Model indicates a change in basic design, while chge and after part HE chge. The space betw
the term Modification represents minor changes the tube and outer casing was fdled with steel
in design or a change in explosive pellets set in concrete (pp 27–28);
Abbreviations are the same as indicated under Type 95 4-kg Practice Bomb housed an ampoule
AMMUNITION contg a smoke compn (p 29)
Bombs, Army (Bakudan Rikugun) Cluster Bombs: Type 2 l/3-kg, Type 3 l/2-kg
The following” Army Bombs are listed in and Type 2 l/2-kg contg TNT 58–60 & RDX
Ref 2 on pages indicated under items: 42 –40% fillers @p 29–32). Containers for
Type 92 15-kg HE contd cast PA or TNT (pp 4–5); these bombs are described on pp 33–36;
Type 99 30-kg HE contd 48/52–RDX/TNT (p 5); l-kg Aircraft Missile consisted of a spherical
Type 94 50-kg HE, Type 3 100-kg HE, Type 94 compressed paper container from which a 3-
Modified HE, Type 1 50-kg HE, Type 1 100-kg inch high tubular neck of compressed cardboard
HE, Type 1 250-kg, Type ’92 250-kg and Type projected. A wooden plug at the base of this
92 500-kg HE Bombs were ftied with cast PA neck housed a friction pull igniter. A central
(PP 6-9); burster chge consisted of granular BkPdr in a
Type 3 100-kg and Type 3 250-kg Skipping silk bag. Surrounding this were 32 cylindrical
Bombs contd paper-wrapped cast PA blocks sheet-metal pellets contg a LE (Low Explosive)
sealed with TNT (pp 10–1 1); chge of K nitrate 55.7, sulfur 16.7, Al 14.6 &
Type 4 100-kg, 250-kg & 500-kg Antishipping antimony sulfide 13.0%. Each pellet had a
‘ Bomb contd paper-wrapped cast PA blocks l/2-inch safety fuse which was in contact with
waled with TNT (pp 12–1 3); burster chge. For its operation the cord of the
l-kg and 5-kg Thermite Incendiary Bombs igniter was pulled and the missile was thrown
contd Thermite as main chge and first fire from the plane. After a short delay the BkPdr
chge (pp 14–1 6); burster chge exploded rupturing the paper body,
Type 97 12-kg Thermite consisted of a thin scattering the expl pellets and simultaneously
steel body contd” two BkPdr chges and three igniting the fuse of the pellets. After a short
Therrnite ftied Mg fire pots (pp 16–18); delay the pellets were detonated. This missile
Type 97 50-kg and Type 100-kg IncendiaW was used in air-to-air bombing (pp 36–7 & Fig 31);
Bombs consisted of thin-steel body fried with 50-kg & 100-kg Pamphlet Containers consisted
400450 rubber bags impregnated with soln of of cardboard case contg a small burster chge and
phosphorus in CS z. The HE chge in the nose paper pamphlets (p 38);
and central burster tube was PA (pp 18–20); Miscellaneous Army Bombs – Illustrations with-
Type 100 50-kg Smoke Bomb consisted of out description of several bombs are given on pp
thin-steel body filled with FS smoke compn 39–40
(Chlorosulfonic acid 41, sulfur trioxide 54& A shorter description, with illustrations, of
sulfuric acid 5%). The HE chge in the nose Japanese Army Bombs is given in Ref 1, pp
and in the burster was PA (p 21); 66–80
Type 92 Gas Bomb contd 50/50–Lewisite/ Bombs, Navy (Bakudan Kaigun)
Mustard Gas (p 22); Introduction
Type 97 15-kg Concrete Bomb was a light sheet Accdg to Ref 2, p 41, Navy bombs were di-
steel cylinder with central exploder tube filled vided into the following classes: ‘land” bombs
with cast PA which was surrounded by steel specially designed for use against land targets;
pellets set in concrete (p 26); “Ordinary” were designed for use against ships.
Type 94 10-kg Substitute Bomb consisted of a They included both GP (General Purpose) and
thick concrete case‘surrounding a steel central SAP (Semi-Armor-Piercing);
tube burster ftied with loose BkPdr. The tube “Special” are designed for special purposes and
 J 16

each class is indicated by a mark number; Type 4 No 6 Mk 1 Bomb was designed to be

“Smoke” were used for concealment purposes; ffled with mustard gas or with any suitable
“Practice” were used for practice bombing; CWA (Chemical Warfare Agent)” (p. 58);
“Target-marker bombs were used as target- Type 99 No 6 Mk 2, Type 99 N06 MK2
marking beacons; Modification 1, Type 1 No 25 Mk 2 Model 1
“Training” bombs were used for trai~ng in and Type 1 No 25 Mk 2 Model 1 Modification
handling; 1 Bombs were filled with Type 98 Expl (pp
“Dummy” bombs were used for training and 58–63);
practice bombing Type 99 No 3 Mk 3 Bomb consisted of a sheet
Individual Navy bombs in these main general metal cylinder contg a canister with 168 WP-
classes were given the Type number (such as filled steel pellets. PA chges were in tail cone
Type 97) which disclosed the year that the and central burster (pp 63–4);
bomb was adopted for service use. In the “land” Type 3 No 6 Mk 3 Model 1 Bomb contd three
and “ordinary” classes, the 1st bomb of a given cylindrical steel canisters, each contg 87 WP-
wt class was not assigned a Type number but filled cylindrical steel pellets; each canister had
was merely indicated by the wt number. Sub- central exploder filled with Type 98 Expl (pp
~equent designs of the same wt were assigned 64–6);
Type numbers. Thus there was a No 6 land Type 2 No 25 Mk 3 Model 1 Bomb contd an
bomb and a Type 97 No 6 bomb. The No in- incendiary chge consisting of Ba nitrate 35.8,
dicated the wt in units of tens of kg. Thus a Al 13.6, Mg 10.3, Fe oxide & synthetic rubber
No 6 bomb weighed 60-kg, a No 25 weighed shavings 13. 1%; two igniter chges (Ba nitrate
250-kg, etc. For “specird” bomb the Mk num- 75.2, Al 24.2 & oil 2%) were located in the nose
ber was given. The term Model usually meant piece and in the tail cone (pp 66–7);
a different design of the bomb in the same Type 3 No 25 Mk 4 Modification 1 Bomb was
general class, while Modification meant a minor of AP design and contd a small chge of Type ‘
change in the design or filling 91 Expl used in all Navy AP ammunition (pp
Type 97 No 6 Land Bomb had a sheet steel 68–9);
body filled with PA or Type 98 Explosive (p 45); Type 99 No 80 Mk 5 Bomb was of forged steel
Type 2 No 6 Land Bomb had sheet steel body and contd a large chge of Type 91 Expl (pp
filled with five 7-kg HE bombs and contd 69–70)
central burster tube filled with HE (PP 46–7); Type 2 No 8 Mk 5 and No 150 Mk 5 Bombs
No 25 Land Bomb and Type 96 No 25 Land were of AP design and used small chges of
Bomb had steel body filled with PA or Type Type 91 Expl (pp 70– 1);
98 Expl (pp 47–9); Type 98 No 7 Mk 6 Model 1 Bomb contd four
No 80 Land Bomb had steel body filled with Thermite-filled electron f~e pots. A central
PA or Type 98 Expl (p 49); channel filled with quick match ran thru the
Type 99 No 6 Ordinary Bomb had steel body length of the bomb. A BkPdr chge was located
filled with PA or Type 98 Expl (p 50); in the circular recess of the nose piece (pp 71–72);
Type 99 No 25, also No 80, OrdinaW Bombs Type 98 No 7 Mk Model 2 Bomb contd a
Model 1 were ftied with Type 91 Expl (pp central Thermite core surrounded by a solidified
50–1 & 53); kerosene, petrol, alcohol, soap mixture. A BkPdr
Type 2 No 50 Ordinary Bomb Model 1 was . burster chge was located in the nose. A copper
ffled with Type 98 Expl (p 52); tube contg quickmatch was located inside
No 3, No 6 & No 25 Ordinary Bombs Model 2, Thermite tube (pp 73–4);
were filled with PA (pp 54–5); Type 1 No 7 Mk 6 Model 3 Modification Bomb
No 50 Ordinary Bomb Model 2 was filled with consisted of a sheet steel cylindrical body contg
Type 98 Expl (p 56); 182 cylindrical pellets arranged around a central
No6Mkl, Type 1 No6Mkl and Type4 cardboard tube contg gray igniter mixture (Ba
No 6 Mk 1 Bombs were filled with mustard nitrate 75, Al 24.5, oil 0.3 & moisture 0.2%).
gas thickened with methacrylate & polyvinyl The pellets (which contd Ba nitrate 35, ferric
alcohol (pp 56–7); oxide 28, Al 18 & synthetic rubber shavings
 J 17

9%) were bound with a string to form rings Brown Powder – Kasshokuyaku (Undercarbonized
(pp 74-5); Black Powder). Known only from documents
Type 3 No 25 Mk 8 Model 1 Bomb was of sheet but was never recovered by US investigators.
steel contg Type 97 Expl (pp 76–7); Use unknown (Ref 1, p 30)
Type 2 No 6 Mk 21 Model 1 Bomb contd BkPdr
igniter and 40 one-kg HE(?) hollow chge bombs, Brown Powder (Navy). This name was assigned
arranged vertically in two rows (pp 77–8); in Ref 1, p 32 to the mixture: Amm chlorate
l-kg Hollow Charge Bomb’ contd Type 98 Expl 51.5, Ba nitrate 34.5, TNN (Trinitronaphthalene) &
and Tetryl booster (PP 79–80); oil 8.2 & wood pulp 5.OfZO.Substance dangerous
Type 2 No 6 Mk 21 Model 2 Bomb contd 36 to burn in large quantity. It was found as a
one-kg HE(?) bombs arranged vertically in booster in preparing bombs for demolition
three rows (pp 80–1);
l-kg Antipersonnel Bomb contd Type 97 Expl Buki. Arm, Weapon
(pp 82-3);
Type 3 No 6 Mk 23 Model 1 Bomb was of sheet Bullet. Dangan
steel contg PA or Type 98 Expl (pp 83–4);
Type 4 No 25 Mk 29 Bomb was cylindrical in Bunri yakuto Separate-loading Ammunition
shape with a central burster chge of HE(?) sur-
rounded by WP incendiary shrapnel (pp 87–8); Burst. Haretsu
Type 5 No 25 Mk 33 Bomb was designed to
detonate upon approach to the earth. It contd Burster. Sakuyaku’
the “all-ways action electrical nose fuze” and
“atmospheric tail fuze”. The bomb contd Bursting Charge. Sakuyaku
HE(?) chge surrounded by steel pellets (pp
92–3); Buryoku. Military Force
Practice Bombs – three types are described on
pp 93–7 Caliber. Kokei
2-kg Window Bomb consisted of sheet metal
cylinder filled with 250 paper strips coated on Cannon. Taiho, Kaho, Kanoho
one side by metal foil which were placed around
an inner vertical tube contg the delay element Cap (explosive). Bakkan
and smokeless pdr ejection chge. Empty space
betw the strips was filled with iron pyrites. Carbine. Kiju
The bomb was thrown by hand from the
plane’s window (pp 115–16), Carlit. Accdg to a Pamphlet of “The Japan
A less detailed description of bombs is given Carlit Co, Ltd”, located before WWII at Chiyoda-
in Ref 1, pp 66–80 (Army) and 90–109 (Navy) ku, Tokyo, Carlit was invented in 1917 by O.
Refs for Bombs: 1) OPNAV 30-3M (1945) Carlson and,’manufd in Japan since 1919. It
2) TM 9-1985-4 (1953) was an Amm Perchlorate expl contg ferrosilicon
& woodmeal. It was used in the same way and
Bomb Fuzes. See under FUZES for the same purposes as Dynamites. Properties
of Carlit are described in the Pamphlet
Booby Traps Yugekiteki jirai). See under Mines In Vol 2 of Encycl, p C68 is described a
(Land) and Booby Traps Japanese Army expl Cirrlit or Karitto consisting
of Amm Perchlorate 66, Si carbide 16, woodpulp
Booster Charge (Denkabakuyaku). See under 12 & petroleum 6%. The same compn was
Gaine given for Kantto in OPNAV 30-3M (1945), p
29, listed here as Ref 1. Its Navy name was
Breech. Hobi Type 88 Explosive (qv) (See also under Karitto)

Breechloader. Kosoho Carriage (Arty). HGga

 J 18

Cartridge (Fixed Ammo). Danyakuh6 Chauyaku. A castable mixture of RDX (Cyclo-

nite) 50 & TNT 5~0, corresponding to Amer
Cartridge Bag. Yakun6 Cyclotol. Used for loading some Artillery Pro-
jectiles. Other RDX/TNT mixtures are listed
Cartridge Case. YakkyCi under Nigotanoyaku Mk 2 (Ref 5, p 364)

Cast (Expl Filling). Chiiten (bakuhatsu) Chikkaen (Army) or Chikka namari (Navy).
Lead Azide (LA), Pb(N ~)z, creamy white to
Cast Iron HE Projectile. Chutetsu ryiidan buff or very light gray pdr; detonates w/o
melting at ca 350°; decompd by acetate soln.
Cavity (in Projectile). Shink6 Most common initiator for detonators and fuzes,
especially where a BkPdr relay is present (Ref
Chakatsuyaku. 2,4,6-Trinitrotoluene (TNT), also 1, p 25&Ref 5, p 364)
called Sansh6ki toru6ru or Type 92 Explosive
(Navy), H3C.C6H2(N02)3; lt yel to buff expl, Chitai suru. Delay
d (tryst) 1.65, mp 80.6°; Brisance by Sand Test -
48.Og sand crushed; Expln Temp – decomp at Chujo kayaku. Cordite
475° in 5 sees; Impact Sensitivity, Bur Mines,
2kg wt 100cm+; PicArsn App 14– 15 inches; Chukei. Relay
Power – 100% TNT, Rate of Deton 6900m/s
at d 1.6. Used by the Japanese Navy straight Chuku no. Hollow
in some 25 & 40mm Shells, while the Army
used it in Grenades, Mines, Demolition Charges Chutai kikan. Recoil Mechanism
and a few Bombs
Also used in the following composite explo- Chiitai stichi. Recoil-operated
sives: A(ko), Chanayhku, Chaoyaku, Chauyaku,
Nigotanoyaku Mk 2, Otsu-B or Type A, Pento- Coal. Sekitan
riru, Seigata (Army) or Type 97H (Navy),
Shoanyaku, Shi5toyaku, Tanoyaku, Type Coast Artillery (Weapons). Kaiganh6
92, Type 97H and others (Ref 1, p 26; Ref 5,
p 363 & Ref 8, p 350) Combat. Sent6
-—.
Chakuhatsudan. Percussion Shell Combat Ammunition. Shokorl danyaku

Chakuhatsu ryusandan. Percussion Shrapnel Combat Vehicles (Sent6 jidosha) and Their
Weapons (Heiki). In the book of Tantum &
Chakuhatsu shinkan. Percussion Fuze, Impact’ Hoffschmidt (Ref 7, Section 4, pp 117–1 35)
Fuze are described and illustrated the following
items:
Chanayaku. A yel castable composite expl con- Tankette, Mod 2592 (1932) (pp 116–17)
sisting of TNT 70 & DNN (Dinitronaphthalene) Tankette, Mod 2594 (1934) (p 118)
30%. Used for loading some Army Artillery Tankette, Mod 2597 (1937) (p 119)
Projs (Ref 1, p 26 & Ref 5, p 364) Light Tank, Mod 2593 (1933) (p 120)
Light Tank, Mod 2595 (1935) (p 121)
Chaoyaku. A lt-yel mixture of PA (Picric Acid) Medium Tank, Mod 2589A (1929) (p 122)
75 & TNT 25%, which melts below 120° and Medium Tank, Mod 2589B (1929) (p 123)
explodes at below 350°; brisance and detonation Medium Tank, Mod 2594 (1934) (pp 124–25)
velocity are lower than those for PA and it is Medium Tank, Mod 2597 (1937) (Special) (p 126)
less sensitive. Press40aded (or rarely cast) in Medium Tank, Mod 2597 (1937) (p 127)
some Army Bombs (Ref 1, p 26 & Ref 5, p 364) Amphibious Tank (p 128)
 J 19

150-mm Self-Propelled Howitzer (p 129) cellulose) contg - Gelatin Dynamites (See

47-nim Tank Gun, Type 1 (1941) (p 130) Geogel). “Faint Smoke” Gelatin Dynamite
5.7-cm Tank Gun, Mod 97 (p 131) contd borax or salt. Nonfreezing Dynamites
Armored Car (Vickers-Crossley, M-25) (p 132) contd NGc (Nitroglycol) or Dinitroglycerol.
Armored Car, Mod 2592 (1932), Naval Type (p 133) Ammonium Nitrate Dynamites contd AN (such
Armored Car, Mod 2592 (1932), “Osaka” (p 134) as Akatsuki). There is also Semigelatine Dyna-
Armored Car, Mod 2593 (1933), “Sumida” (p 135) mite, such as Enoki No 2 Dynamite (Ref 1, p
Nofe: There are also listed: motorcycle, motor- 29). See paper of K. Sassa& I. Ito in Ki5gyo-
tricycle, scout car, locomotive truck, several KayakuKy5kaishi 32, No 6 (Nov–Dec 1971)
trucks, several prime movers, armored car re- translated by Mrs Geti Saad at the BurMines
covery vehicle and two tractors (pp 136–54) in 1972
(See also under Additional References at the
Combat Weapons are described in the book of end of this Section)
W.H. Tantum IV & E.J. Hoffschmidt, Editors,
entitled: “Second World War COMBAT VE- Danchaku. Impact (of Projectile)
HICLES Japanese”, Published by WE Inc, Old
Greenwich, Connecticut, Vol 2 (1968), listed as Dandio. Trajectory
Ref 7 at the end of this Section. Included
among others are: Dandogaku. Ballistics
hrfiarztry: Small Arms Weapons, Pistols, Rifles
and Machine Guns (pp 39–78) Dangan. Projectile, Shell, Bullet
Artillery: Antitank, Antiaircraft, Light and
Heavy Field Guns (pp 79–1 15a) Dantai. Body (of Projectile or Bomb)
Combat Vehicles: Tanks, Self-Propelled Guns,
etc (pp 116–54) Dantei. Base of Projectile
Miscellaneous Weapons: Rockets, Mortars,
Mines, Grenades, Telescopes and Ammunition Dantei shinkan. Base Fuze; Tail Fuze
(pp 155-92)
Dantio. Nose of Projectile or Bomb; Point of
Combination Fuze. Fukudo shinkan Projectile

Combustion. Nensh6 Danto bakkan. Point Detonating Fuze

.
Combustion Chamber. Nensh6shitsu Danyaku. Ammunition

Complete Round. DanyakutG (Fixed Ammo) Danyakuto. Cartridge; Complete Round

component. K6seibunshi Danyoku. Fin of Bomb

Cordite. ChiijG kayaku Denkayaku. Booster Charge. See under

Gaine
Cyclonite or RDX. Shouyaku

Denki bakkan. Electric Primer

Cyclotol (50/50–mx/TNT). Chauyaku

Dagger. Tanken Denki raikan. Electric Cap

Dainamaito. Dynamite Denki tenkagu. Electric Blasting Machine; Exploder

NG (Nitroglycerol) contg composite expls from
buff to brown color. Accdg to documents there Deflagration. Totsunen; Bakunen
were diatomaceous earth contg, NC (Nitro- ‘
 J

J 20

Delay. Chitai sum filled with cast, wrapped PA; and 30-kg Can
contd’30kg of PA charges, rounded or square
Delayed-Action Bomb. Chid6 bakudan c) Substitute Army Demolifl”on Explosives. The
following are listed in Ref 1: Entoyaku (qv)
Delayed-Action Fuze; Delay Fuze. Chidi5 shinkan (p 28), Ennayaku (qv) (p 28), Dainamaito (qv)
(p 29), Shoanbakuyaku (qv) (p 29), Karito (qv)
(p 29) and Ammonyaku (qv) (p 29)
Delayed-Action Mine. Chidli jirai E. Demolition Clocks. The following types are
described and illustrated in Ref 2, pp 252–55:
DEMOLITION CHARGES (Hakaiyaku) and a) Twenty-Four Hour Demolition Clock (p
EQUIPMENT (Sogu) 253; Fig 191, upper)
Following information is given in Ref 1, pp b) Type 99 Long-Delay Demolition Clock (p
28–29 & 233–36 and in Ref 2, pp 30 & 252–55 253; Fig 191, lower)
Japanese equipment consisted of: c) Seven and One-Half Day Demolition Clock
A. Safety Fuses and Safety Fuse Igniters. (p 255, no Fig)
Several types of fuses with rate of burning of d) Type 92 Seven-Day Demolition Clock (p
30, 32 and 45 seconds per foot were used (p 255; Fig 192)
234). The Igniters were: Trigger Type (Fig F. Demolition Block, shown in Fig 211, p 159
381 on p 233); Pull Type (Fig 382 on p 234) of Ref 1, consisted of a cast-iron cylinder
and Type 99 Demolition Tube Igniter (p 233) (4%x6 inches or 4%x4% inches) contg blocks
B. Blasting Caps. Three types of non-electric of PA. The body was mounted on a stick 21
and four types of, electric caps were known (p inches long. When the device was fired from
234) an Army Mortar, two Pull Igniters in the charge
C, Detonating Cord, Type 97, described on p ignited a delay train of 7 seconds
234, contd a core of PETN (Shoeiyaku), sur-
rounded by cotton, hemp and waterproof layers. DEMOLITION TUBES. Under this title are de-
Diameter 1/4 inch and Detonation Velocity scribed in Ref 1, pp 236-37 several demoli-
6000m/sec tion items in the form of tubes, such as:
D. Demolition Explosives consisted of the fol- a) llarrgakve Torpedo. The model described
lowing: in Ref 1, p 236 looks different from Model
a) Plastic Explosive Koshitsu (qv) (Army) con- 99 (1939) described in Ref 2, pp 21 5–16 and
sisted of RDX (Shouyaku) 80 & vegetable oil in Ref 7, p 186. This torpedo consisted of a
20%, made into rolls 4 inches long, weighing steel tube with shoulders welded to both ends.
4 oz each. Issued for field use in three rolls One end was internally threaded to take the
packed in a paper package (Ref 1, pp 28 & 234) igniter locking collar while the other end was
b) Prepared Charges. Three main (standard) threaded externally to take the pointed nose
Army demolition bIocks, 2x2x1-inch size were cover. The igniter system consisted of two pull
used: 1) PA (Shimose bakuyaku); 2) Haishoku- igniters screwed into an igniter holder which
yaku (qv) and 3) Nigotangyaku (Tanoyaku) fitted into the igniter locking collar. The rings
(5(1/50-TNT/RDX) (pp 28–30 & 234 of Ref 1 of the igniters were connected by lines to the
and p 230 of Ref 2); 4) Combined Demolition lanyard holder. The igniters were simple match
Blocks – two, three or four TNT and PA compn pull igniters, friction type, with a BkPdr
blocks were provided with a hole to receive the delay. of 8 seconds, an initiant, and a base chge
detonator (p 235 of Ref 1); 5) Demolition of Tetryl. Each torpedo unit had outside dia-
Cans were rectangular made of zinc. Three meter of 1-13/32 inches, total length 51 feet,
sizes are described in Ref 1, p 234: 1-kg Can weight 10 lbs, filled with 3 lbs of 36.4/63.6–
was filled with cast, wrapped PA; 5-kg Can was TNT/RDX as Bursting Charge. To prepare the
 J 21

torpedo for use, the storage caps were removed Depth Bomb; Depth Charge (Bakurai). Accdg to
from the required number of tubes and were Ref 1, p 61, the depth chges of Japanses Navy,
screwed end for end together. Then the pointed like its mines but urdike its torpedoes, are ob-,
nose cover was screwed onto one end, while at solete in design
the other end the igniter locking collar was The following types were used during WWII:
screwed into it. After placing the torpedo on Type 88 Depth Charge was a metallic barrel
the ground or barbed wires, etc, the safety pin 30.5 inches long and 17.7 inches in diam. This
of igniter was removed and the firing lanyard size was standard for all known depth charges.
pulled sharply (See Fig 162, p 216 of Ref 2 It was filled with 327 lbs of cast PA (Shimose).
and description and Fig on p 186 of Ref 7) It had “filling end” and “pist~l end”. The
The bangalores were used primarily for de- hydrostatic pistol was operated by water pressure
struction of wire entanglements, but also to clear and could be set to fire at depths of 82 or 148
passagesthru mine fields and destroy railroad ft by varying the opposing spring pressure (p
tracks. They may be rigged as booby traps 62 of Ref 1);
(Compare with US Models described in Vol. 2 Type 91 Model 1 Modification 1 Depth Charge
of Encycl, pp B 16–B 17) was similar to above and contd 220 lbs of Type
b) Bamboo Tube, filled with explosive and fitted 88 (qv) Expl. Operated at depths of 82 or 164
with a pull igniter is shown in Fig 386 on p ft of water (p 62);
237 of Ref 1 Type 95 Depth Charge (Fig 33) was the regular
c) Finned Bangalore Tube, shown in Fig 387, issue charge until the appearance of the Type 2.
p 237 of Ref 1 and in Fig 299, p 376 of Ref 2, It contd 220 lbs of Type 88 Expl. Slow ships
was similar to a regular Bangalore, except that it dropped the chge to slow down its rate of descent
was made of two pieces with fins attached to so that the ship could escape the danger area be-
the after-body. This section was made to fit fore the chge exploded. The hydrostatic pistol
into the barrel of the Type 98 Projectile Dis- (Fig 34 on p 62) could be set for a depth of
charger. A combination Instantaneous-Short 98 ft with parachute or 197 ft w/o one;
Delay Nose Fuze was fitted into the tube. Type 95 Mod 1 contd 325 lbs of Type 97 or
Diameter of tube 1-15/16 & length 78-3/8 98 Expl (p 62);
inches; total weight 17 lbs, 14 oz Type 2 Depth Charge (Fig 35 on p 63) was
d) Type 99 Demolition Tube was 44 inches long loaded with 240 lbs of Type 1 Expl. This
depth chge and its hydrostatic pistol (Fig 36 on
and weighed 35kg. The fuze was actuated by
p 63) were almost direct copies of British
a pull cord and had 7 seconds delay (Ref 1, p
models. The pistol could be set for depths of
237) “
98, 197, 292, 390 and 480 feet (pp 62–3);
e) Obstacle Demolition Tube was over 35 feet Type 2 Mod 1 Depth Charge contd 357 lbs of
long and weighed 102kg. Its construction was Type 98 Expl ‘or Type 97 as an alternate filling
similar to those above but, the fuze was actuated (p 63);
by electrical means (Ref 1, p 237) Type 2 Mod 2 Depth Charge was filled with
either Type 1 or 4 Expl (p 63);
Denkayaku. Booster Charge. See under CAINE 50 Kilogram Army Depth Charge (Fig 37 on
p 64) was 20 inches long, 13 inches in diameter
Denki bakkan. Electric primer and carried a chge of approx 75 lbs of TNT,
The firing mechanism (instead of hydrostatic
Denki tengaku. Electric Blasting Machine; Exploder
pistol) was housed in a well at one end of the
case. It was probably used on “suicide boats” (qV);
Type 3 120 Kilogram Army Depth Charge
Density. Mitsudo
(Experimental) was 24% inches long and 15%
inches in diameter; filled with 200 lbs of HE
Density of Loading. s~ten hiju (no data). It was fired by a pull igniter instead
 ,

J 22

of a hydrostatic pistol. The charge (Fig 38 on Dummy Projectile. Giseidan

p 63 of Ref 1) was rigged on Army “suicide
crash boats”. The charge, was also used as a Duralumin. Jurarumin
Mine and could be f~ed electrically “by means of
Demolition Charges planted beside it (Ref 1, Dynamite. Dainamaito (qv)
p 223)
“E” (Explosive). A light-yellow castable expl
Destruction. Hakai mixture of Trinitroanisole 60 & AN 40%; cast
density 1.60; Power by Ballistic Mortar 108%
Detonating Cap. Raikan (PA=1OO%). No info about its uses (Ref 5,
p 364)
Detonating Charge; Detonating Explosive.
Kibakusai Eikadan. Time Shell

Detonating Cord. Dtibakusaku Eika shinkan. Time Fuze

Detonating Fuze. Shinkan; Bakkan Eikodan. Tracer Bullet

Detonation. Kibaku; Bakuhatsu Eiko danyaku. Tracer Ammunition

Detonator. Kibakuyaku Ekka. Liquid Fire

Device. Dogu Sochi, Shikake Electric Current. Denryu

Dobakusaku Detonating Cord Electric Firing Device Type 3 for Proximity

Fuzing is described in Ref 2, pp
of Bombs
Dokaraikan. Nonelectric Cap 188–89 with Fig 137

Dokasaku. Safety Fuse; Powder Train Electric Primer. Denki bakkan

Dokasen. Explosive Train; Powder Train Electric Wire. Densen

Dokuen. Poisonous Smoke Electron. Denshi

Dokugasu. Poisonous Gas Electron Bomb. Elekutoron sh6idan .”

Double-Base Propellant. See Nitoroguriserin Emmaku. Smoke Screen

muenyaku under PROPELLANTS
Emmaku hoshaki. Smoke Projector
Drill Ammunition. Giseidan
Enka. Signal Rocket
Drill Bomb. Gibakudan
Enkapikurin. CMoropicrin
Drop Test. Rakka shiken
Enka shingo. Pyrotechnic Signal
Dud. Fuhatsudan
Ennayaku. A light-yellow expl mixture of K
Dumdum Bullet. Damudamu dan chlorate 80, MNT (Mononitrotoluene) 15 &
castor oil 5%; extremely sensitive to mechanical
Dummy Ammunition. Renshiiyi5 danyaku action. It was used by the Army, as Substitute
 J 23

Demolition Charge and as Substitute Main Finnad Bangalore Torpedo. See under DEMO-
Charge for Hand Grenades and Mortars (Ref 1, LITION TUBES
p, 28 & Ref 5, p 364)
Fireworks. Enka
Enoki Dynamite No 2. See under Dainamaito
Firing (Discharge of a Firearm). Hassha
Enshuyo bakudan. Practice Bomb
Firing Devices. See under Igniters or Firing Devices
Enshuyo dangan. Practice Shell
Firing Pin (Striker). Gekishin
Enshuyo jirai. Practice Land Mine
Firing Pin of Fuze. Kakki
Enshuyo kirai. Practice Sea Mine
Fixed Ammunition or Fixed Round. Kanzen
Enshuyo tekidan. Practice Grenade yakuto

Entai. Trench; Shelter Fixed Gun. Koteiju

Entoyaku. A light-yellow expl mixture of K FLARES (Shomei) and Flare Bombs (Shomeidan)
chlorate 80, DNT (Dinitrotoluene) 16 & castor The following Japanese Army Flares (ex-
oil 4%; used for the same items as Ennayaku cluding Parachute Types) are described in Ref
(Ref 1, p 28) 1, pp 238–43 :
Flares for 50-mm Type IOth Year Flare Dis-
Equipment. Sogu charger (p 238 + Fig 388 on p 239) had heavy
cardboard cylindrical bodies, 6-1/8 inches long,
Erosion (of Gun Barrel). Fushoku ffled with various color flare compositions. A
proplnt container was attached at the base;
Exploder. Bakuhaki 50-mm 10th Year Type “A” Flare (p 238 &
Fig 389 on p 239) was a heavy cardboard
Explosion. Haretsu; Bakuhatsu cylinder 6% inches long, which contd a filling
of an incendiary type which burned with an
Explosive. Bakukatsubutsu; Bakuyaku. See intense white flame. It was fired from the Type
under individual name: Akatsuki, Angayaku, 89 Grenade Discharger. A cylindrical proplnt
Chakatsuyaku, etc and under “Unknown Name container was attached at the base;
Explosives” 81-mm Mortar Signal Flare. Its Green Type
was a light iron cylindrical case 3 inches in
Explosive Bullet. Bakuretsu shojudan diam & 7-3/8 inches long loaded with green
flare compn. Attached to the base was a pro-
Explosive Coal, Food Can and Toothpaste. See plnt container (p 239);
under Sabotage Devices 8 l-mm Mortar Parachute Smoke Flare was similar
to above but contd smoke producing compn
Explosive Train (in Fuze). Do~sen (p 239);
Flare Signal Cartridges were cardboard cylinders
Exterior Ballistcs. ‘l@ai dand~gaku 3?4”XI / 16“ filled with green, red or white flame
producing compns. They were fired from the
Factory. K6jG Type 97 Very Pistol (p 239);
Flare Signal Rocket Mk 1 Flare consisted of
Field Gun; Field Piece. Yasenho cardboard cylinder attached to a stick, to the
end of which was f~ed a 6% ft length of rope.
Filler. Sakuyaku A pull tape at the base of the rocket case
 J 24

covered a length of fuse which was lit to fire Illuminating Flare Bomb was of thin iron, conical
the rocket (p 240); in shape with a hemispherical nose welded at
Type 93 4-cm Signal Flare was in two types: the bottom. Length 22% inches, diam at top
a) Trailing White Stars and b) Green Comet. 6% inches. Its fdler was ignited by a pull
They are described on p 240 and illustrated in igniter, resulting in a brilliant greenish-yellow
Fig 391; light (p 241, Fig 394 of Ref 1);
Safety Fuse Flare, 3?4 inches long and l% Type 96 Floating Landing Flare was a sheet
inches in diam, was housed in a cylindrical paper metal flare bomb with four sheet metal fins
container closed at the base with a wooden plug and a brass nose. Total length 16% inches,
to which a short length of safety fuse was diam 5 inches. Its flare mixt filler was ignited
attached. Above the plug were small expelling by a pull igniter, When dropped form an air-
& ignition chges which blew the flare and its plane it floated in water while producing an
red paper parachute out of the container. The extremely bright light to signal landing spots
flare burned for 23 seconds. It could be fired during the night ( p 241, Fig 395 of Ref 1 and
from the 30-mm Rifle Grenade Discharger (p p 98 of Ref 2 with Fig 74);
240 & Fig 392) Navy Ground Signal Flares were cylindrical
The following Japanese Army Parachute cardboard containers 3% inches long 1% inches
Flares are described in Ref 1, pp 250–51 and in diam, ffled with red, white or green compns.
in Ref 2, pp 22–5 with Figs 18, 19 & 20: Used to signal aircraft from the ground (p 242,
Type 90 Small Model Parachute Flare was a Fig 396 of Ref 1);
sheet-steel cylinder (with conical nose) 26% Type 94 Float Flare, called in Ref 2, p 107
inches long & 2-7/8 inches in diam contg 4 Type 94 Float Light, was tinplate cylinder, 12
lbs of an Illuminating Compn of Ba chlorate inches long & 2% inches in diam, with a hemi-
75.2 & gum 24.8% and a BkPdr ignition” chge. spherical nose. A lead in the nose and a buoy-
The flare burned for 2-2/3 minutes with an ancy chamber at the base section kept the flare
intense greenish-white flame. A detailed de- straight in the water. The body had water
scription is given on pp 22–3 with Fig 18; inlet holes in the nose and the side seated by
Type 1 12-kg Parachute Flare was a sheet steel tear-off strip and a removable end cap. Before
cylindrical (with conical nose) case 37 inches dropping from a plane, the tear-strip and end
long & 4-3/16 inches in diam filled with 15 cap were removed to allow the water, after
lbs of an ilhrminant which was ignited by BkPdr impact, to enter thru the nose inlet holes, thus ‘
chge. Compn of illuminant was as indicated wetting Ca carbide in the forward end. This
under Illuminants in the text. The Illuminant generated acetylene gas. Simultaneously, water
burned for 1?4 to 3 reins with a greenish-white entered thru the side inlet hole to wet Ca “’
flame. A detailed description is given on pp phosphide gas in the after end of the flare,
24–5 with Fig 19; thus generating phosphine. When acetylene
Type 3 Parachute Flare was a sheet steel cylin- passed thru the tail opening, it was ignited by
drical (with rounded nose) case 42% inches long the phosphine which spontaneously inflames on
& 6% inches in diam filled with 15 lbs of 11- contact with the air ( p 242, Fig 397 of Ref 1
‘luminant, such as described in the text under and with more detailed illustrations on p 106
I’s and a BkPdr Igniter. A detailed description of Ref 2);
is given on pp 25–6 with Fig 20 Type 94 Mod 1 Float Flare was a larger flare
The following Japanese Navy Flares (ex- than Type 94. Length 20% inches & diam 4%
cluding Parachute Types) are described in Ref inches (p 243, Fig “398 of Ref 1);
1, pp 241–43 and some of them in Ref 2, pp Type 94 Mod 2 Float Flare was a smaller version
98–100 and 106–08: of Type 94. Length 9% inches & diam 2-3/8
Navy Hand Signal Flare was cardboard tube’ 12% inches (p 243, Fig 399 of Ref 1 and in Ref 2,
inches long fried with a flare mixture and fwed pp 108–09, Fig 81);
on a wood handle. The flare was ignited by a Type O Model 1 Float Flare was similar in
pull igniter wire ‘which extended down the tube construction and operation to Type 94. Length
(p 241, Fig 393 of Ref 1); 13?4inches & diam 2-7/8 inches (p 243, Fig
 J 25

400 of Ref 1 and in Ref 2, pp 108–09, Fig 81); burned with bright white light during 4-2/3
Type 94 Experimental Float Light, described in reins (Ref 1, pp 253–54, Figs 427 & 428). De-
Ref 2, p 107 and illustrated in Fig 80 of p 106, tailed description is on pp 105 & 107, with
consisted of tin plate cylinder 21% inches long Fig 79 in Ref 2;
and 4% inches in diam. It contd Ca carbide & Type 94 Float Light is described as Type 94
Ca phosphite. Its operation was exactly the Float Flare in Ref 1, p 242 and also in this
same as the Type 94 Float Flare described above; Section, under FLARES
Navy Flare Ball was a large cardboard sphere 9
inches in diam with a dome top covering a Floating Flare (Fuhy6 shiiimei). See under
paper-covered BkPdr Fuse and a dome bottom FLARES
contg BkPdr chge in a celluloid cap. The main
container carried a cluster of 12 flares attached Float Lights, Type 94, Type 94 Experimentrd,
to a large green tissue parachute. The flare Type 94 Model 2 and Type O Model 1, de-
cluster was bedded in a quantity of cottonseed scribed in Ref 2 on pp 107–09 with Figs 80
which fflled most of the lower half of the sphere. & 81 as Float Lights are described here as
A pull wire permitted removal of the top dome “Float Flares” under FLARES
and allowed access to the BkPdr fuse for ig
nition (Ref 1, p 247, Fig 409) Floating Mine (Fuhy6 suirai). See under
The following Japanese Navy Parachute MINE, SEA
Flares are described in Ref 1, pp 25 1–54 and
Ref 2, pp 100–05 with Figs 76, 77, 78 & 79: Floating Smoke Items. See under “Smoke
5-Kilogram Parachute Flare Model 2 Modification Floats”
1 consisted of a light sheet steel ~ylindrical
body 25-1/8 inches long & 3-1/8 inches in diam, Fosugen. Phosgene
contg 5% lbs of Illuminant (qv under I’s), a Pull
Igniter and a Parachute. The unit burned for Fragmentation Bomb (Sairetsu tbka bakudan).
1?4reins giving brilliant white light. Detailed See-under BOMB
description is on pp 100–01 with Fig 76 in
Ref 2; Fragmentation Grenade (Sairetsu teryiidan).
Type O Parachute Flares Model 1 and Model 1 See under GRENADE
Modification 1, each consisted of sheet steel
cylinders 421%inches long & 6?4 inches in diam, Frangible Grenade. Kaembin
contg 66 lbs of Illuminant, a Fuze and a Para-
chute. They burned for 3-2/3 reins with a Friction Primer. Monkan
bright white light (Ref 1, p 252, Figs421 & 422).
Detailed description is on pp 102–03 with Fig Fuel Oil. Nenry@nr
77 in Ref 2;
Type O Parachute Flares Model 2 and Model 3, Fuhatsudan. Dud
Modification 1 consisted of sheet steel cylindri-
cal bodies 35% & 391%inches long and 6% inches Fuhatsu suru. Misfire
in diam each. Each contd 66 lbs of Illuminant,
a Fuze and a Parachute. The flares shed a Furytu suirai. Drifting Mine
bright white light during 3-2/3 seconds (Ref 1,
p 253, Figs 425 & 426). Detailed description Fuse (Kay5hen or Fytizo). See under Demolition
is on pp 103–04 with Fig 78 k Ref 2; Equipment
Experimental Model 11 Parachute Flares consisted
of sheet steel cylindrical bodies 431%inches long Fuse, Safety. D6kasaku
& 9% inches in diam, provided with fins. One
of the models had conicrd nose while the other Fusetsu kirai. Anchored Mine
had ogival nose. Each unit contd 68 lbs of
Illuminant, a Fuze and a Parachute. The flare Fusetsu suirai. Submarine Mine. See MINE, SEA
 J 26

FUZES (Shinkan) Type 3 Nose Initiator A-3(e) (pp 162–63)

Japanese Fuzes are divided into Bomb Fuzes Type 2 No 50 Ordinary Bomb Model 1 Fuze
and Projectile Fuzes which, in turn, are sub- A-3(f) (pp 163–64)
divided into Army and Navy Fuzes A-3(g) Bomb Fuze (pp 165–66)
A. Bomb Fuzes are described in OPNAV 30-3M A-5(a) Nose Fuze (pp 166–67)
(1945), listed here as Ref 1, pp 80–88 (Army Type 99 No 25 Ordinary Bomb Fuze B-2(a)
Bomb Fuzes) and pp 110–21 (Navy Bomb Fuzes). (pp 168-69)
More complete description is given in TM 9-1985-4 Type 99 No 80 Mk 5 Bomb Fuze B-2(b) (pp
(1953), listed here as Ref 3, pp 123–54 (Army 169–70)
Bomb Fuzes) and pp 155–87 (Navy Bomb Fuzes) Type 15 Tail Fuzes Model 2 & Model 1 B-3(a)
Individual fuzes of each service are generally & B-3(b) (pp 170–72)
int exchangeable for use in bombs of that service, B-5(b) and B-5(c) Tail Fuzes (pp 172–75)
but not interchangeable for use in ordnance of Type 97 Rail Initiator B-6(a) (p 176)
the other service B-9(a) and B-1O(a) Tail Fuzes (pp 177-79)
The following Army Bomb Fuzes are listed Type 99 Special Bomb Tail Fuze C-l(a) (pp
in Ref 2 on pages indicated below: 179–80)
Type 93 Instantaneous–Short Delay A-2(a) (PP Type 99 Special Bomb Nose Fuze C-2(a) (pp
123–24) 181-82)
Type 12-Year Instantaneous A-2(b) (PP 124–25) D-2(a), D-2(b) and D-2(c) Aerial Burst Tail
Type 99 Instantaneous–Short Delay A-2(c) (PP Fuzes (pp 182–85)
126–27) D-3(a) Aerial Burst Nose Fuze (pp 186–87)
Type 1 Instantaneous A-2(d) (pp 127–28) Fuze for Type O Parachute Flare, Model 1
Type 92 Nose Fuze A-4(a) (p 129) D-4(a) (pp 187–88)
Fuzes for Type 3 Bomb A-6(a) and A-6(b) (PP Type 3 Electric Firing Device for Proximity
129–32) Fuzing of Bombs (pp 188–89)
Fuze for Type 2 Bomb A-7(a) (PP 132–33) B. Projectile Fuzes are described in OPNAV
Type 4 Two-Second Delay Fuzes A-8(a) & A-8(b) 30-3M (1945), listed here as Ref 1, pp 166–69
(pp 134-36) (Army Projectile Fuzes) and pp 191–94 (Navy
Type 12-Year Tail Fuze B-l(a) (pp 137–38) Projectile Fuzes). More complete description is
Type 1 15-Second Delay Fuze B-l(b) (PP 138–39) given in TM 9-1985-5 (1953), listed here as
Type 92 Tail Fuze B-4(a) (p 140) Ref 3, pp 391–426 (Army Projectile Fuzes)
B4(a) Tail Fuze (p 141) and pp 5 18–43 (Navy Projectile Fuzes)
Experimental 3.5-Second Delay Fuze B-7(a) The following Arm y Projectile Fuzes are
(pp 141-43) listed in Ref 3 on pp indicated below:
Type 4 Five-Second Delay Fuze B-8(a) (PP Type 93, Type 100, Type 2 and Type 2 Modified
143–44) Small Instantaneous Fuzes (pp 391–94)
Type 1 Long-Delay Fuze C-3(a) (pp 144–47) Type 4 Super Detonating Fuze (p 395)
Aerial-Burst Fuzes D-l(a) & D-l(b) (PP 147–49) Ho 301 Impact Fuze (p 396)
Type 1 Aerial-Burst D-5(a) & Combination Fuze Type 88 Fuzes: Small Instantaneous, Short-
D-5(b) (pp 149–51) Delay and Instantaneous (pp 397–400)
Type 1 Antiwithdrawal Fuze E-l(a) (pp 151–53) Types 90, 93 & 100 Instantaneous Short-Delay
Remote Control Radio Fuze (p 153) ‘(pp 401-04)
The following are Navy Bomb Fuzes de- Finned Bangalore Torpedo Fuze (pp 404–05)
scribed in Ref 2 on pp indicated below: Type 98 Interior Fuze (pp 405–06)
A-l(a), A-l(b), and A-l(c) Nose Fuzes (pp 154–55) Type 89 Small Time Fuze (pp 406–07)
Type 97 Mk 2 Nose Fuze Model 2 A-3(a) (PP Type 89 Powder Time Fuze (pp408-09)
156–57) Auxiliary Detonating Fuze (pp 409–10)
Type 1 Nose Fuze Model 2 A-3(b) (PP 157–59) Type 3rd & 5th-Year Combination Powder Time
Type 2 Nose Initiator A-3(c) (pp 159–60) and Impact Fuzes (pp 41 O–12)
Type 97 Mk 2 Nose Fuze Model 1 A-3(d) (pp Type 100 Mechanical Time & Impact Fuze (pp
160–62) 412–13)
 J 27

Type 2 Combination Powder Time & Impact Oshokayaku was the main Booster Charge, while
Fuze (pp 414–15) Tetryl (Meiayaku) and RDX (Shouyaku) were
Type 94 Small Delay Base Fuze (pp 41 5–16) used in Sub-Boosters) (p 26)
Type 92 Small Short Delay Base Fuze (pp Accdg to Ref 1, p 121 and Ref 2;p 191,
416–17) Japanese Na~y Fuzes utilized a characteristic
Small Mk 2 & Mk 1 Base Detonating Fuzes Gaine which incorporated within itself the en-
(pp 417-19) tire expl train. The Gaines were similar in ex-
Medium Mk 1 Impact Base Fuze (p 420) ternal appearance but varied in size and internal
Type 88 Small (Howitzer-Mortar) Base Fuze construction. They were generally made of
(pp 421–22) brass, cadmium plated and lacquered. More
Type 88 Small (Gun) Base Fuze (p 422) recently some Gaines were made of steel
Type 95 Large Mk 2 Mod 1 Base Fuze (pp A Table listing Navy Gaines used during
423–24) WWII is given in Ref 1, p 121, while on p 122
Type 95 Medium Base Fuze (pp 425–26) are given external views of six Gaines. PA
(Oshokayaku) was used as a main Booster Charge
Fuze Cap. Shinkamb6 (p 31), Tetryl (Meiayaku) as Sub-booster, and
as Auxiliary Booster 70/30 TNAnisole/HNDPk4
Fuze Detonator. Shinkan no kibakuzai (H2 Kongo–H2 Mixture), abbr for Type 98
Expl (p 31)
Fytizo. Fuse Following Navy Gaines are listed and illus-
trated in Ref 2 on pages indicated:
Type 97 Land Bomb Gaine “A” and Type 99
GAINES (Fukut6) and BOOSTERS (Denkayaku) Ordinary Bomb Gaine “A”; length 4% inches,
Generally speaking Gaine is a container depth 1-3/8 inches. Explosive Train: Primer
. (sheath) for a Booster. More detailed info compn in upper plug; BkPdr delay (0.03 see)
about Boosters is given in Vol 2 of Encycl, pp over flash pdr relay in middle plug; Lead Azide
B243-R to B246-R and about Gaines in Vol 6, detonator over Tetryl in lower plug and PA
pp G6-L to G7-L Booster (p 192& Fig 140)
Japanese Gaines are divided into Army Gaines Type 97 Land Bomb Gaine “B” and Type 99
(Ref 1, pp 88–9 and Ref 2, p 190) and Navy Ordinary Bomb Caine “C”. Same size and Expl
Gaines (Ref 1, pp 121–22 with Table and Ref Trains, but their delays were 0.2 & 0.1 see,
2, pp 191–92) respectively (p 193, Fig 141)
Accdg to Ref 1, p 88 and Ref 2, p 190, Type 15 Ordinary Bomb Gaine. Same size and
Japanese Army Fuzes utilized a characteristic Expl Train as above, but its delay was selective
type of Gaine which differed greatly from that from fractional to 1.5 ‘sees (p 194, Fig 142)
used in Navy Fuzes. Gaines used in Army Bombs Type 92 Land Bomb Gaine Modification 2.
are shown in Fig 107, p 88 of Ref 1 and in Same size but it was Instantaneous and its Expl
Fig 138 of Ref 2. They were of brass con- Train was: MF (Mercuric Fulminate) over
struction and were screwed into the Fuze. Tetryl in an inverted copper cup in upper plug;
There were three Types, of which Types I & no delay chge; Tet ryl pellet in lower plug and
11 were used in the Nose, while Type II was used PA Booster (p 195, Fig 143)
in the Tail Fuzes. Types I and 111were ignited Type 96 Land Bomb Gaine. Same size as above,
by the flash from the Primer in the Fuze, while and Expl Train same as in Types 97, 99 & 15 with
Type H Gaine was pierced directly with the delay chge absent (p 196, Fig 144)
firing pin (because it was used in Fuzes having Type 4 Gaine for Skipping Bomb. Same size as
no internal Primer) above with Expl Train: Primer compn in upper
Army Boosters were either contained in a plug; circular BkPdr Delay Train (1 O to 11 sees)
brass cup threaded into the Fuze around the and Relay in middle plug; Primer compn over LA
Gaine, or in a paper cylinder housed in the main Detonator over Tetryl pellet in lower plug; PA
expl chge of the Bomb Booster (p 197, Fig 145)
Accdg to Ref 1, p 25, PA under the name Type 1 Mk 2 Bomb Gaine “A”. Same size and
 J 28

Train as above, but delay was 3.5fi.0 sec (p as of glass construction were dangerous to use.
198, Fig 146) Rifle (as well as Mortar) Grenades were often
Type O Mk 5 Bomb Caine, length 6% & depth modified Hand Grenades.
1% inches. Same Expl Train as above but The following Grenades are described in Refs
delay was 0.2 sec (p 199, Fig 147) 1 & 2 on pages indicated under each item:
Electric Bomb Gaine, Instantaneous, length Type 91 Hand, Mortar or Rifle Grenade had a
5-3/8 & depth 1-3/8 inches. Expl Train: The cast iron cylindrical body 3% inches long & 2
Electric Blasting Cap fitted into hollowed-out inches in diam. It had 50 serrated segments and
cavity in the PA Booster. Leads from the cap contd 65g of powdered TNT. Its delay was
ran up to a femrde plug which was attached by 3 sees (Ref 1, p 195 & Ref 2, p 225 with Fig
a special adapter to the standard Gaine body 169 on p 224)
(p 199, Fig 148) Type 97 Hand Grenade had a cylindrical, serrated,
Type 2 Small Model Bomb Gaine Model 1, cast iron or aluminum body, 4 by 2 inches, contg
Instantaneous. Length 3, depth 13/16 inches. powdered TNT. It was similar to Type 91 ex-
Expl Train: MF cap over Tetryl in upper plug; cept that the base of Type 97 was solid and could
PA Booster (p 200, Fig 149) not take a propelling charge which is required for
Practice Bomb Gaine, Instantaneous. Length conversion to Rifle or Mortar Type. Therefore,
3-1/8, depth 11/16 inches. Expl Train: MF it could only be used as a Hand Grenade Delay
in upper plug; Tetryl Booster (p 200, Fig 150) 4–5 seconds (Ref 1, p 195 & Ref 2, p 226 with
(See also Magazines) Fig 170)
Type 99 Hand Grenade had a cast-steel cylindri-
Gasu. Gas, Chemical Agent cal body 3% by 2 inches with smooth surface,
filled with cast PA. Delay 4–5 sees(Ref 2, p
Gasubakudan. Gas Bomb 227 with Fig 171). In Ref 1, pp 195–96, this
Grenade was subdivided into Type “A” (Kiska
Gasudan. Gas Shell, Chemical Shell Type) (Fig 299) and Type “B” (Fig 300)
Type 4 Pottery Hand Grenade had spherical
Gasu tekidan. Gas Grenade terra cotta body 3 inches in diam with wall
7/16 inch thick. It contd 3.5 oz of Type 88
Gekishin or Gekkei. Firing Pin Explosive and had 4–5 sees delay (Ref 2, p
228 with Fig 172 & Ref 1, p 197)
Glide Bomb. Kakku bakudan Type 23 Pull Type Hand Grenade had a cylin-
drical cast-steel body 3%’ by 2 inches, with five
Glycerin. Guriserin transverse depressions, used instead of serrations.
It contd 39.5g of granular TNT and had a 5%.-
Gomu. Rubber sec delay (Ref 2, p 229 with Fig 173 & Ref 1,
p 196)
Graphite. Sekiboku Type 98 Stick Hand Grenade had cylindrical,
cast steel body, 7% inches long and 1-5/16 inches
Grapnel. Hikkake-ikari in diam, with smooth surface. It contd 3 oz of
cast PA (Shimose) and had a 4–5-see delay
GRENADES (Tekidan). There are Hand Gre- (Ref 2, p 230 with Fig 174& Ref 1, p 196)
nades (Tery~dan), R if Ie Grenades (Jiiy6 tekidan) Type 3 Conical Antitank Hand Grenade, called
and Mortar Grenades (Kytih6 tekidan) in Ref 1, p 196, “Type 3 Conical Hand-Thrown
Accdg to Ref 2, p 225, the Japanese Armed Mine”, existed in “large” and “small” sizes.
Forces developed both before and during WWII The basic principles of construction were the same
a fairly extensive line of Grenades, This type in both cases, but variations occurred in measure-
of Ordnance primarily used by ground Forces ments, weights and the expl charges. Each Gre-
was developed by the Army, but was also used nade consisted of a cone-shaped expl chge (Type
by the Navy Ground Defense Units. Many Gre- 94 for large and Pentolite for small), a metal
nades were improvised and some of them, such cone and a wooden ring base, all contd in a
 J 29

silk bag. A fuze was inserted and a grass or of RP. (red phosphorus) to the base. The capsule
hemp tail attached to the apex of the chge. The was well protected in the carton (which held
expl chge was cast in the form of a truncated the Grenade) by several layers of cardboard
cone, thus making the Grenade Hollow (Shaped)- and sawdust. Before launching the bottle, a
Charge Type. It was thrown against tanks. rip cord was pulled to open the carton and the
Large type had body 6% inches long and diam igniter capsule was secured to the base of the”
at the base 4-3/8 inches, while smaller type had bottle by the rubber harness. When the bottle
5-7/8 & 4 inches, respectively. Length of the was thrown with force against a hard target it
tail was 14 inches (Ref 2, pp 230–32 with scattered and the friction betw the pieces of
Fig 175 and Ref 1, p 196) RP caused instant ignition of inflammable ma-
Sling Hand Grenade had a cast steel cylindrical terial. The viscous nature of the filling pre-
body which had a metal ring attached to its vented undue splashing and insured adherence
tapered wooden base plug covered with rein- to the target (Ref 2, pp 236–38 with Fig 180
forcing cloth. Overall length 5-7/8, diam 1-13/16, & Ref 1, p 201)
falling 1 oz of TNT and delay 4 or 5 sees. Its Hydrocyanic Acid (Seison) Frangible Grenades
fuze was friction-igniter type located in the nose. were round glass bowls, 3.9 inches in diam contg
Grenade could be thrown either by hand or by 12.2 fl oz of Cu-stabilized ca 80% strong HCN
a sling attached to the base ring (Ref 2, p 232 aq soln which acts as a very storng systemic
with Fig 176 & Ref 1, p 198) poison. There were two types differing in
l/2-kg Incendiary Hand or Mortar Grenade had minor details (Ref 2, pp 238–39 with Fig 181’
brass cylindricrd body, 5.6 inches long & 2.0 & Ref 1, p 201)
inches diam filled with WP (white phosphorus) Frangible Smoke Grenade consisted of a clear
and fize. For projecting it from Mortar, Model glass flat bottomed round flask 2.6 inches in
89, a steel propellant container was screwed into diam, contg 4.1 oz of titanium and silicon
the base of the body. Delay was 4 to 5 sees. tetratetrachloride. It was closed with rubber
(Ref 2, pp 233-34 with Fig 177) stopper and crown cap. Being thrown against
Incendiary Stick Grenade had light steel cylin- a hard object, the bottle broke, releasing the
drical body with hemispherical ends and wooden liquid which in contact with air produced a
handle threaded into the base. Length of body smoke screen (Ref 1, p 201 with Fig 315 and
13.2 inches, diam 2.1 inches and length of Ref 2, p 239)
handle 5.3 inches. The body was filled with 41 40-mm Hollow-Charge Rifle Grenade was light
rubber pellets, each impregnated with a soln of metal cylinder, 1.58 inches in diam, with a
WP in carbon disulfide. The pellets were scat- semiconical shaped head. Overall length 7.98
tered by means of a small central burster chge. inches. It was made in two parts, threaded to-
It is possible that the Grenade was filled some- gether and fitted with a brdlistic cap and cone
times with a SP smoke filling (Ref 2, pp 234– to give a hollow-charge effect. The forward
35 with Fig 178 and Ref 1, p 200) part contd 3.81 oz of 50/50–RDX/TNT cast
Molotov Cocktail, called “Frangible Incendiary around the cone, while the after part had a rifled
Grenade” in Ref 1, p 200. Its body consisted collar near the base and contd the Fuze and
of a Japanese beer bottle into the top of which Expl Train. The Grenade was fired from a cup
was tightly fitted an “all-way” action fuze. The launcher attached to the standard 6.5-mm rifle
bottle, 11% inches long & 2-1/3 inches in diam (Ref 2, pp 239-40 with Fig 182)
was filled with ca 12 oz of an inflammable 30-mm Hollow-Charge Rifle Grenade was a
benzene-type liquid (Ref 2, pp 235–36 with smaller version of the above: overall length
Fig 179) 6.25 inches, diam 1.18 inches and wt of HE
Phosphorus-Ignited Molotov Cocktail used a chge 1.75 oz (Ref 2, p 241)
bottle 9% inches long & 2-1/8 inches diam, which Model 3 Modification 1 Rifle Grenade was si-
contd 9.5 oz of 1570 soln of polymethylmeth milar to the Type 99 Hand Grenade (known as
acrylate in benzene and sealed with a crown “Kiska”, described above in Ref 2, p 227)
type cap. An adjustable rubber harness held a with a tail assembly added. It contd 3 oz of
flat circular glass igniter capsule, contg 1 oz TNT as Main Charge and was intended to be
 J 30

fired ‘from the spigot type Grenade Launcher with Fig)

(Ref 2, pp 241-42 with Fig 183) Conical-Antitank Hollow-Charge Hand Grenade
Smoke Rifle Grenade had a light-metal cylin- (p 176 with 2 Figs)
drical body, 2 inches in diam with fins. It Pottery Hand Grenade (p 177 with 3 Figs)
contd a mixture of hexachloroethane 56.2, High Explosive Rifle Grenade Model 3 (p 177
Zn pdr 27.6, Zn chloride 2.9 & Zn oxide with Fig)
13.4% (adds to 100~1%). It was used with a Hand Stick Grenade, High Explosive (p 178
special adapter which fitted over the end of a with 2 Figs)
rifle barrel (Ref 2, pp 243–44 with Fig 184) Hand Stick Grenade, Incendiary (p 178 with 2
Small Incendiary Rifle GRenade had a light- Figs)
..
metal cylindrical body 1-7/8 inches in diam
filled with WP (white phosphorus)., It was Grenade Discharger (Tekidant6) and Grenade ‘
launched from a spigot type Rifle Grenade Launcher (Rifle) (Tekidanki). A Grenade can
Launcher (Ref 2, pp 244–45 with Fig 185) be launched by hand, by rifle, by mortar or by
Improvised Grenades. Accdg to Ref 1, p special Grenade Launchers or Dischargers. These
202 and Ref 2, p 225 a large variety of Gre” it’ems were usually modified rifles or mortars.
nades was made from such items as small There were also special adapters ‘which fitted
ammunition, small bombs & shells, pipes, paper barrels of rifles. Most Rifle Grenades could be
and wood. This was probably due to a shortage fired directly from rifles
of materials. Most improvised items were in- The following special devices for launching
effective and dangerous to use ( grenades are listed in Ref 1:“
The following improvised Grenades are listed 50-mm Type 10th Year Grenade Discharger was ‘
in Ref 1, pp 202–03: the forerunner of the “Knee Mortar” (p 158)
a) Gas pipe, closed at both ends, filled with an Type 89 Grenade Discharger, known as the
expl and fitted with a .22 cartridge case and “Knee Mortar” had a rifled bore and a provision
safety fuse as igniter for varying the range with f~ed angle of eleva-
b) 25-mm shell case filled with an expl and tion (pp 158-59)
fitted with a pull igniter or a length of fuse The following devices are described in the
c) Heavy paper or braided cord container book of T~tum & Hoffschrnidt, listed as Ref 7:
filled with an expl and fitted with fuse 50-mm “Grenade Discharger Model 10 (1921) is
d) 1/2-kg Army bombs removed from their the same’as listed but not described above and
containers, armed and thrown by hand (Fig in Ref 1, p 158. It was smooth-bore and
318) weighed 51%lbs. It could be carried by one
e) A very effective conical Grenade was con- soldier. It was used to discharge Model 91
structed from the tail section of the Navy 30- Hand Grenade pyrotechnic signals and smoke
kg Practice Bomb. The tail cone was removed shells. Range 175 yds (p 155 with Fig)
and the space around the burster tube was 50-mm Grenade Discharger Model 89 (1929) was
filled with granular PA. Then a grass or hemp cord rifled-bore and weighed 10% lbs. Range for
was attached and the B-6(a) Practice Bomb Tail Model 91 Hand Grenade was 200 yds. It was
Fuze fitted to the cone. After arming the Fuze also used for pyrotechnic signals, incendiary
by hand, the bomb was thrown (Fig 319 on p shells, etc (pp 156–57 with several Figs)
203) Rifle Grenade Launchers. The following types
The following Grenades are described and are described and illustrated on p 179 of Ref 7:
excellently illustrated in the book of W.H. 1) Type 2 or Cup Type Launcher which was
Tantum IV and E.J. Hoffschmidt, “Second patterned after the German Launcher fitted
World War-JapaneseCombat Weapons”, Vol 2 over the front sight of the rifle and had a short
(1968), WE Inc, Old Grennwich, Com 06870, rifled barrel (See Fig). It fired both the
listed as Ref 7: 30-mm and 40-mm Hollow Charge Rifle Gre-
Hand Grenade Model 91 (1931) (p 173 with 2 Figs) nades, which could penetrate 3-7/8 inches of
Hand Grenade Model 97 (1937) (p 174 with 2 Figs) mild steel plate
Hand Grenade Model 99 (1939) (Kiska) (p 175 2) Type 100 or Kiska Type Launcher, shown in
 J 31

Fig, consisted of a tube which could be at- place of PA (Picric Acid)

tached to either 6.5-rnrn or 7.7-mm Rifle. The 70/30 mixt had Expln Temp 237–46°;
Ordinary ball ammo was used to launch the Brisance by Sand Test 102% TNT; Power by
Grenade (the expanding gas from the fired Ballistic Mortar 109% TNT; Rifle Bullet Test
cartridge was utilized to expel the grenade from 20% detonations; and Impact Sensitivity by
the launcher), a feature which enabled the rifle PicArsn Test 12.5 inches (TNT 14). It was re-
to be carried with the launcher attached and ported to be’ toxic, not very stable, and re-
ready for use as either a rifle or as a Grenade active with metals in the presence of moisture.
Launcher. The Type 99 Kiska Grenade was the Used pressed by Army and Navy as an Auxiliary
only type used with the Launcher. Maximum Booster in some Bombs and Shells (Ref 1, pp
range was 100 yds (p 179) 31 & 32 and Ref 5, p 365)
3) Spigot Type Grenade Launcher consisted of
a rifled barrel threaded to an adapter. It was Haensosan bakuyaku. See Type 88 (Ko)
attached to either the 6.5-mm or 7.7-mm Rifle
at the rear of the front sight. It was used to Haishokuyaku (Gray Powder). A dark-gray,
fue Type 91, Type 3 HE, and several types of non-toxic expl compn: No 1 Mixture con-
Smoke and Incendiary Grenades (pp 179–80 sisted of Amm Perchlorate 76.9, RDX 17.0,
with 3 Figs) silicon carbide 1.3 & paraffin 4.8%; relative
Power & Brisance greater than for PA, but it
Gun (Ht5) and Howitzer (Ryiidarnpi5). See is less sensitive to impact and friction. Used in
under ARTILLERY AND ITS WEAPONS Army Standard Demolition Blocks; No’2 Mixture
consisted of Amm Perchlorate 48, GuN (Guani-
Gun Barrel. H6shin dine Nitrate) 20, RDX 25 & paraffin 5%. It
was a commercial mining expl, and also used in
Guncotton. Menkayaku Army Demolition Blocks (Ref 1, p 28 & Ref
5, pp 365–66)
Gunpowder. Kayaku or Black Powder. Koku-
shokuyaku, also called Yuenyaku (Nonsmoke- Hakaito. Bangalore Torpedo. See under DE-
less Powder) MOLITION TUBES

Gyokei suirai or Gyorai. Torpedo Hakai yaku. Demolition Charge

Gyorai. Torpedo Hako bakudan. Armor-Piercing Bomb

Gyorai jitsuyo tobu. Torpedo Warhead Hakodan. AP Projectile

H2 Kongo (H2 Mixture) or Type 98’ (Explo- Hako ryudan. AP-HE Projectile
sive). Lemon-yel expl compns consisting of
TNAns (Trinitroanisole) 60–70 & HNDPhA Haktu or Ryukyu. Mortar
(Hexanitrodiphenylamine) 40–30%
The 60/40 mixt was cast-loaded to a density Hakugekine. Trench Mortar; Infantry Mortar
of 1.65; its mp 65–70°, Expln Temp 264° &
higher; Brisance, by Copper Cylinder Crusher Hakurin. White Phosphorus; WP
Test 100% (PA= 1OO%);Power by Ballistic
Mortar 96% (PA= 100); Deton Velocity by Hand Grenade. Teryiidan. See under GRENADE
Dautriche Method 7050m/see; Impact Sensitivity
with 15kg Weight 14cm (max wt for no explns); Haretsu. Burst, Explosion
Friction Sensitivity 60kg (max pressure betw
two rubbing surfaces for no explns). Used, Hasai boryaku. Sabotage
under the name Type 98, in Navy Bombs,
Depth Charges, Sea Mines and Torpedoes in Hassha. “Discharge (of a Firearm)
 J 32

Hasshadan. F’rOjectfle Hikoki. Airplane

Hatsuen or Hatsuendan. “Smoke Bomb or SheU Hikosen. Airship; Dirigible

Hatsuen tekidan. Smoke Grenade Ho Gun; Artillery

Hatsuento. Smoke Pot; Smoke Candle Hobi. Breech (Arty)

Hatsuenzai. %hoke Agent Hodan. Shell

HE (High Explosive) Projectile. Ryiidan Hohei. Infantry

Heavy Artillery. Jiih6hei Hoei. Artillery

Heavy Gun. Jiih6 Hoko. Muzzle (Arty)

Heavy Machine Gun. Juki Hollow (Shaped) Charge [Ta(dan)] Japanese

Ammunition (Senk6ryIidan)
Heiki. Ordnance, Weapon, Arm In the paper by A.J. Dere, “Adaptation of
the Hollow Charge Principle of Explosives”,
Heikibu. Ordnance Department (Japan) published in Ordnance Sergeant, Vol 10, p 13
(Ott 1945), it was stated that Japanese used
Heiki seizosho. Ordnance Factory during WWII, the following Hollow Charge
(HoC) items:
Heikisho. Ordnance Depot (Japan) 75-mm HoC Projectile for Type 41 Regimental
or Mountain Gun
Heineiyaku. Trinitrophenetole (TNPhnt) or HoC Rifle Grenade, diam 2.7 inches, overall
Ethyl Picrate, C2H5 .0.C6H2(N02)3; mw 257.16, length 7.08 inches, which could be fired from a
N 16.34%; yellowish trysts, mp 78 ; less power- 6.5-mm Infantry Rifle, was modified and several
ful, less brisant and less sensitive to impact than of them were enclosed in a large bomb casing.
TNAnisole; called Type 91 Expl by the Japanese This ensemble could be dropped on airfields to
Navy. Deton Vel of TNPhnt 6880m/sec vs 7640 darnage grounded aircraft
for TNAns [Blatt, OSRD Rept 2014 (1944)] Accdg to TM 9-1985-4, listed here as
Accdg to Ref 3, p 321, Heineiyaku was used Ref 2, the Army Type 2 l/3-kg Cluster Bomb
as an alternate HE Filler (instead of TNT) in contd Hollow Charge of 50/50 –RDX/TNT (pp
Type 90 7-cm (75-mm) HE Long-Pointed Pro- 29–30 with Fig 25). There were also Type 3
jectile and in Type 94 7-cm (75-mm) High Ex- Conical Antitank Hand Grenade with HoC (pp
plosive Projectile (Not listed in Ref 1) 230–31 with Fig 175) and 30 & 40-mm HoC
It is listed as Keineyaku in Ref 5, p 366 and Rifle Grenades (pp 239–41 with Fig 182)
is stated that it can be used as a Bursting Charge In TM 9-1985-5, listed here as Ref 3, the
in Projectiles ,as a Booster Charge, either alone following HoC projectiles are described:
or in mixtures with PA Type 3 7-cm (70-mm) Army HoC Projectile
(PP 305-06 with Fig 238)
Heishi. Soldier Type 2 7-cm (75-mm) Army HoC Projectile (pp
328–29 with Fig 257)
Herikoputa Helicopter In the book of W.H. Tantum IV & E.J.
Hoffschmidt, “Japanese Combat Weapons”,
High Explosive. K6kyii bakuyaku WE Inc, Old Greenwich, Corm (1968), listed here
as Ref 7, are described the following HoC items:
High Explosive Shell. K6kyti ry~dan or a) Conical Antitank HoC Hand Grenade (p 176
Jiraidan with Fig). Their construction is identicaJ with
 J 33

Grenade described in Ref 2, pp 230–31 Igniter System for Bangalore Torpedo is de-
b) Antitank “Lunge Mine”. ‘fiis interesting de- scribed under Demolition Tubes and in Ref 2,
vice described on p 184 (with Figs) of Ref 7, pp 215–17 with Fig 162
consists of a conical-shaped hollow charge en- Mechanical Pull Igniter (pp 246–47 with Fig 186)
cased in a steel container, which was attached Friction Pull Igniters were: Red Type (length
at its apex to a long wooden handle. Three legs, 2% inches) and Black Type (length 3-1/16 inches)
equally spaced around the wide base of the cone (p 248 with Fig 187)
provided proper stand-off distance. A well in Waterproof Safety Fuse Igniter (pp 248–49
the apex of the chge contained the detonator with Fig 188)
which is activated by a striker. To operate the Trigger-Type Safety Fuse Igniter (pp 249–50
device the soldier removed the safety pin, and with Fig 189)
then using bayonet tactics, lunged forward Booby-Trap Firing Device (pp 250–51 with
striking the base of the cone squarely against the Fig 190)
tank. When the legs of the mine struck the tank, Time Firing Device Mk 1 (pp 256–57 with
the long handle was driven forward breaking Fig 193)
the shear pin, and the striker was driven into Chemical Delay Firing Device (pp 257–58 with
the detonator, initiating expln of the chge Fig 194 of Ref 2)
which could penetrate steel plates 4 to 6 inches Firing Devices used in Land and Sea Mines
thick. This mine was considered as a “suicide are listed under MINES
weapon” (See also Ref 2, pp 208–09 with Fig
155) Illuminating Compositions (Shomei henso).
The following compositions are listed in
Hoshaki. Projector; Discharger Refs 2 & 3:
Illi.rminant for Type 90 Small Model Parachute
Hoshayaku. Propellant Flare consisted of Ba chlorate 75.2 & gum 24.8%.
The Flare, contg 4 lbs of compn, burned for
Hoshin. Gun Barrel; Gun Tube 2-2/3 reins with an intense greenish-white light
(pp 22-24)
Howitzer. Ryiidampii See under ARTILLERY Illuminant for Type 1 12-kg Parachute Flare
consisted of Ba nitrate 77, Al 8.8, Mg 4.4, S
Hydrocyanic Acid. Seisan 2.2 & paraffin 4.5 parts. The Flare, contg 27
lbs of compn, burned up to 3 reins with a
Hyoteki. Target greenish-white light (pp 24–25)
11.luminant for 5-kg Parachute Flare Model 2
IGNITER (Tenkayaku or Tengaku) or FIRING Modification 1 consisted of Ba nitrate 55.5,
DEVICE (Hakkasochi). This includes: Igniting Al 11.0, Mg 18.0 & wax 9.1 parts. The flare,
Primer (Tenka bakkan); Igniting Fuze (Tenka contg 51%lbs of compn, burned for 11%reins
shinkan) and Firing Mechanism (Gekihat su kikan) with brilliant white flame (pp 100– 101 of Ref 2)
Igniters are used for igniting propellant charges, Illuminant for 14-cm (140-mm) and 15.5-cm
pyrotechnics, some fuzes, demolition charges and (155-mm) consisted of Ba nitrate, Mg & wax
some special items. The simplest igniters are (Pp 493 & 504 of Ref 3)
safety matches and squibs which are used to ig-
nite safety fuses Illuminating Projectile (Shell) (Sh6meidan).
In Ref 1, pp 233–34 are described devices The following projectiles are listed in Ref 3:
to ignite demolition charges which are briefly Type 95 7-cm (70-mm) Illuminating Projectile
described here under DEMOLITION CHARGES (PP 306-07 with Fig 239)
AND EQUIPMENT Type 90 7-cm (75-mm) Illuminating Projectile
In Ref 2 are described the following items: (PP 338-39 with Fig 265)
Type 3 Electric Firing Device developed by the 12-cm (120-mm) Illuminating Projectile (pp
Navy experimentally for Proximity Fuzes (pp 477–78 with Fig 389)
188–89 with Fig 137) 14-cm (140-mm) Illuminating Projectile (p
493 with Fig 404)
 J34

15.5-cm (155-mm) Illuminating Projectile (p 2.6% to form an “Incendiary Soap”, one of

504 with Fig 415 of Ref 3) the Sabotage items (p 263)
The following Incendiaries are listed in Ref
Impact. Shtigeki 3 for Army Projectiles:
a) Unknown Incendiaries in 20-mm HEIncend
Impact Fuze. Sh6geki or Chakuhatsu shinkan Projectiles on pp 282–84; 20-mm HEIncend-
Tracer (p 284); 20-rnm Intend (Self--Destroying)
Incendiaries. (Sh6sei). (p 285); Type 2 & Type 2 Modified 20-mm
Accdg to Ref 2, the following incendiaries HEI (p 286); 37-mm HEI Projs (pp 289–91);
were used by the Japanese during WWII: Type 90 7-cm (75-mm) Intend (p 337)
a) Thermite as in Army l-kg and 5-kg Intend b) Incendiary consisting of Ba nitrate, Al, Mg
Bombs (pp 15–18) & wax, as in Type 4 20-rnm HEI (Ma 202)
b) Rubber bungs (1 by 1 inch) impregnated Proj (pp 287–88)
with soln of phosphorus in CS2 as in Army 50 c) Solution of WP and rubber pellets in CS2
& 100 kg Intend Bombs (pp 18–20) as in Army 7-cm (75-mm) Liquid Intend Proj
c) WP (white phosphorus) fried steel pellets (pp 339-40)
as in Navy Type 99 No 3 Bomb (pp 63–64) The following Incendiaries are listed in Ref 3
and Type 3 No 6 Mk 3 Model 1 (pp 64–65) for Navy Projectiles:
d) Steel cylinders contg an Intend mixture of d) WP in Al canister surrounded by graphited
Ba nitrate 35.8, ferric oxide 27.2, Al 13.6, flake NC (p 442)
Mg 10.3 & synthetic shavings 13.1%, as in Type e) WP as in 25-mm HEI Proj (pp 447–48);
No 25 Mk 3 Model 1 (pp 66–68) Type 2 and Type 5 HEI (p 452); 12-cm (120-mm)
e) ‘fhermite-filled electron firepots as in Type IncendShrapnel (pp 482–83)
98 No 7 Mk 6 Model 1 (pp 71–72) f) Steel pellets filled with a dry mixture of Mg
f) Central thermite core surrounded by solidi- 54, Ba dioxide 26, rubber 15, ferric oxide 1.5
fied kerosene, petrol, alcohol mixture as in & sulfur 3% as in 12.7-cm (127-mm) Incend-
Model 2 of above Bomb (pp 72–73) Shrapnel (pp 485–86)
g) Cylindrical Intend pellets (consisting of Ba g) Unknown Incendiary as in 15-cm (152-mm)
nitrate 35, ferric oxide 28, Al 18 & remainder IncendShrapnel (p 500 of Ref 3)
synthetic rubber resembling Thiokol arranged The following Incendiaries used in Japanese
around centrrd cardboard tube contg Igniter Mortars are listed in Ref 3:
mixt (Ba nitrate 75.0, Al 24.5, oil 0.3 & moisture h) Incendiary Mixture of K nitrate 47.7, Al
0.2%) as in Type 1 No 7 Mk 6 Model 3 Modifi- 21.7, S 19.9, Sb trisulfide 6.1 & wax 2.8% as
cation 1 Bomb (pp 74–75) in Type 89 50-mm IncendMortar (pp 375–76)
h) Intend Shrapnel consisting of short lengths i) WP, carbon disulfide and rubber pellets as
of steel pipe ffled with WP, as in Type 4 No 25 in Type 94 90-mm IncendMortar (pp 386–87)
Mk 29 (pp 87–88)
i) White Phosphorus as in l/2-kg Intend Hand Incendiary Bomb (To% sh~idan). See under BOMBS
or Mortar Grenade (pp 233–34) and Small In-
tend Rifle Grenade (pp 244–45) Incendiary Cylinder Mk 1 “A” Large. See Ref 1,
j) Any inflammable benzene-type liquids, as p 249
in Molotov Cocktail (pp 235–38)
k) Thermite as in Metal Incendiary Cylinders Incendiary Grenade. (ShGiy6 tekidan). See
shown on p 261 of Ref 2 under GRENADES
1) Mixture of K chlorate, sulfur, ground coal
(or sugar), iron fdings and wax to form an Incendiary Projectile or Shell (Sh6idan). See
“Incendiary Brick”, one of the Sabotage De- under ARTILLERY AMMUNITION
vices (p 262)
m) Mixture of Ba nitrate 30.4, paraffin 19.4, Indicator (Shijiki). See Markers or Indicators
Mg 11.3, Al 11.1, rosin 10.9, ferrosoferric
oxide 9.1, NC 4.4 & gritty siliceous material Infantry. Hohei
 J 35

INFANTRY WEAPONS (Hohei heiki). Under Iperitto gasu. Mustard Gas

this title are described and illustrated on pp
39–78 of the book of Tantum & Hoffschmidt, Iron. Tetsu ,
listed here as Ref 7, the following weapons:
9-mm Revolver, Mod 28 (1898) (p 39) Jakusoku. Reduced Charge
8-mm Automatic Pistol “Nambu” (pp 40–41)
7-mm Baby “Nambu” (p 41) Jet. Funshutsu
8-mm Automatic Pistol, Mod 14 (1925) (pp
42–43) Jibaku. Self-Destroying
8-mm Automatic Pistol, Mod 94 (1934) (pp
44-45) Jidoho Automatic Gun
35-mm Pyrotechnic Pistol, Mod 10 (p 46)
Triple Barrel Signed Pistol (p 47) Jidohu. Automatic Rifle
6.5-mm Rifle, Mod 38 (1905) (p 48)
6.5-mm Carbine, Mod 38 (1905) (p 49) Jippo. Ball Ammunition
6.5-mm Cavalry Carbine, Mod 44 (1911) (p 50)
7.7-mm Paratrooper Rifles, Mod 99 (1939) and Jirai. Land Mine
Mod 2 (1942) (pp 51–53)
6.5-mm Sniper’s Rifle, Mod 97 (1937) (p 54) Jiraidan. High Explosive Shell
8-mm Submachine Gun, Type 100 (1940) (p 55)
8-mm Paratrooper’s Submachine Gun, Type 100 Jirai fusetsu. Mine Field
(1940) (p 56)
6.5-mm Tank Machine Gun, Mod 91 (1931) (p 57) Jisei kirai. Magnetic Mine
6.5-mm Heavy Machine Gun, Mod 3 (1914) (PP
60–61) Jitsudan. Live Ammunition
6.5-mm Light Machine Gun, Mod 96 (1936) (PP
62–63) Jubi kikan. Breech Mechanism
7.7-mm Light Machine Gun, Mod 99 (1939) (p 64)
7.7-mm Paratrooper’s Machine Gun, Mod 99 Juho. Heavy Gun”
(1939) (p 65)
7.7-mm Tank Machine Gun, Mod 97 (1937) Juhohei. Heavy Artillery
(pp 66-67)
7.7-mm Heavy Machine Gun, Mod 92 (1932) Juken. Bayonet
(pp 68-69)
7.7-mm Lewis Machine Gun, Mod 92 (1932) Juki or Jukikanju. Heavy Machine Gun
(pp 70-71)
13-mm AA Machine Gun, Mod 93 (1933) (PP Juko. Muzzle (SA).
72–73)
20-mm Automatic AA/AT Cannon: Mod 98 Jusensha. Heavy Tank
(1938) (pp 74-75)
20-mm Automatic AT Jushin. Rifle Barrel
20-mm Automatic AT Rifle, Mod 97 (1937)
(pp 76-77) Juyo tekidan. Rifle Grenade
25-mm Dual & Triple Automatic AA/AT Cannon,
Mod 96 (1936) (p 78) Kainbin. Frangible Grenade

Initiator. K6kyTs tenkayaku; Kibakosochi Kaen hasshaki. Flame Thrower

Instantaneous Fuze. Shumpat su shinkan Kagakudan toshaki. Chemical Mortar

Interior Ballistics. T6nai dand6gaku Kagaku heiki or Kaheizai. Chemical Agent, CWA
 J 36

Kagakusei tekidan. Chemical Grenade Kibakuzai. Primer Charge. See Chikkaen

(Army) or Chikka namari (Navy), meaning LA
Kagkusei tokagan. Chemical Bomb (Lead Azide) and also Raik6 (Army) and Raisan
suigin (Navy) for MF (Mercuric Fulminate)
Kagakusha. Chemist, Scientist (Ref 5, pp 366& 369)

Kago. Chemical Composition Kidoishiki kaho. Mobile Artillery

Kaho. Gun (General) Kihei. Cavalry

Kaiganho. Coast Artillery Guns Kihtu. Carbine

Kaigun. Navy Kikanho. Machine Cannon

Kakki. Firing Pin Kikanju. Machine Gun

Kakkoho. Smooth Bore Gun Kirai. Mine (Sea)

Kanoho or Kanon. Cannon (as opposed to Kiri Nos 1, 2 & 3. Gelatin Dynamites Nos 1, 2 & 3
Howitzer (called RyiIdanp6)
Ko (Explosive). Japanese Type Explosives, such
Kanzen yakuto. Fixed Ammo, Fixed Round as Type 88 (Ko)

Karitto. Army explosive, originated as commercial Kochu. Bore (Gun)

expl Calit (qv). Its Navy modification is Type 88
Explosive (qv) Kodan. Flare, Sigml Rocket, Star Shell

Kasen. Pyrotechnics Kodo. Gallery of Mine

Kasen hasshaki. Pyrotechnic Projector Koyo. Factory, Shop

Kasshokuyaku. Brown Powder. Accdg to docu- Kojoho. Siege Gun

ments it was “Undercarbonized Black Powder”.
Use unknown, but presumably as a substitute Kokakuho. Dual Purpose Gun (Navy)
for BkPdr (Ref 1, p 30& Ref 5, p 366)
Kokei. Caliber
Keiho. Light Artillery
Kokuki. Aircraft
Keikikanju. Light Machine Gun
Kokushokuyaku. Black Powder or Yuenyaku.
Keineyaku. Accdg to Ref 3, p 321 it is Nonsmokeless Powder. Composition is not given.
Heineiyaku (qv) Used by the Army as a Main Charge in 20-mm
Machine Gun Ammo, as an ejector chge in
Ken. Bayonet 70-mm Mortar Shells, Shrapnel Shells & Pyro-
technics; in Delays, Relays & Igniters for Bomb
Keyaki. Gelatine Dynamite & Projectile Fuzes; and as a “Substitute Charge”
for some Bombs, Grenades and Projectiles
Kibaku. Detonation (Ref 1, p 27& Ref 5, p 366)
Also used by the Navy as an ejector charge
Kibakuyaku. Initiating Composition. See for Illuminating Shells and Pyrotechnics (Ref
Bakufun (Ref 1, p 25) and Raibun (Ref 1, p 25) l,p 33)
 J 37

kokyu bakuyaku. High Explosive Land Mine. See under MINES

kokyu rytudan. HE Shell Lead @b). Namari

Koseisendan Semi Steel Cast Projectile Lead Azide (LA). See Chikkaen (Army) &
Chikka Namari (Navy)
Kosen Groove, Rifling
Liquid Fire. Ekka
Koshaho Antiaircraft Gun
Livens Projector. Ribensu shiki
Koshitsu (Plastic) or Oshitsuyaku (?). A brown,
putty-like expl compn consisting of RDX 80 Load or Charge (of Explosive). S6yaku
to 85 & oil 20 to 15%. Brisance by Sand Test
108% TNT; Power by Ballistic Mortar 125% Long-Range Gun. Enkyori shagekihi5
TNT; Detonation Velocity 7400m/sec vs 6900
for TNT; Impact & Friction Sensitivity – same L-Shoan. Ammonium Nitrate Dynamite
order as for TNT; retains plasticity betw 0°
(32”F) & 37.8°(1000F), becoming brittle be- Machine Cannon. Kikanh6
low 0° and starting to exude oil above 37.8°.
Used in Demolition Cartridges 4 inches long and Machine Gun. Kikanjli
1.5 inches in diam and Hollow (Shaped) De-
molition Cartridges (being 2 1‘%0more effective
than TNT Shaped Charges) (Ref 5, p 367) Magazines. There are severrd itaems called
Accdg to Ref 1, p 28, the term Koshitsu magazines. One for rifles and pistols is Dans~
(meaning “plastic”) may be a part of designa- (in Japan), one for storage is Danyakuko and
tion. Its compn was RDX 80 & vegetable oil one is a cylindrical item which can be fitted
20%, and it was used in Demolition Rolls. to any Fuze that takes a standard Gaine (qv).
There seems to be another plastic expl contg Magazines are used to initiate Low Explosives
RDX which was a mixture with NG such as BkPdr but never used in a HE fdled
Bomb
Ko-Shuanbakuyaku. Ammonium Nitrate No Army Magazine Gaines are listed in
Dynamite Refs 1 & 2, but Navy Magazines are listed in
both Refs 1 & 2. In Ref 1 are listed on p 121
Kotetsuban. Armor Plate Type 98, Mk 6, Model 1 and Model 2 Bomb

I Kuchu haretsu. Air Blast

Gaine Magazines with 0.03-sec Delay and In-
stantaneous, with Fig 185 on p 122. The same

I
Magazines are listed in Ref 2 on p 201 with
Kuchu hatsuendan. Smoke Bomb more detailed illustrations (p 201)

Kugun. Air Force Magnesium Bomb. Maguneshiimu shtiidan

Kurai. Aerial Torpedo Magnetic Mine. Jihoku

Kyodan. Heavy Shell; Heavy Bomb Markers or Indicators (Shishi-Keiki)

These devices can serve astarget indicators
Kyuho. Artillery Mortar signaling landing spots, navigation markers,
disaster spot markers, etc
Kyuhodan. Artillery Mortar Shell The following items, which might serve as
Markers or Indicators are described in Ref 1:
Kyunen Kaseka. Quickmatch Navy Type 96 Floating Landing Flare (p 241,
Fig 395)
LA. Abbrn for Lead Azide (See Chikkaen) Ground Signal Flare (p 242, Fig 396)
 J 38

Type 94 Float Flares (pp 242–43, Figs 397 Matsu. Blasting Gelatin
to 400)
Army Smoke Candles (pp 243–44, Fig 401)’ Mechanical Time Fuze. Takeishiki bakkan
Navy 40-kg Floating Smoke Generator (pp 244–
45, Fig 402) Meiayaku (Army), Sanshoki (Navy?) or Mechiru
Navy Smoke Float (p 245, Fig 404) Nitroamin. Tetryl or 2,4,6-Trinitrophenyl-
Navy Smoke Flare (pp 245–46, Fig 404) methylnitramine,
Type 2 Target Indicator (p 246, Fig 405) CH3
Navy Navigation Markers: (02 N)3C6H2.N<
Type O Model 1 & Model 2 (p 246, Figs 406 N02; mw 287.16, N 24.39%;
& 407) cream to yellow trysts, density 1.73, mp 130°;
Type 2 Model 11 (p 246, Fig 408) Brisance by Sand Test 126% TNT; Impact ,
Cardboard Type (p 246, no Fig) Sensitivity with 2kg Wt, BurMinesApp 26cm vs
Navy Type 2 Model 1 Torpedo Marker (p 249, 100 for TNT; Ignition Point 257° in 5 reins;
Fig 413) Detonation Velocity 7850m/s vs 6900 for TNT;
The fo~owing items which might serve as Power by Ba!listic Mortar 130% TNT [AMCP
Markers or Indicators are described in Ref 2: 706-177 (1967), p 335]
Navy Type 94 Float Lights (pp 106–08). Used by Japanese in pressed state as a stan-
See under FLARES dard Sub-Booster in Army and Navy Shells and
2-kg and 43-kg Smoke Floats (pp 109–1 O). occasionally as the sole Booster in Navy 25-mm
See under Smoke Floats Shells and as Burster in some Bombs and Shells.
Navy Sea Markers Type O, Model 1, Model 2 Also used in composite explosive Tan6yaku (qv)
were light metrd cylinders with rounded nose (Ref 1, pp 26,31 & 33; Ref 5, p 367)
and conical tail, provided with fins. They contd
fine Al’ dust with 6.5% Zri dust. On impact Menkayaku (Guncotton). Comp with Sh5kamen
with water the plug in the nose was forced into (Nitrocellulose)
the body forcing the tail portion to be freed
from the body, thereby scattering A1-Zn pdr, Menyaku. Same as Menkayaku
1 oz of which covered 118 sq ft of water. Used
as distress indicator (pp 11O– 11, Fig 84) ‘ Military (adj). Rikugun no
Navy Sea Marker Type O Cardboard Type, on
impact with ,water broke and scatterd A1-Zn MlNES. Jirai (Land), Kirai (Sea), Suirai
pdr over the surface of water (p 112) (Amphibian or Water) and Booby Traps
Type 3 No 6 Target Marker Bomb consists of (Y~gekiteki jirai)
a steel cylinder with round nose and conical Accdg to Ref 1, p 210 & Ref 2, p 203, al-
tail, provided with fins. me fiiing consisted though the use of Land Mines by the Japanese
of WP-filled steel pellets contd in steel canisters. Forces was not as extensive as it was in Europe,
The space not occupied by pellets was surrounded they were important defensive weapons in the
by loose WP. The canisters were covered with Pacific War. Also, because of the Japanese lack
heavy wax coating. The nose-piece contd a of effective A/Tk Artillery and the inequality of
Gaine well surrounded by charge of Type 98 Armored Forces, mining and similar tactics be-
Expl (p 113, Fig 85) came a mainstay of defense against mechanized
Type 2 2-kg Target Indicator consisted of a equipment
Bakelite cylinder with round nose and tail Three features of land mining methods were
provided with fins. The filling consisted of especially important: 1) The relatively small
liquid FM (Titanium Tetrachloride). This number of standard, mass-produced mines and
smoke mixture was scattered when the bomb firing devices; 2) The prevalent use of extremely
was released from a plane, hit the target and large expl charges which was wasteful and 3) The
broke @p 113–14, Fig 86) emphasis was placed on various types of con-
trolled mines instead of by enemy activated
Masutadu gasu. Mustard Gas ones. Firing devices operated by lanyards or
 J 39

poles were very common made of the same material. It was filled with
Japanese minirig techniques were character- TNT (5% lbs) and contd a fuze. A spring held
ized by an rdmost complete lack of uniformity the cover off the fuze, ‘but a pressure of 50 lbs
In Chapter VI of Ref 1, entitled “Japanese was sufficient to activate it (pp 210-11, Fig 157)
Mines and Booby Traps” are briefly described Type 3(A) Antivehicular & Antipersonnel Mine,
and rather poorly illustrated various Army and known as “Flower Pot”, consisted of a terra’
Navy Land Mines (pp 210 to 228) cotta, low cylinder ffled with Type 88 Explo-
More comprehensive descriptions, with good sive or with 50/50–Amatol. The fuze located
illustrations, are given in Chapter 3 of Ref 2 on top of mine could be activated by pressure
for the following Land Mines: of ca 22 lbs (pp 21 l–12, Fig 158). Described
Type 93 A/Tk (Antitank) and A/P (Anti- in Ref 7, p 182 as “Navy Type 3 (Flower Pot)
personnel) Land Mine, known as “Tape Mea- Land Mine-Small”
sure” Mine, was a light metal cylinder 6% inches Type 3(B) A/Vehicular & A/P Land Mine con-
diam and 1% inches high, fdled with 2-lbs of sisted of a wooden box filled with Type 88
cast PA and Booster of pressed PA. It was Expl (p 213, Fig 159)
activated by pressure on Percussion Primer. lo- Beehive A/p Land Mines, recovered on Okinawa,
cated on top of Mine (PP 202–03, Fig 152). consisted of serrated cast-iron, hemispherical
Described in Ref 7, p 183 as Land Mine Model casing ffled with ca 5’,lbs TNT. A pressure of
93 (1933) one person on a fuze located on the top was
Anti-Vehicular “Yardstick” Land Mine was an sufficient to initiate expln (p 214, Fig 160)
oval tube 3.35” x 1.8” in diam and 36” long, 5-kg Hemispherical A/Tk Land Mine consisted
formed by two halves of sheet steel welded to- of light metal casing filled with a HE (?) and .
gether. It contd 8 blocks of cast PA wrapped a fuze mounted opposite the flat bottom. It
in paper (wt 6 lbs) and a Fuze which could be was a suicide weapon, intended to be placed
activated by strong pressure sucli as of a vehicle against an armored vehicle either by hand or by
(PP 204-06, Fig 153). Described in Ref 7, means of a pole attached to the case (p 215,
p 187 with Figs Fig 161)
Type 99 Armor-Penetration Land Mine was Bangalore Torpedo, described here under DE-
canvas disc 4.75” in diam & 1.5” wide, filled MOLITION TUBES could be used as a Land
with cast blocks of 50/50–RDX/TNT forming Mine (PP 215–17, Fig. 162)
a circle. Four magnets were attached around the Pressure and Traction Land Mine consisted of a
circumference, which were designed for at- wooden box, the lid of which was held in place
tach~g the mine to the side of a tank or other against the internal fingers on the top by stout
vehicle. (pp 206–07, Fig 154). Described in springs, one in each corner. A wooden block
Ref ,7, p 181 as “Magnetic” Antitank Mine was secured by two bolts to the underside of
Model 99 (1939) the lid and served to operate the pull igniter
Antitank “Lunge” Mine (p 208, Fig 155) is by pressure exerted on the cover. It was ftied
also described here under “Hollow Charge with 2 lbs of cast PA or TNT (pp 217–18;
Japanese Ammunition” and in the book of Fig 163)
Tantum & Hoffschmidt, listed as Ref 7 (p 184) Friction-Fuzed Land Mine consisted of a wooden
Suction-Cup Mine consisted of sheet metal box 13“ long, 3” wide and 2.37” high contg
cylinder ffled with ca 4.5 lbs of 53/47 –RDX/ 5 blocks of cast PA or TNT (3.5 Ibs), detonator
TNT and provided on top with a 5 ft pole. or igniter. TO the igniter was attached a trip
Two suction cups at the bottom of the mine wire which extended out thru the end of the
secured it to target when pressed. Ignition box and was secured to a tree or other f~ed
was made by two Friction Pull Igniters which object (pp 2 18–19, Fig 164)
were lashed to the bottom of pole (p 209, Improvised Land Mine consisted of a rectangular
Fig 156) tin box with a cover fastened by friction tape.
Dutch A/Tk–A/P Land Mine, known as Two holes were roughly punctured in the cover
“Mushroom Mine” consisted of a pressed steel thru which a grenade fuze or detomtor pro-
low cylindrical body and a dome-shaped cover jected. Contained in the box were: one Type
 J 40

91 Hand Grenade and 12 blocks I%”by %“of Ref 2, but the following Navy Sea Mines are
66.6/33 .3–RDX/Al compn, each wrapped in described in Ref 1, Chapt 111,under Japanese
waxed paper. Itcould beusedasan A/Tk Underwater Ordnance (pp 34–53):
Mine when fuzed with an armed grenade or as Contact Mines were generally spherical, with
an A/P Mine or Booby Trap when armed with several lead, steel horns screwed into the mine
pull or tension detonator (p 219, Fig 165) case. Horns were of several types but the most
~-Strip Land Mine consisted of 31 100-kg common was a lead chemical horn, such as
bombs stacked around PA blocks in which described above under Type JE Antiboat Land
electrical detonators were inserted. The ensemble Mine. Some contact mines had a long copper
was under a turf-covered piece of sheet iron wire antenna extending out of the top or
that would close the circle and fire the charge bottom of the case. Should a steel ship touch
if the iron were lifted or depressed. A clock- the antenna while both were immersed in sea
work was also inserted to fire the chge if the water, the mine would explode. Moored con-
iron were not depressed (p 220, Fig 166, upper tact mines usually had some type of safety me:
half) chanism to render them inactive if they borke
Improvised Antitank Land Mine consisted of a adrift, as well as devices to make sure the mines
wooden board serving as a base of Mod 99 were safe while aboard the mine-laying ship,
Armor-Piercing Mine on top of which was placed submarine, or plane (p 34) .
2 lbs prepd chge of PA. Two Hand Grenades Influence Sea Mines, were of various shapes, but
were placed at both sides of AP Mine and the usually they were cylindrical, like a bomb in
ensemble was covered with a board. Pressure appearance. They did not require contact with
on the board fired fuzes in grenades and this a ship in order to fire, and hence could be laid
f~ed by sympathetic detonation AP Mine and on the bottom many feet below the ship. Any
prepd charge of PA (p 220, Fig 166, lower half) physical change which took place in the water
Type JE Antiboat Land Mine consisted of a around the mine to the ship’s passageover it
hemispherical steel body 20.24” in diam & could be utilized to actuate the firing mechanism.
10.62” high contg 46.5 Ibs of Type 98 Expl, However, the most common types were magnetic
with PA Booster and Electrical Tetryl Deto- and acoustic. Any mine without horns or antenna
nator. There were two handles and two acid- was almost certairdy either an influence mine, or
lead horns on upper half of the mine. The mine else a Controlled Mine, connected by an elec-
was laid in water, flat-bottom down, and if one tric cable to the shore and fired by sending a
of the horns wa$ bent or crushed, an acid vial current thru that cable (p 35)
inside was borken, allowing the acid to drain Following is the list of Japanese Sea Mines
onto two plates of a small battery which generated used during WWII:
sufficient current to fire the detonator. As the Type 88 Model 1 Contact Mine consisted of two
wiring was series-parallel, either horn on being light-metal hemispheres separated by a cylin-
touched would act independently to fire the drical belt and provided by four chemical horns
charge (pp 221 –22, Fig 167) on upper hemisphere. It was filled with 396
Note: This mine is identical with Naval Anti- lbs of block-fitted Shimose. The depth setting
boat Mine described on p 185 of the book of hydrostat and mooring cable were provided (p
Tantum & Hoffschmidt, listed here as Ref 7. 36, Fig 1)
It was believed that the mine was designed for Type 92 Moored Controlled Mine was ellipsoidal
anti-invasion purposes to be placed in shallow in shape, 55 by 41.5 inches, filled with 1100 lbs
water against landing craft, vehicles and tanks of Type 88 Explosive. The combined control
Type JG Antiboat Land Mine, which existed in and mooring cable entered the mine thru the
5 modifications, each being actuated by a single base plate. An electric detonator and booster
chemical horn screwed into the top. The mines assembly were bolted to the chge underneath
were either bell-shaped or of a truncated cone. the top cover plate. A microphone to detect
Each contd 22 lbs of Type 98 Explosive. The the presence of ships was also provided (p 36,
mines were fired when chemical horns were Fig 2)
broken (PP 222–23, Fig 168) Type 92 Model 1 contd Type 1 Explosive and
No Sea (Amphibian) Mines are described in was without microphone (p 36, no Fig)
 J 41

Type 93 Model 1 Moored Contact Mine was located the hydrostatic arming switch. The tail
sphere-shaped 34 inches in diam and contd section broke free of the mine after laying and
220 lbs of Type “98 Explosive. Four chemicrd floated on the surface. The mine proper was
horns were located around the upper hemisphere, suspended vertically ca 6 ft under the surface
while the detonator was housed at the base (pp of water by a cable attached to the buoyant
36–7, Fig 3) tail. When the tail was separated from the
Type 93 Model 4 had six horns and was loaded mine, three sensitive switch horns sprang out
with Type 1 Explosive (p 38, Fig 4) around the base of the suspended mine. About
Type 94 Model 2 was a ground controlled hemi- 5 lbs pressure on any of the horns could fire
spherical mine with a base diam 28 inches and the mine (p 43, Figs 14 & 15)
height 25 inches, contg 190 lbs of Type 88 Type 96 Mine was ellipsoid in shape and contd
Explosive. The firing cable entered the Booster 120 lbs of Type 88 or Type 97 Expl. It was
and Detonator well thru the side of the case reported to be attached to antisubmarine nets.
(pp 38-39, Fig 5) The firing mechanism of mine was of the ten-
Mark 5 Model 1 Moored Contact Mine had sion type which detonated the mine when an
spherical case contg 180 lbs of Shimose. Four enemy’s submarine fouled a panel of the net
chemical horns were fitted to the upper hemi- (pp 44-45, Fig 16)
sphere (p 39, Fig 5) Banana Mine was the moored contact type pro-
Mark 6 Model 1 Moored Contact Mine had vided with four chemical’ horns and loaded with
spherical case, 41 inches in diam, contg 478 275 lbs of Type 88 Expl (pp 44-45, Fig 17)
lbs of Shimose. Four chemical horns were set JM Mine was moored, pear-shaped, contact mine
in the upper hemisphere (pp 39–40, Fig 7) which had no horns. The jolt received by the
Mark 6 Model 3 contd 440 lbs of Type 88 pendulum firing mechanism, when a ship struck
Expl and was provided with six horns (p 40, the mine, closed an electrical contact and fired
no Fig) the detonator. . The mine was filled with ca
Small Model Mine Model 1 was hemispherical 110 lbs of a HE (?) (pp 44-45, Fig 18)
in shape, 20 inches in base diam & 10 inches Pomegranate Mine was a Vickers antenna mine
high which contd 45 lbs of Type 98 Expl. purchased before WWII. It was spherical, 41
Two chemical horns were located on the upper inches in diam, with six chemical horns on the
surface of the case. It was set on the ground upper hemisphere and two addnl ones welded
in shallow water (pp 40–41, Fig 8) to the lower hemisphere. An upper antenna and
Small Model Mine Model 2 was truncated cone- float and/or lower antenna were secured to the
shaped case, 14 inches in base diam & 12 mine. No data for HE fdler (pp 44-45, Fig 19)
inches high, contg 22 lbs of Type 98 Expl. A Type 3 Mine was the first Japanese attempt to
single chemical horn was placed on top of the use influence mines, copied from German S
mine (p 41, Fig 10) Mine. Their cylindrical Al caseswere either 7
Type 3 Mark 1 Aircraft Mine Model 1 was or 11 feet long and 21 inches in diam. No data
cylinder 53 inches long and 24 inches diam, for HE used and the description of the mine
provided with a parachute and four chemical given in Ref 1, p 46 is hard to understand
horns. It was ftied with 240 lbs of Type 98 Mark 2 Mod 1 Explosive Hook was actually a
Explosive.. The detonator and booster were device for mine sweeping rather than a mine.
located in a tube running tramwersely thru the It was a cylinder 8 inches in diam and 10
mine case. It was dropped from an aircraft or inches long, loaded with 33 lbs max of Type 88
surface moored (p 42, Figs 11 & 12) Expl or Shimose. The device was towed under-
Type 3 Model 2 Aircraft Mine Model 2 was an water and when one of the four projecting arms
aircraft-laid drifting mine similar in appearance welded to the body fouled a mine mooring
to fin-tailed bomb, 6 ft long and 14 inches in cable, the device was electrically fired from the
. diarn. It was filled with’ 123 lbs of Type 98 towing ship (pp 46–47, Fig 21 of Ref 1)
Expl cast in the spherical nose. The detonator Addnl Ref on Mines: Ishikawa Seisakusho Co,
and booster were housed in a transverse tube Ltd, “Catalog of Various Types of Japanese
running thru the bomb, while further aft was Land and Amphibian Mines”, (1955), Kanazawa,
Japan
 J 42

Minefield. Jirai fusetsu chitai inches long attached to a pedestal resting on

a base plate. It was muzzle-loaded and was
Minethrower. Hakugekih6 fued by a continuous pull firing mechanism,
operated by a lever on the outside of discharger
Mobile Artillery. KidMiki kahG body. Used for firing 91 Hand Grenade, Pyro-
technic Signals and Smoke Shells (p 155)
Molotov Cocktail (Tenage kaenbin). See under 50-mm Grenade Discharger Model 89 (1929)
GRENADES had steel rifled-bore barrel 10 inches long at-
tached to a pedestal, resting on a base plate.
Monkan. Friction Primer The propellant chge was placed at the bottom
of barrel, held at 45 degree angle, and this was
Mooring Line. Keiryilsaki followed by projectile inserted thru muzzle
(with safeties removed). Then the trigger which
MORTARS (Kytil@ and SHELLS (Dangrrn) protruded thru a lengthwise slot in the pedestal
The following Mortars are described and il- was pulled and fued the proplnt. It was used
lustrated in the book of Tantum & Hoffschmidt, for firing Model 89 HE Shell, Model 91 Hand
listed as Ref 7: Grenade, Model 95 Smoke Shell and Incendiary
70-mm Mortar Model 11 (1922) was a rifled Shell. Range 700 yds for shell, 200 for Grenade
bore weapon which fired HE, Smoke or Illu- (p 156 of Ref 7)
minating Shells, Range 1700 yds (p 159) 32-cm (320-mm) Spigot Mortar. The spigot
8 l-mm Mortar Model 3 was a smooth-bore shown k Fig on p 170 of Ref 7 was a cylinder
weapon, forerumer of Mortar Model 97 (1937). 31.7 inches long with outside diam 10.1 inches.
It was manufd at Yokosuka Navy Arsenal. No A cavity was machined in its upper end for the
data given for length of barrel and Shells used propelling charge. In the bottom of the cavity
(p 162) there was a threaded recess for the igniter as-
81-mm Mortar Model 99 (1939) was a short sembly. An igniter train hole passed from it
25.5 inches), smooth-bore, muzzle-loading to the base of spigot. The steel mounting plate
weapon of high trajectory. Used HE Shells. in the shape of a dome was attached to a steel
Range 3200 yds for 7.2-lb Shell (p 163) base plate which rested on three layers of
8 l-mm Mortar Model 97 was similar to US heavy wooden beams
8 l-mm Mortar M 1 with length of tube (in- Accdg to Ref 3, pp 389–90, the Shell fired
cluding base cup) 49.5 inches. Fired HE by Spigot Mortar was cylindrical in shape (re-
Shells (p 165) semblirig a bomb) with ogival nose and finned
90-mrn Mortar Model 94 (1934) was smooth- tail section hollowed out to inside diam of
bore, muzzle-loading weapon with length of 10.12 inches and length 14.5 inches so that it
barrel (including base cup) 11.7 inches. Used could fit over the spigot. The shell contd
HE or Incendiary Shells. Range ca 4050 yds 103 lbs of Shimose as main chge and PETN as
with 11 .9-lb Shell (p 167) booster. Its Fuze was Type 98. The propel-
90-mm Mortar Model 97 (1937) was a “Stokes- lant chge – single-base with BkPdr as Igniter
Brandt type weapon, very similar to US 81-mm was placed in a brass pot which fitted into the
Mortar M 1. Length of barrel (interior) 48 recessed portion of the spigot tube. The chge
inches, range 4050 yds for 11.8-lb HE or In- was contd in a cardboard container having a
cendia~’ Shells (p 168) flash tube passing thru its vertical axis, thru the
150-mm Mortar Model 97 (1937) was smooth- brass pot and screwed into the spigot. Also
bore muzzle-loading weapon with length of there was a drilled and tapped hole near the
tube (internal) 66 inches. No data for its range forward end of the tail section of the shell
and shells used are given (p 169) into which the igniter tube screwed. When in
There were also two Grenade Dischargers position, the igniter tube was in close proximity
which resembled Mortars in appearance: to the end of the brass flash tube which led
50-mm Grenade Discharger Model 10 (1921) into the proplnt chge. Variations in range
consisted of a steel smooth-bore barrel 9.5 could be obtd by varying the number of in-
 -1
J 43

crements selected for the proplnt chge friction cap attached to parachute cord. Any
The following Shells for use in Army enemy plane touching a parachute cord of any
and Navy Mortars are described in Ref 3: of the seven HE cylinders would cause an ex-
Type 89 58-mm HE Mortar Shell was a light plosion” (Ref 3, pp 178–80, Fig 302 and Ref 7, ,
steel cylinder with conical nose housing a Fuze. pp 160–61)
It was filled with 5.4 oz of TNT and it was fired Type 97 and Type 100 81-mm HE Mortar
by NC-DPhA flaked proplnt fired from Type 89 Shells were in the shape of streamlined bombs.
Grenade Discharger (pp 272–73, Fig 296) Its Main Charge was TNT (ca 1,2 lbs), Booster-
Type 95 50-mm Smoke Mortar Shell was a PA and proplnt which is described here under
forged steel cylinder with conicrd nose housing PROPELLANTS. Was fired from Type 97 or
a Fuze. It contd 3.7 oz Hexachloroethane 99 Mortars (pp 380–81, Figs 303 & 304)
Smoke Mixture and was fired by NC-DPhA 81-mm Parachute HE Mortar Shell was cylin-
flaked proplnt. ~Fired from Type 89 Grenade drical in shape. Its Main Charge was RDX
Discharger (pp 374–75, Fig 297) (one block) and TNT (two blocks) – total wt
Type 89 50-mm Incendiary Mortar Shell was 4 oz. Its primer, ejection and delay charges
a sheet metal cylinder with hemispherical nose. were BkPdrs, but no data for its propellant are .
It contd 10.7 oz of Incendiary Mixture and its given. Was fired from 81-mm Smooth Bore
base was NC proplnt and two BkPdr delays. Mortars (pp 381–82, Fig 305)
Fired from Type 89 Grenade Discharger (pp 8 l-mm Parachute HE Smoke Mortar Shell was
375–76, Fig 298) similar in construction to HE Shell, except that
Type 11-Year 70-mm HE Mortar Shell was a its Maih Charge was Tetryl and it contd a smoke
light steel cylinder with conical nose housing a pellet (?) (pp 383–84, Fig 306)
Fuze. Its Main Charge was 15.2 oz TNT with 81-mm Parachute-Flare Mortar Shell was cylin-
Booster 1.6 oz of PA. Was fired by NC-DPhA drical, similar to 8 l-mm HE Mortar Shell, ex-
flaked proplnt. Fired from Type 11-Year 70-mm cept that it contd a flare compn for which no
Rifled Mortar (p 378, Fig 301) data were given (pp 384–85, Fig 307)
70-mm HE-AA Barrage Mortar Shell consisted Type 94 HE and HE Semisteel Mortar Shells
of a light-steel outer shell contg 7 canisters in were in the shape of streamlined bombs. Their
each of which was an HE cylinder and parachute. Main Charge was TNT (2.35 lbs), with pressed
A turned steel base was welded to the outer PA as Booster. Compn of proplnt not given.
shell, and provision was made for reception of Was fired from Type 94 or 97 90-mm Mortars
a delay train holder, a shell proplnt container, (PP 385-86, Figs 308& 309)
and an end cover. The delay train led to a Bk- Type 94 90-mm Incendiary Mortar Shelt was
Pdr chge which ejected the canisters from the similar to Type 94 HE, except that it contd
shell. Total wt of Main chge 12.84g of RDX, Incendiary filling consisting of WP, CS2 & 40
with Booster of LA (Lead Azide) cylindrical rubber pellets (2.2 lbs). It also
We are not describing the construction contd Burster Chge and Proplnt of unknown
of this shell in detail because it is very compli- compn (pp 386–87, Fig 310)
cated and requires detailed illustrations. It Type 2 120-mm HE Mortar Shell was stream-
suffices to say that the Shell was fired by lined in shape, contg 6.0 lbs of TNT with
dropping it into a smooth-bore Mortar, 4 feet RDX/Wax Booster. No data for proplnt. Was
long, attached to a base plate, a rectangular fired from Type 2 120-mm Smooth Bore Mor-
wooden block and an iron rod which was stuck tar (pp 387–88, Fig 3 11)
into the ground to hold the Mortar upright. Type 96 150-mm HE Mortar Shell was stream-
This weapon, known as 70-mm AA Barrage lined in appearance contg 12.9 lbs of TNT as
Mortar, was fired at the time of approach of Main Charge with PA as Booster. Compn of
low-flying enemy aircraft so that it released proplnt is given under PROPELLANTS. Was
from each shell 16 parachute-provided cylinders fired from Type 96 150-mm Smooth-Bore
which were suspended in the air forming a Mortar (p 388, Fig 312)
kind of barrage. Seven of these cylinders contd Type 97 150-mm HE Mortar Shell was a shorter
HE chge of RDX-LA which was connected to a version of Type 96. It contd 9.98 lbs of TNT
 J 44

and RDX/Wax Booster. Its proplnt was the Nitroglycerol (Nitoroguriserin). Described in
same as for Type 96 (pp 388–89, Fig 3 13) Vol 6 of Encycl, under, GLYCEROL TRl-
32-cm Spigot Type Mortar Shell is described NITRATE, pp G98ff. It was used in Dynamites
under 32-cm (320-mm) Spigot Mortar (See under Dainamaito) and in Double-Base
Propellants (See under PROPELLANTS)
Mountain Artillery. Sampi5hei
Nose (of Projectile). Dant6
Muenkayaku or Muenyaku. Smokeless Propel-
lant. See under PROPELLANTS I Nose Fuze. Dant6 shinkan

Munitions. Gunjuhin Obturation. Kinsoku

Mustard Gas. Masiitado gasu; Iperitto gasu Offensive. Kosei

Muzzle. H6ko (Arty); Jiik6 (Small Arms) Onayaku. A yellow, castable expl compn con-
sisting of PA (Picric Acid) 50 & DNN (Dinitro-
Muzzle-Loader. Zens6h6 naphthalene) 50%, which melts below 120°.
Its Brisance, Power and Rate of Detonation were
Muzzle Velocity. Shosoku lower than those for straight PA and it was less
sensitive to Impact than PA. Used as Bursting
Naval. Kaigan no Charge in Artillery Projectiles, such as in 7-cm
(75-mm) HE-AA Proj, listed in Ref 3, p 318
Navigation Markers. See under Markers and There was also, accdg to documents, mixture
Indicators of PA 80 & DNN 2070 which was identical with
Frantsuzskaya Sines’ used by the Russians (Ref
Navy. Kaigun 1, p 26&Ref 5, p368)

Nigotanoyaku-Mk 2. Pale-ye] or cream expl Oshitsuyaku. Accdg to Ref 5, pp 367 & 368,
mixts of TNT & RDX (70/30, 60/40 & 50/50). it is identical with Koshitsu (qv)
Its 50/50 Compn is called in Ref 2, p 30 “Army
Mk 2 Explosive” or Tan6yaku, but accdg to Oshiyaku. A yel, press-loaded expl compn con-
Ref 5, p 373, Tan5yaku contd TNT, RDX & sisting of PA 90 & wax 10YO. It was much less
7–10% Tetryl. Accdg to Ref 5, p 368, the sensitive to Impact & Friction than straight PA
50/50 version was called Chauyaku and had lower Brisance, Power and Rate of De-
Nigotanyaku expls were used in many types tonation. It was used as Bursting Charge in
of Army Ordnance (Ref 1, p 27). Accdg to nose of some Armor-Piercing Projs, such as
Ref 5, p 368, they were used in Bombs, Shells, Type 95 7-cm (70-mm) AP Proj listed in Ref 3,
Land Mines and Bangalore Torpedoes. The p 309 (See also Ref 1, p 26 & Ref 5, p 368)
53/47 –TNT/RDX version was used in Demoli-
tion Charges Oshokuyaku (Army), Shimose bakuyaku (Navy)
or Pikurinsan. Picric Acid (PA), HO.C ~H2(N02)3;
. Nitoroguriserin
muenyaku. Nitroglycerol or mw 229.11, N 18.34%; yel trysts, density 1.76,
Double-Base Propellants. See under PRO- mp 122°, Brisance by Sand Test 113% TNT;
PELLANTS Explosion Temp 320° (decomp); Power by
Ballistic Mortar 112% TNT; Rate of Detonation
Nitrocelluloses (Sh6kamen), such as described 7350m/sec for cast (Shimose) vs 6900 for TNT;
in Vol 2 of Encycl under CELLULOSE, were Impact Sensitivity by BurMinesApp with 2-kg
used in NC Propellants (Sh6kayaku) or Single- weight 85cm vs 100 for TNT [AMCP 706-177
Base Proplnts. See under PROPELLANTS (1971), p 288], Used by the Japanese Army as
a press-loaded Booster Charge in Bombs, Shells,
Nitrocotton. Menkayaku Mines and Standard Demolition Charges. Used
 J 45

cast, under the name of Shimose, as Bursting Power by Ballistic Mortar 99% TNT; Rate of De-
Charge in some Bombs, Shells, Torpedoes & tonation 6850m/s vs 6900 for TNT. Used in
Mines. Also used in some expl compns, such as composite expls: Type 1, Type 1 Mk 5P5, Type
Cha3yaku, Onayaku & Osh@aku (Ref 1, pp 1 Mk 6 and others (Ref 5, p 369)
25,26 & 31 and Ref 5, p 369)
Point Detonating Fuze. Dantobakkan; Danto
Otsu-B, Type A or A (ko) A dark
Explosive. shinkanen
green expl compn of TNT 60, HNDPhA (Hexa.
nitrodiphenylarnine) 24 & Al pdr 16Y0. Used Powder (Kayaku; Bakuyaku). See PROPEL-
by the Navy for loading Torpedo Warheads, LANTS
Sea Mines and Depth Charges. It was identical
with German expl compn Schiesswolle 18 oder Powder Bag. YakunB
TSMVI-101, described in PATR 2510 (1958),
p Ger 177-L (See also Ref 1, p 32 & Ref 5, Powder Charge. S6yaku
p 361, under “A (ko) Explosiv~)
Powder Train. D6kasen
Paper Balloons. See Balloons, Paper
Primer. Bakkan
Parachute Flare (Ch6k6 sh6meidan). See under
FLARES , Primer Charge. Kibakusai

Penetration (of Projectile). Shintetsu Projectile (Dangan; Shadan). See under AMMU-
NITION
Pentolite. See Pentoriru
PROPELLANTS (H5shayaku).
Pentoriru (Pentolite). A pale yel or cream expl There were 1) Smoke Propellants (or Non-’
compn of PETN (Pentaerythritol Tetranitrate) smokeless Propellants), called Yuenyaku, which
50, coated with TNT 50%, density 1.65, Bri- were Black Powder called Kokushokuyaku
sance by Sand Test 125!Z0TNT, Explosion (Ref 1, p 27) and Brown Powder called Kassho-
Temp – decomposes at 220° in 5 sees;Power kuyaku (Ref 1, p 30). They are described here
by Ballistic Mortar 126% TNT, Impact Sensi- under K’s and 2) Smokeless Propellants of
tivity by BurMinesApp with 2-kg wt 34 cm vs, general term Muenkuyaku or Muenyaku.
100 for TNT; Rate of Detonation for cast The following Smokeless Propellants were
7465m/sec vs 6900 for TNT [AMCP 706-177 used by the Japanese:
(1971), p 272]. Used in Navy 20& 30-mm A) Nitrocelhdose or Single-Base Propellants
Projs (Ref 1, p 33) and in some Shaped Charges (Shdcayaku) contd NC (Nitrocellulose) (ca
(Ref 5, p 369) (See also Ref 3, p 441) 12.5% N) 98 & DPhA (Diphenylamine) 2%.
Used to propel many projectiles (Ref 1, p 30).
PETN (Pentaerythritol Tetranitrate). See A slightly different formulation is given on p 33
Shoeyaku of Ref 1: NC 98.0, DPhA 0.8, DNT 0.95 &
graphite 0.25%
Picric Acid (PA) (Pikurinsan). See Oshokuyaku Single-base proplnts were subdivided accdg
(Army) and Shirnose Bakuyaku (Navy) to shape and sizes of grains into Mk 1 (squares
of flat strips); Mk2 (squares); Mk3 (strips);
Pikurinsan Ammonia (Ammonium Picrate) is Mk 4 (strips) and Mk 5 (strips) (Ref 3, pp 346
described as Explosive D’ in AMCP 706-177 & 357). There were also graphited proplnts
(-1971), P 136> (OZN)SCtSH*.0NH4; mw 246.24, made of single-perforated cylinders. They were
N 22.76%; yel trysts, d 1.72, mp–decomp at used in Types 97 & 98 20-mm Ammunition
265°; Brisance by Sand Test ca 92% TNT; (Ref 3, p 280)
Explosion Temp, decomp in 5 sees at 3 18°; B) Double-Base (NC–NG) Propellants included:
Impact Sensitivity BurMinesApp, 2-kg Wt > 100cm; a) NC 67.8, NG 29.3, DPhA 0.7 & NaCl 2,.2Y0.
 J 46

Used for propelling some Mortar Projectiles Raigeki suru. Torpedo

(Ref 1, p 30)
b) NC 65.6, NC 29.2, Ethyl Centrality 3.7 & Raikan: Percussion Primer or Cap
NaCl 1.5%. Used for propelling many Artillery
Shells (Ref 1, p 33) ~ Raiko (Army) or Raisansuigin (Navy) “Thunder
c) NC 60.0, NC 34.5, Ethyl Centrality 3.0 & Mercury”. Afercuric Fulminate, Hg(ONC)2; mw
Diphenylformamide 2.5%. Used to propel 284.65, N 9.84%; white to gray pdr, d 4.43,
Type 1 47-mm HE & AP Shells (Ref 3, pp mp–decomp or detonates without melting;
298–99), Brisance by Sand Test–ca 55% TNT; Expln
d) Smokeless Double-Base Propellant B aruilyzed Ternp 210° in 5 sees; Impact Sensitivityy,
in US: NC 63.50, NC 27.71, Ethyl Centrality BurMinesApp, 2-kg wt–5cm; Power by Trauzl
3.8, Diphenylformamide 3.68, volatiles 1.30, Test–51% TNT; Rate of Deton 5000 at d 4.0.
graphite 0.45 and ash 0.34%. Consisted of (AMCP 706-177, listed as Ref 8, p 201). Used
single perforated cylinders of various lengths straight by the Japanese in Instantaneous Fuzes,
for use in 20-cm HE Spin-Stabilized Rockets in Blasting Caps and in mixture called Bakufun
(Ref 3, p 372) (Ref 1, p 25 & Ref 5, p 369)
e) NC & graphite 58.0, NC 7.1, DNT 25.7,
DPhA 0.5 & K nitrate 8.7%. Used to propel Rakkasan. Parachute
Type 97 81-mm HE Mortar Shell (Ref 3, p 380),
Type 96 & 97 150-mm HE Mortar Shells (Ref Range (of Weapon). Shatei
3, pp 388 & 389)
f) Propellant for “Baka” Rocket Bomb: NC Remit. Hand6 suru or K6za sura
59.9, NC 26.9, MNN (Mononitronaphthalene)
6.1, EtCentra.lite 2.9 & volatiles 1.3%(Ref 2, p 118) Relay. Denkeiki
g) Special DT6 Double-Base Propellant: NC
60.0, NC 29.3, EtCentralite 2.85 & MNN (Mono- Rempatsuju. Magazine Rifle or Repeating
nitronaphthalene) 6.14% consisted of single- Rifle
perforated grains. Was used to propel 12-cm
Incendiary-Shrapnel Rocket (Ref 3, p 514), Rentaiho. Regimental Cannon
20-cm HE Rocket (Ref 3, p 515) and 45-cm
HE Rocket (Ref 3, p 516) Report (Explosion). Bakusei

Proving Ground. Shiken shagekijti Resshahohei. Railway ArtilleW

Proximity Bomb, Type 5 NO 25 Mk 33 is de- Ricochet. Chi5dan

scribed in Ref 2, p 93, Fig 70 on p 92
Rifle. Sh5jD
Pyrotechnic Pistol. Shing5 kenjti
Rifle Grenade. Jliy6 tekidan
Pyrotechnics. Shing5dan
Rikugun. Army, Land Forces
Pyrotechnic Signal. Kasen shingo
Rin. Phosphorus
Quickmatch. Kyiinen kasaku
ROCKET (or Roketto) (Funshindan) or Rocket
Raibun (Enka)(Thunder Powder or Smoke and Ammunition Raketto Danyaku) can be defined
Fire) consisted of K chlorate 60 & Arsenic as any self-propelled, unguided missile which is
Sulfide 40%. Lt gray to tan powder used in fired from a device called a Lruncher, as was
fuze and pyrotechnic primers. Comp with Ger Faustpatrone, Russian Katiusha or Amer
Bakufun (Ref 1, p 25; Ref 5, p 369, where its Bazooka. Japanese launchers are briefly de-
compn is erroneously given as K chlorate 60 & scribed here under ROCKET LAUNCHERS.
Antimony sulfide 40%) Each Rocket Missile carried its own propeller
 J 47

type motor (described here under Rocket ROCKET LAUNCHERS and PROJECTORS
Motors) and a warhead contg an HE, Incendiary (Roketto Hasshaki).
or Chemical Agent (Vol 1 of Encycl, p A384-R) Accdg to Refs I &R, Japanese Rocket
(See also ROCKETS) Launchers were mostly wooden troughs, others
were guide rails and steel barrels (tubes).
ROCKET BOMBS (Roketto bakudan). Launchers were provided with some electric
The following Navy Rocket Bombs are listed ignition device. The most practical launcher
in Ref 2: was used by the Japanese Army under the
Type 5 No 1 Mk 9 Model 1 and Type 3 No 6 name: Type 4 20-cm Rocket Launcher, de-
Mk 9 Bombs were fii stabilized and closely re- scribed in Ref 1, p 204 and shown in Fig 320
sembled American Aircraft-launched Rockets. on p 206. It consisted fo a metal tube on a
Both carried HE Fillers and small charges of mounting permitting fine adjustments in eleva-
Propellant (p 71 of Ref 2;’ no Fig) tion and train. The launcher was in three parts
Type 3 No 6 Mk 27 Rocket Bomb Model 1 which could easily be disassembled for trans-
was fro-stabilized, aircraft-launched, designed portation. A rate of fire of from 1 to 2 rounds
for use against formations of large enemy per minute could be obtd
planes. It was cylindrical in shape with conical Other launchers listed and illustrated in
nose section which contd a Fuze, a Burster Ref 1 were:
Charge and an Incendiary Shrapnel, consisting 20-cm Rocket Launcher consisting of a wooden
of WP (White Phosphorus) fdled steel pellets. trough, 7 feet long, held in an inclined position
Its cylindrical part contd Ballistite type Pro- by a biped (p 205 & Fig 329 on p 209)
pellant in grains 350mm long and 19.2mm in 20-cm Rocket Launcher consisted of a steel
diam. Its tail section was constricted to form barrel (tube) mounted on 10-ft wheels (p 205
a venturi for the escape of driving gases. This & Fig 330 on p 209)
Rocket, rdong with Type 3 No 1 Mk 28 Model 45-cm Rocket consisting of a wooden trough
1, was the only Navy Rocket which was actually mounted on wheels. Was good for one shot
under production at the end of WWII (p 84 & only (p 205 & Fig 331 on p 209)
Fig 65 on p 85) Special Mark 1 Model 21 Launcher for 250-kg
Type 3 No 1 Mk 28 Rocket Bomb Model 1 Rocket Bomb consisted of a wooden trough
was to a certain degree similar to Type 3 No 6, 22 feet long (p 25)
except that it contd HE Filler instead of In- 12-cm Incendiary Shrapnel Rocket Launcher
cendiary (pp 86–87, Fig 66) consisted of a wooden trough installed fore and
“Baka” Piloted Rocket Bomb was a suicide aft on “Suicide Boats” (qv). Later models
weapon designed to be controlled by a human were adjustable in elevation (p 25)
pilot. It resembled a plane, was carried be- In the book of Tantum & Hoffschmidt
neath -the fuselage of a bomber and released (Ref 8), the following Rocket Launchers and
near its target. Three Type”4 Mk 1 Rocket Rocket Projectiles are described and illustrated:
Motors provided propulsion after “Baka” was 20-cm Rocket Projectile and Launcher (p 171).
released from the mother plane. The entire HE me ground-launched Rocket, 2 1.05cm in diam,
content of the “Baka” (1 135 lbs of Type 91 described here under ROCKETS was fired from
Expl) (Trinitroanisole) was in the warhead of a trough-shaped launcher ca 7 ft long, which
the nose. “Baka” was’19 ft 10 inches long with weighed ca 175 lbs. Range of 1970 yds at
wingspread 16 ft 5 inches. Its warhead had Nose 50 degree elevation was claimed (See also Ref 1,
and Tail Fuzes (pp 116–17, Fig 88) p 205)
Type 4 Mk 1 Launching Rocket (“Baka” Motor) Rocket Launcher and Rocket Motor Model 10
was cylindrical in shape with conical nose and (p 172) was designed to propel the 60-kg air-
venturi tube tail. It contd 97.8 lbs double-base craft bomb out of an inclined trough. The
proplnt of compn listed under PROPELLANTS, launcher was constructed of wood and metal
item f. Three of such devices, located in fuselage with legs made of iron pikes. The launcher
of “Baka”, served as the main propulsion units channel was a right angle wooden trough, ca
(Ref 2, p 118, Fig 89) 20 ft long with a motor and bomb positioner
 7

J 48

made of 1/f I-inch pierced sheet metal. The rear Electric Igniter with BkPdr charge. The unit
of launcher was attached by a pin to a base was launched from a crude wooden trough
plate. Elevation was controlled by cables run mounted on a biped forward and a steel base
from the base plate to the legs, and between them plate aft (Ref 2, pp 119–20, Fig 90)
The Rocket Motor resembled a blunt short-
bodied, fin-stabilized, bomb provided with a ROCKETS (Roketto) or ROCKET PROJECTILES
venturi tube at its rear. The propellant (12.94 (Roketto Dangan)
lbs) which consisted of three cylindrical sticks Japanese Rockets are subdivided into Army
tied in a silk bag, was in a cylindrical container Rockets (Ref 1, p 204 & Ref 3, pp 371–72)
located above the venturi tube. The chge was and Navy Rockets (Ref 1, pp 204–05 & Ref 3,
ignited by an Igniter Pad and an Igniter Fuze pp 514–16)
in the forward part of the motor by means of The following Rockets are described with
wires leading to a small Hand Blasting Machine. illustrations:
When f~ed the motor propelled the Rocket Type 4 20-cm Army Rocket was spin-stabilized,
from the launcher and then dropped off. cylindrical in shape, 37 inches long, (including
Ranges up to 1300 yds were claimed, but ac- ogive nose) weighing 180 Ibs and contg HE chge
curacy was very poor of TNT and Ballistite as propellant (Ref 1, p 204)
These devices are described in Ref 2, pp 20-cm HE Army Spin-Stabilized Rocket, cylin-
120–2 1, Fig 91), under the title “Type 3 and drical in shape, 38.58 inches long (including
Model 10 Bomb Launching Devices”. The de- ogive nose), weighing 186.3 lbs and contg cast
scription includes the compn of proplnt used TNT as HE Filler and Smokeless Double-Base
in Rocket Mortar as: NC 65, NC 30, Et Powder B, described here as item d, under
Centrality 3.0 & NaCl 2.0%. It was code- Propellants (Ref 3, pp 371–72)
designated by the Japanese as “343 DT2” Note: This Rocket seems to be identical ‘with
and was ignited by an electric squib the one described in Ref 1, p 204
Navy Rockets were HE (two kinds) and In-
Rocket Motors (Roketto Hasshaki) are devices cendiary (one kind). They are listed in Ref 1,
designed to provide propulsive power (propel pp 204-05, but not described. The following
or launch) to a Bomb or Rocket Projectile of are described in Ref 3:
an inclined trough or barrel called Launchers 12-cm Incendiary-Shrapnel Spin-Stabilized Rocket
One of such Rocket Motors is described and was cylindrical in shape with ogive nose, overall
illustrated in the book of Tantum & Hoffschmidt length ca 28.5 inches, weight 51 lbs, which in-
(Ref 7, p 172) under the title “Rocket Launcher cluded Fuze, 4.75 oz PA burster chge, 10 lbs
and Rocket Motor Model 10”. It is briefly 10.75 oz of Incendiary cylinder contg WP
described here under Rocket Launchers. They pellets, 7 lbs 5 oz Special DT6 Propellant
are also described in Ref 2, pp 120– 1 (listed as item g under PROPELLANTS) and
Another Rocket Mortar (Type 4 Mk 1) is Ignition Mechanism. It was launched from a
described here under ROCKET BOMBS as a wooden trough mounted one on each side of
device used to propel “Baka” Piloted Rocket the cockpit of a Suicide Boat (qv) (Ref 3Y p
Bomb (Ref 2, p 118) 514, Fig 423)
There was also “Special Mk 1 Rocket Motor 20-cm HE Spin-Stabilized Rocket had an artfl-
Model 21” which consisted of a cylinder 80.3 lery-projectile shape body, overall length (w/o
inches long & 11.8 inches in diam with rounded Fuze) 40.28 inches, weight ca 200 lbs, which
nose and a venturi tube attached at the rear. included: Fuze 38.58 lbs cast Type 91 Expl
This unit was designed as an integral type bomb (TNAns), Fuze, Propellant (1 8.3 lb) Special ~
pusher for launching 250-kg Bombs from ground DT2 (no data) or Specird DT6 (listed as item g
launchers for land bombardment. Its motor under PROPELLANTS) and Ignition Mechanism.
weighed 429.2 lbs, while wt of proplnt was Three signal-round launchers were desi~ed for
178.2 lbs, consisting of 20 sticks of “343 this Rocket., Two of them were trough-type,
Special DT2” which qontd NC 65, NC 30, Et while the 3rd was a barrel type launcher. In
Centrality 3.0 & NaCl 2.0%. It was ignited by addn a triple-mount trough was used (Ref 3,
 J 49

p 515, Fig 424). Same Rocket is described in ture of K chlorate, sulfur, ground coal (or sugar),
Ref 8, p 171 iron filings and wax compressed in the shape of
45-cm HE Spin-Stabilized Rocket was cylin- a regular US brick. It was coated with paint to
drical in shape with conical nose, length (w/o give it the appearance of a glazed brick. As
Fuze) 67.5 inches, weight 1514 lbs, which in- there was no Igniter, one of the methods used
cluded 401.0 lbs of Type 98 Expl (PA), 131.5 to ignite the brick was to place some K per-
lbs Special DT6 Proplnt (listed as item g under manganate on top of it and pour coned sulfuric
PROPELLANTS) and Ignition system. A crude acid over it (p 262, Fig 199)
wooden-type launcher was used with this Rocket Incendiary Soap consisted of a mixture of Ba
(Ref 3, p 516, Fig 425) nitrate 30.4, paraffin 19.4, Mg 11.3, Al 11.1,
rosin 10.9, ferroso-ferric oxide 9.1, NC 4.4’&
Roketto. See ROCKETS gritty siliceous material 2.6%, compressed into
a regular soap bar. Its method of ignition by
Roketto-shiki tekidan. Antitank (A/Tk) Rocket the Japanese is not known
Following items which are actually Sabotage
Ryudampo. Howitzer Devices are described in Ref 1, pp 23 1–32:
Sucker Traps were devices set in living quarters,
Ryusandan. Shrapnel Shell abandoned equipment, etc, mainly for the pur-
pose of lowering the enemy’s morale. Besides
SABOTAGE DEVICES (B5gy6 s6chi; Hasai the various Booby Traps described here under
b~ryaku). MINES, the following items were used by the
Under this term may be included any item Japanese:
intended to produce malicious injury to people, Explosive Radio, contd HE charge occupying
machinery, tools, etc; practiced mostly during the space obtd after removing all batteries
the wars except one. When the switch was turned on,
The following Japanese Sabotage Devices are the electric circuit closed (p 231, Fig 377)
described in Ref 2, pp 258–63: Explosive Phonograph. An electric contact on
Explosive Toothpaste consisted of a toothpaste the pick-up was so arranged that sufficient
tube fried with 4.23 oz of a mixture of RDX movement of the arm to play a record would
80.2 & mineral oil with wax 19.8% and provided close the circuit and set off the charge of ex-
with an Igniter (p 258, Fig 195) plosive, concealed with battery under floor-
Explosive Coal consisted of thin earthenware board (p 231, Fig 378)
cent ainers of irregular shape coated with a Explosive Telephone. A pull-igniter fitted to an
bituminous type paint. Each piece was filled expl chge was placed inside a telephone. The
with RDX and contd an Igniter with Detonator line from the’ igniter was secured to the crank
and a small chge of BkPdr. When exposed to of the telephone so that an attempt to ring
fire the heat eventually ignited the BkPdr chge, would set off the charge (p 232, Fig 379)
which in turn set off the Detonator and RDX “Tin Can” Booby Trap consisted of a regular
(p 259, Fig 196) American tin can which was filled with expl
Explosive Food Cans consisted of regular tin chge and provided with a friction pull igniter
cans with American labels such as “Libby’s and trip wire (p 232, Fig 380)
Strawberries”. They contd 1.37 lbs of a mixt
of RDX 78.3 & mineral oil 21.7’% and were Safety Fuze. D6kasaku
provided with an Igniter, Delay and Detonator
(PP 260-61, Fig 197) Safety Pin. Anzensen
Metal Incendiary Cylinders were 6% inches
long and 2% inches in diam filled with Thermite Sairetsu teryudan. Fragmentation Grenade
(Incendiary) and provided with two Igniters,
Delay and First Fire Charge consisting of KC103, Sairetsu toka bakudan. Fragmentation Bomb
Sb2S3 &Al pdr (pp 261–62, Fig 198)
Incendiary Brick consists of an incendiary mix- Sakuma Dainamaito. One of the Japan Dynamites
 J 50

Sakura No 1 & No 2. Blasting Gelatin Sentei. Groove, Rifling

Sakuretsu. Burst, Explosion Sento. Battle, Combat

Sakuyaku. Bursting Charge Sento bakugekiki. Fighter Bomber

Sampoei. Mountain Artillery “ Sentokan. Battleship

sandanju. Shotgun Shadan. Projectile

Sanshoki mechiru nitroamin (Tetryl). See Meiayaku Shakunetsuzai (Therrnite). An incendiary mix-
ture of AI & Fe304, which can be ignited by
Sanshoki toruoru or Type 92. See Chakatsuyaku Mg. Used in admixture with BkPdr or HE’s
for loading some incendiary items of Ammuni-
Seacoast Artillery. Kaiganho tion, while the majority of such items contd
WP(White Phosphorus)
Sea Markers. See under Smoke Floats and under Following incendiary items contd Thermite:
Markers and Indicators l-kg and 5-kg Thermite Incendiary Bombs
(Ref 2, p 15) “
Seigata (Army), Type 97H (Navy) (German Type 98 No 7 Mk 6 Model 1 Incendiary Bomb
liexarnit). A lt yel to orn, castable expl mis- (Ref 2, p 71)
ture of TNT 60 & HNDPhA (Hexanitrodiphenyl- Metal Incendiary Cylinders, used as a Sabotage
amine) 40%. Density 1.65 (cast), Brisance by Device (Ref 2, p 261)
Cu cylinder crusher test 96% of PA; Expln
Temp 3020+; Impact Sensitivity, 14cm max for Shakyori. Range
no explns with 5-kg wt; Power by Ballistic
Mortar 92% PA; Rate of Deton 7 100m/s vs Shaped Charge. See Hollow Charge [Ta(dan)]
6900 for TNT. It was used at the beginning of
WWII for loading some Torpedo Warheads, but Shell. H6dan
later replaced by A(ko) (Type A Expl); was
also used in some Depth Charges and Navy Shikan. Adapter
Rockets (Ref 1, p 32 & Ref 5, p 370)
Shimose Bakuyaku (Navy) or Oshokuyaku (Army)
Self-Propelled Guns. guns mounted on
All
combat vehicles may be considered Self-Pro- Shingodan. Pyrotechnic;
pelled Guns. These vehicles include Tankettes
(Ref 8, pp 117-19), Tanks (p 120-29) and Shingo kasen. Signal Rocket
Armored Cars (pp 132–35). Only one of these
is listed as “self-propelled”. It is 150-mm Self- Shingo kenju. Signal Pistol, V&y Pistol
Propelled Howitzer, Type 38 Year (1905) which
is mounted on medium tank chassis. Its detailed Shinkan. Fuze
description and illustration are given on p 129
of Ref 8 Shinkan kibakuzai. Fuze Detonator

Semisteel Bomb. Koseisen bakudan Shin-kiri or Shinkyoryoki. Gelatin Dynamite

Senshaho. Tank Gun Shinko. Cavity (of Projectile)

Senso. War Shinshoku. Erosion, Corrosion

Sensuikan. Submarine Shintetsu. Penetration (of Projectile)

 J 51

Shin-toku shoan. Ammonium Nitrate Dynamite Shogeki. Impact; Shock

Shiraume. Gelatin Dynamite Shogeki shinkan. Impact Fuze

Shoan bakuyaku. An AN (Ammonium Nitrate) Shoidan. Incendiary Shell

explosive used in Army Substitute De
compn
molition Charges: AN 79, DNN (Dinitromph- Shoiyo bakudan. Incendiary Bomb
thalene) 10, sawdust 1 & NaCl lWO. TNT
could replace DNN (Ref 1, p 29 & Ref 5, p Shoiyo tekidan. Incendiary Grenade
371)
Shoju. Rifle
Shoanbakuyaku Nos 104 & 201. Ammonium
Nitrate Dynamite Shokaki. Small Arrns

Shoanyaku. A series of cord-mining expls Shokamen. Nitrocelh.rlose (NC)

manufactured at the Uji Factory (Kyoto Pre-
fecture): Shokayaku (Nitrocellulose Propellant). See
No 1.. AN 70, DNN 9, woodmeal 1 & NaCl 20% under PROPELLANTS
No 2. Same as Shoan bakuyaku (See previous
item) Shokuhatsu jirai. Contact Mine
No 5. AN 64, TNT 12, woodmeal 3, wheat
starch 1 & NaCl 13% Shomeidan. Illuminating Shell; Parachute -
No 7. AN 75, DNN 9, TNT 1.5, woodmeal 1.5 Flare
& NaCl 13%
Special; AN 64, DNN 3, TNT 7, GuN (Guani- Shonayaku. Yel-brn expl mixture of AN 90
dine Nitrate) 2, Na nitrate 2, woodmeal 2 & & DNN 10% used for loading cast semisteel
NaCl 20% Shells, Land Mines and Demolition Charges.
These expls were reported to have Impact It was suitable for tunnel work because it did
Test Vrdue with 2-kg Weight ca 80cm and Gap not give toxic fumes (Ref 1, p 27 & Ref 5, p
Test Values 100 to 150mm. Some of the mix- 372)
tures were used for military purposes (Ref 5,
p 371) Shosan. Nitric Acid

Shobenyaku. See Anbenyaku Shosoku. Muzzle Velocity

Shoeiyaku. Pentaerythritol Tetranitrate (PETN), Shotgun. Sandanjii

C(CH20N02)4; mw 316.14, N 17.72%; wh
trysts, d 1.77, mp 14 1°; Brisance by Plate Dent Shotoyaku (Amatol). A mixture of AN 50&
Test 129% TNT; Explosion T~mperature 225° TNT 50% of brown color, d (cast) 1.59, mp
(decomp. in 5 sees); Impact Sensitivity BurMines- 810+, Brisance by Plate Dent Test 52% TNT;
App, 2-kg Wt 17cm (VS 100+ for TNT); Power Expln Temp 265° (dec in 5 sees); Impact Sen-
by Ballistic Mortar Test 145% TNT; Rate of sitivity BurMinesApp 2-kg Wt 95cm; Power by
Detonation 8300m/sec (Ref 8, p 276). Pressed Ballistic Mortar 124% TNT; Rate of Detonation
PETN was used in Army 7.7 & 12.7-mm Fuze- 6430m/sec (Ref 8, p 16). Was used in same’
less Projectiles and 20-mm MC Projs. Also in Bombs and in Semisteel (high C cast iron)
Boosters. Its mixt with TNT is called Pentoriru Shells. Was reported to be found in some Navy
(qv). PETN with 8.5% wax was used for loading Mines (Ref 1, p 27 & Ref 5, p 372)
20-mm Shells. Its mixtures with RDX were
used in 7.7 & 12.7-mm Projectiles. PETN was Shouyaku or Tanayaku (RDX or Cyclonite),
also used in Incendiary Mixtures (Ref 1, p 27 02N.N–CH2— N.N02
& Ref 5, p 372)
H2C–N(N02)–CH2; mw 222.13, N 37.84%;
 J 52

wh trysts, d 1.82, mp 204°; Brisance by Plate Smoke Grenades. See under Grenades
Dent Test 135% TNT; Expln Temp 260° (dec
in 5 sees); Impact Sensitivity, BurMinesApp, Smokeless Powder (Muenkayaku). See under
2-kg Wt 32cm; Power by Ballistic Mortar 150% PROPELLANTS
TNT; Rate of Deton 8180m/sec (Ref 8, p 60).
Straight RDX was used as Booster and Sub- Smokeless Powder B. See item d under PRO-
Booster in some Army Fuzes, and as Bursting PELLANTS
Chge in 20-mm HE Shells. When desensitized
with wax, it was used in 37-mm HE Shell Smoke Powder. Yuenyaku (Nonsmokeless
(Ref 1, p 26& Ref 3, pp 282 & 290) Powder) (Ref 1, p 27)
The following expl compns, contg RDX,
Angayaku, Chauyaku, Haishokuyaku, Koshitsu, Smoke-Producing Materials. Following are
Nigotanoyaku-Mk 2, Tan5yaku, Type 94M examples of materirds used by the Japanese
Explosive and Unknown Name Explosives were for producing smokes:
used as Bursting Charges of Bombs and Shells a) FS Smoke, chlorosulfonic acid 41, sulfur
(Ref 5, p 373) trioxide 54 & sulfuric acid 5%. Used in Type
100 50-kg Smoke Bomb (Ref 2, p 21)
Shrapnel Shell. Rylisandan b) Mixture of titanium & silicon tetrachloride;
used in Frangible Smoke Grenade (Ref 2, p 239)
Single-Base Propellants. See under PROPELLANTS c) Mixture of hexachloroethane (HC) 56.2,
Zn 27.6, “Zn chloride 2.9 & Zn oxide 13.3%;
Smoke. Kemurie (en) used in Smoke Rifle Grenade (Ref 2, p 243)
d) White phosphorus (wP), used in Type 90
Smoke Agent. Hantsuenzai 75-mm Smoke (WP) Projectile (Ref 3, p 336)
e) WP in Type 13-Year 150-mm Smoke (lVP)
Smoke Bomb (Hatsuen bakudan). One of such Projectile (Ref 3, p 367)
bombs is described here under “Markers and f) Berger Mistures, probably similar to the ones
Indicators” and also in Ref 2, p 113-R as Type described in Vol 2 of Encycl, p 102-L, were used
2 2-kg Target Indicator. A larger Bomb, in Smoke Candles listed in Ref 1, p 255 (Compn
weighing 155 lbs, called Type 3, No 6 Target ,. of Japan mixture not given)
Marker Bomb is also described here and in g) Hexachloroethane (HC) Mixture used in Type
Ref 2, p 113-L 95 50-mm Smoke Mortar (Ref 3, pp 3 & 14)
h) WP, presumably was used in 140-mm Navy
Smoke Candles (Hatsuent6). See under Smoke Smoke Projectile (Ref 3, p 494)
Pyrotechnics i) FM (Titanium Tetrachloride) used in Navy
Type 2 Target Indicator (Ref 1, p 246)
Smoke Floats are devices seining as “Sea j) Tannic Acid smoke compn used in Type 94
Markers”. Following are examples: 4-kg Practice Bomb (Ref 2, p 28)
2-kg Smoke Float was a bomb-resembling “de-
vice, weighing 4.75 lbs, thrown by hand. It Smoke Projectile or Shell (Hatsuendan). See
contd an igniter and a smoke-producing compn under AMMUNITION and in Ref 3, pp 336, 367,
(no data) (Ref 2, II 109. Fig 82). 374 & 494
43-kg Smoke Float consisted of long conicrd
nose and cylindrical tail contg a parachute. Smoke Projector. Emmaku h~shaki
Its nose section contd smoke compn and an
igniter. It was thrown from a plane (Ref 2, Smoke Pyrotechnics (seizo-jtitsu). The following
p 110, Fig 83) (See also under Smoke Pyro- devices are described in Ref 1, pp 243–46 and 255
technics) Army Smoke Candles. Exclusive of self-project-
ing and floating smoke candles, all smoke candles
Smoke Generator (Hatsuenku). See under Smoke were of the same basic construction, differing
Pyrotechnics only in size and falling. This type of candle con-
 J 53

sisted of a cylindrical sheet metal container with which extended inside to the bottom of the drum.
a removable metal cover held in place by adhesive An inflated rubber tube was attached to the lugs
tape. The cover protected a match head in the top around the drum to float it in water. In operation,
of the candle and contained a wooden scratch the safety pin in the firing assembly was removed
block. To ignite the candle, the scratch block was and the plunger was struck to fire the detonator
rubbed against the match head which, after a few and ignite the fuse, a wick, and start the com-
seconds delay, ignited the Main Filler. The candle bustion of a slow-burning chge. As pressure from
was thrown to, or placed at the spot where smoke the burning built up in the upper part of the drum
was required (Ref 1, p 143). A list of Smoke the FS smoke mix (See item a under Smoke-
Candles l/2-kg, l-kg and 10-kg is given on p 255. Producing Material) in the lower part was forced
As Main Fillers Berger Mixture, HC (Hexachloro- out thru the emission tube. Upon contact with
ethane) and other smoke-producing mixtures air, a dense white smoke was formed (Ref 1, pp
were used 244–45). Navy Smoke Float had an aerial bomb
Army SelfProjecting Candles usually consisted of body, ca 18 inches long, with three tail fins. It
an outer tube sealed at one end by a wooden was ffled with yellow or black smoke mixtures,
block and provided with protective metal covers an igniter and a small ejection chge. It was drop-
held on each end with adhesive tape. The smoke ped from a height less than 700 meters to serve as
mix was held in a snug-fitting inner container. an aircraft navigation marker (p 245, Fig 403)
A match head in the block at the base of the Navy Floating Smoke Flare had a long conical
candle was ignited by the scratch block contd in nose section and shorter cylindrical tail section
the’ top metal cover. This ignited a delay fuze with parachute. Overall length 51 inches. The
which set off the proplnt chge and shot the inner body contd an ejection chge, pull igniter, delay
tube container outward. A delay element was train and a smoke mixture. It was dropped from.
ignited by the expln and in turn set off the smoke an aircraft and a parachute slowed the descent of
mix. A rod encircled the candle and extended the flare and the delay train permitted the flare
along the length of the canclle to form a spike to hit the surface of the water before the smoke
which was inserted into the ground to support mix was ignited (pp 245–46, Fig 403)
the candle at the desired angle for firing (Ref 1, ,, Navy Type 2 Target Indicator had a bomb-shape
p 243). Same smoke mixes are listed in Ref 1, thhi bakelite body, 17 inches long, 3 inches in
p 255 diarn, ffled with FM (Titanium Tetrachloride)
Army Type 94 Floating Smoke Candle consisted smoke mix. The bomb had no fuze because its
of a cylindrical metal tube 31?4inches long and 3% light body was designed to break (when dropped
inches diarn, equipped with a supporting ring to ~‘from a high altitude) on hitting water, thus re-
which an automobile rubber tube was attached. leasing the smoke mix (Ref 1, p 246 & Fig 404 on
It was inflated to support the candle floating in p 245)
water. The ffling was either Berger Mixture
(Type 94A) or HC (Type 94B). A metal top Smoke Screen. Emmaku ‘
covered the fuze pocket which was closed during
shipment. Two types of firing mechanisms were Smoke Signal. Hatsuen shing~
used. One type was the ordinary hand grenade
igniter without a blasting cap detonator; this gave Smooth-Bore. Kakk6 n~
a delay of 8 sees. The other type was a friction
igniter initiated by a small piece of wood painted Sokosha Armored Vehicle
with abrasive, This produced a delay of up to
30 sees..The candle burned for ca 3.5 reins, pro- Spigot Type Mortar. See under MORTARS
ducing a dense white smoke which hovered close andin Ref3, p 389&Ref 7,p 170
to the surface of water (Ref 1, p 243, Fig 401)
Navy 40-kg Floating Smoke Generator consisted Stabilizing Fin. Dan-yaku
of a welded steel drum 14 inches high& 12 inches
in diam, equipped with carrying handles, a falling Stick Charges, 50-mm were projectiles fired
hole, a fuze with ignition system, and’a spray tube from Type 98 Discharger: They consisted of
 J 54

square cast-iron boxes mounted on wooden Taisensha jirai. Antitank Mine

poles. Each box contd blocks of PA (Picric
Acid) with two Pull Igniters. When the pro- Taka Nos 1, 2 & 3. Gelatin Dynamites
jectile is fired these pull igniters are initiated
and in turn set off the bursting chge after a short Tama. Bullet
delay. A Blk Pdr proplnt in silk bags, indepen-
dent of the projectile, is also fired by a pull Tanayaku (?). See Shouyaku
igniter inserted in the side of the launcher
tube. Stick charges may be considered as a spe- Tankei. Ogive
cial type of army mortar (Ref 3, pp 377–78)
Tanken. Dagger
Submarine. Sensuikan
Tanks (Tanku) and Tankettes are listed here under
Sucker under Sabotage Devices and
Traps. See Combat Vehicles and described, with ilhrstra-
inRef 1, pp 231–32 tions, in the book of Tantum & Hoffschmidt,
pp 116–29, listed as Ref 7
Suicide Boats (Army & Navy). The craft were
lightlight plywood, gasolene-driven speedboats Tank Gun. Senshaho
15 to 20 feet long. The Army boat (Ref 1,
Fig 39 of p 65) had mounted on its sides two Tanoyaku. See under Nigotanoyaku and in Ref
120-kg depth charges, which released when the 5, p 373, where No 1 consists of RDX 60, TNT
boat struck its target. Some boats had a 3rd 30& Tetryl lWO, and No 2’consists of RDX 55,
depth chge mounted over the stern TNT 38& Tetryl 7%. They were used as cast-
The Navy boat, shown in Fig 40 had a 640-lb loaded carton charges for various projectiles
chge of Type 98 Expl chge built into the nose.
The boat was exploded electrically upon contact Tekidan. Grenade (qv)
with the target, or by throwing a switch in the
cockpit. A stand-by pull igniter firing device Tekidanki. Rifle Grenade Launcher
was also fitted into the chge
Tekidanto. Grenade Discharger
Suirai hasshakan. Torpedo Tube
Tekishaho. Howitzer. See under ARTILLERY
Suiraitel. Torpedoboat
Tekkodan. Armor-Piercing Projectile
Sulfuric Acid. Ryiisan
Tenagedan. Hand Grenade. See under GRE-
Taiho. A/Tk Gun [Kah6-Gun (general)] NADES

Taijinteki jiral. Antipersonnel Mine . Tenka bakkan. Igniting Primer

Taiku. Antiaircraft Tenka shinkan. Igniting Fuze

Tail Fin. Anteiban Tenkayaku. Igniting Charge

Tail Fuze. Dantei shinkan Terumitto (Thermite). See Shakunetsuzai

Taisenshadan. Antitank Bomb Terumitto shoidan. Thermite Bomb

Taisenshafunshindan. Antitank Rocket Teryudan. Tenagedan

Taisensha funshin toshaki. Antitank Rocket Tessen keitei. Trip Wire

Launcher
 J 55

Tetryl. See Melayaku Type 90 Torpedo contd 880 lbs of Type 94

or Shimose (Obsolete; replaced by Type 93)
Thermite. Terumitto. See Shakunetsuzai Type 93 Model 1 Mod 2 contd 1080 lbs of
Type 97 Expl; was 29 ft 6 inches long& 24
Thermite Bomb. Termitto shtiidan inches in diam; used in destroyers and cruisers.
It was the standard Navy torpedo and a very
Thermite Grenade. Termitto tekidan superior weapon. There was also a Model 3
carrying 1700 lbs of Type 97 Expl
TNAns (Trinitroanisol). See Type 91 Explosive Type 91 Modsl, 2,3,3 (Special), 4,6 and 7
(Navy) were standard aircraft torpedoes of diam 17.7
inches and 17 ft 3 inches to 18 ft 10 inches
TNPhnt (Trinitrophenetol). See Heineiyaku long which carried 340 to 900 lbs of Shimose,
Type 94,97 or 98 Expl
TNT (Trinitrotoluene); Sanshi5ki toru6ru or Type 92 Mod 1, used in submarines, was copied
Type 92 Explosive (Navy). See Chakatsuyaku from the Germans and contd 660 lbs of HE
(no data). It was electrically driven, while
To. Sword other Japanese torpedoes were steam-driven
Type 94 Mod 1, used in submarines, was 22 ft
Toka hakodan. Armor-Piercing Bomb long &21 inches in diam. It contd 870 lbs of
Type 97 or Shimose
Tokei bakudan. Time Bomb Type 94 Mod 2, used in aircraft, was 17 ft 4
inches long and 17.7 inches in diam. It contd
Tokeishiki bakkan. Mechanical Time Fuze 460 lbs of Shimose
Type 95, apparently the most common sub-
Toku shiraume Nos 1, 2 & 3. Gelatin Dyna- marine weapon, was 23 ft 6 inches long and 21
mites inches in diam. It contd 880 lbs of Type 98
Expl
TORPEDOES (Raigeki suru or Gyorai). Accdg Type 97, used in midget subs& PT boats, was
to Ref 1, p 54, the JapaneseTorpedoes of WWII 18 ft 5 inches long and 17.7 inches in diam. It
were of designs developed during 20 years of contd 790 lbs of Type 97 Expl
research. They were unrivaled in speed and Type 2, used in midget subs, was of the same
range, yet carrying an extra weight of explo- size as Type 97. It contd 774 lbs of Type 97
sives. They had cigar-shaped bodies and usually Type 2 (Specird) was an aircraft torpedo, which
were steam-driven. Besides the HE ffling and carried 650 lbs of Type 97
engine, they carried machinery necessary to ~ No torpedoes are listed in Refs 2,3,5 and 7 .
keep the torpedo on a set course and at a set
depth to its target. A typical torpedo is shown Torpedoboat. Suiraitei
in Fig 25 on p 54
A table on p 60 of Ref 1 lists torpedoes used Torpedo Tube. Suirai hosshakan
before and during WIWI, of which several Types
are marked “obsolete” or “obsolescent”: Torpedo Warhead. Suirai-bakuhatsusen-tbbu
Type 44 Mk 2 Mod contd 400 lbs of Type 97 or
98 Expl (Obsolete) Tracer (Eikodan) and Tracer Ammunition
6th Year Type contd 450 lbs of Shimose (obso- (Eik6dan-yaku). Many projectiles contg tracers
lete) are listed in Ref 3, but no compns of tracers
8th Year Type Mk 2 Mod 2 contd 850 lbs of are given
Shimose or Type 98 Expl (Obsolescent)
Type 89 Mod 1 contd 625 to 660 lbs of Type Trajectory. DandG
94, 97 or Shimose (Obsolescent, including its
Mod 2) Trinitroanisol (TNAns). See Type 91 Explosive
 J 56

Trinitrophenetol (TNPhnt). See Heineiyaku sisting of Amm Perchlorate 80, talc 10, ferro-
silicon 8 & chloronaphthalene 2’70. Its apparent
Trinitrotoluene (TNT). See Chakatsuyaku or d was 1.24; Brisance 89% PA; Expln Temp
Type 92 Explosive (Naiy) 455°; Impact Sensitivity 18cm (max for no
explns with 5-kg wt); Power by Ballistic Mortar
“TYPE” A series of explosives
Explosives. 84% PA& Rate of Deton 3600m/sec. Used presi-
used by the Japanese Navy, which are listed in loaded in Sea Mines and Depth Charges (Ref 5,
Refs 1, 5 and below: p 375)
Type A (Explosive) or A (ko). See Otsu-B Type 4 Mk 2, K2. A gray expl compn consisting
Type K (Explosive).A series of expls based on of Arnm Perchlorate 89, woodpulp 5 & coal’
mixtures of inorganic salts, developed during tar 6%. Its apparent d was 1.0; Brisance 70%
WWII. Their compns are not given but they PA; Expln Temp 470°; Impact Sensitivity 34cm;
are probably similar to German Ersatzspreng- Power 82% PA & Rate of Deton 3900m/sec.
stoffe (Substitute Explosives), listed in Vol 5 Used press-loaded in Sea Mines and depth ‘
of Encycl, pp E121–E122 Charges (Ref 5, p 375)
Type 1 (Explosive). A greenish-yel expl compn Type 4 Mk 3, K3. A lt gray expl compn consisting
consisting of Ammonium Picrate 81, Al 16, of Amm Perchlorate 47, Amm Sulfate 32, ferro-
sawdust 2 & heavy oil 1%. Its Brisance by Sand silicon 20 and chloronaphthalene 1%. Its ap-
Test was lower than that of TNT; Expln Temp parent d was 1.20; Brisance 83% PA; Expln
475 0; Impact Sensitivity, comparable to TNT; Temp 470°; Impact Sensitivity 20cm; Power 8 1%”
Power 136% TNT & Rate of Deton 4300m/sec. PA and Rate of Deton 2900m/sec. Used press-
It was used as press-loaded chges for Depth loaded @ Sea Mines and Depth Charges (Ref 5,
,.
Bombs or other Underwater Ordnance (Ref p 375)
l,p32&Ref5, p374) Type 4 Mk 4, K4. A white expl compn con-
Type 1, Mk 5, P5 (Explosive). A dark-grn sisting of Na Chlorate with K chlorate 88 & pe-
expl compn consisting of Amm Picrate 81, troleum oil 12Y0. Its app d was 1.05; Brisance
ferrosilicon 16, woodpulp 2 & heavy oil 1%. 77% PA; Expln Temp 580°; Impact Sensitivity
Its apparent density was 1.16; Brisance by Cu 14crn; Power 81% PA and Rate of Deton, not
Cylinder Crusher Method 99% of PA; ‘Expln given. Used press-loaded in Sea Mines and’
Temp 450°; Impact Sensitivity 15cm (maxi- Depth Charges (Ref 5, p 376)
mum for no explns with 5-kg wt); Power by Type 4 Mk 5, K5. A gray expl compn consisting
Ballistic Mortar 72% PA& Rate of Deton 4100 of Amm Perchlorate 55, Amm Nitrate 29, ferro-
m/see. Used press-loaded in some Depth Charges silicon 10, woodpulp 5 & heavy oil 1%. Its ap-
(Ref 5, p 374) parent d was 1.05; Brisance 92% PA; Expln
Type 1 Mk 6, P6. A dark-grn expl compn con- Temp 450°; Impact Sensitivity 28cm; Power
sisting of Amm Picrate 86, ferrosilicon 11, wood- 81’ZOPA; and Rate of Deton, not gjven. Used in
pulp 2 & heavy oil 1%. Its apparent d was 1.13; Sea Mines & Depth Charges (Ref 5, p 376)
Brisance 95% PA; Expln Temp 450°; Impact Type 4 Mk 6, K6. A gray expl compn”consisting
Sensitivity 13cm ‘(max for no explns with 5-kg of Na Chlorate 84, woodpulp 6, & petroleum
wt); Rate of Deton 4620m/sec. Used press- oil 10%. Its appt d was 1.,35;Brisance 78% PA;
loaded iriDepth Charges (Ref 5, p 374) ‘ Impact Sensy 17cm; Power 67% PA and Ra~eof
Type 2 (Explosive). See,B4 (Incendiary) Deton, not given. Used in ‘sea mihes & Depth
Type 4 (Explosive) (Navy). A gray expl compn Charges (Ref 5, p 376) +
consisting of “Amm Perchlorate 79.2, ferrosilicon Type 4 Mk 7, K7. ~ dark-gray expl compn con-
16.4, Al & Fe pdr 1.0, heavy oil 2.5 & unac- sisting of Na Chlorate 84, woodpulp 5, charcoal
counted 0.9%. Its properties are not given, but 8 & coal tar 3%. Its appt d was 1.2’; Brisance
it was stated in Ref 5 that they were similar to 82% PA; Expln Temp 385°; Impact Sensy 25cm;
Type 88 Explosive (qv), except that it did not Power 63% PA and Rate of Deton, not given.
bum as easily. Used in Depth Charges (Ref 1, Used in Sea Mines & Depth Charges (Ref 5, p
p32&Ref5, p375) .: 376)
Type 4 Mk 1, K1. A it-grayish expl compn con- Type 88 (Explosive) (Navy) or Karitto (Army).
 J 57

A gray expl compn consisting of Amm Perchlor- Bombs and Shells as replacement for Shimose
ate 66, silicon carbide 16, woodpulp 12 & pe- (melting at high temp of 122.50). Was also
troleum 6%. Its props are not given, except that used for composite expls: A (lco) or Type A
it was stated in Ref 1, p 31, that it was dangerous (Explosive), described here as Otsu-B; Type 2
to bum and very sensitive to friction. In Ref 5, (Explosive), described as B4 (Incendiary); E
p 377 it was stated that it was nonhygroscopic, (Explosive); Type 98 (Explosive), described here
stable in storage and produced on burning very as H2 Kongo; Type 94M (Navy) and some other
poisonous, fumes. expl compns (Ref 1, p 32, Ref 5, p 377 and
The Navy used this expl compn loosely pack- Vol 1 ofEncycl,ppA450–451, under Anisole)
ed in Mines and Depth Charges, while the Army
used it under the name of Kan”tto in Substitute Type 92 (Explosive). This term is applied by
Demolition Charges. It was proposed to use it the Navy to straight TNT which was used in
also as a Solid Rocket Propellant Naval 25-mm & 40-mm Shells. TNT was de-
This expl compn was used under the name of scribed here as Chakatsuyaku
Carlit for industrial purposes and is described in The term Type 92 is also applied to a compn
Pamphlet of “The Japan Carlit Co, Ltd” located consisting of TNT 66 & Al pdr 34% which was
before WWII in Chiyoda-ku, Tokyo. There are cast-loaded in Navy 25-mm Shells. This mixture
several formulations of Carlit, but all of them originated in Germany under the name of Tn”-
contain some Amm Perchlorate, but none 66’j& tonal. A similar mixture, but contg TNT 80&
(Pamphlet of Carlit Co and Ref 5, p 377) Al 20% was used in the US and described in
AMCP 706-177 (1971), p 386 (See Ref 1, p 33
Type 88 (Ko) or Haensosan-bakuyaku, called by & Ref 5, p 378). Example of use of 66/34 mix-
“The Japan Carlit Co, Ltd” Carlit Kuro (Black), ture in 25-mm HE Proj is described in Ref 3,
was a gray expl compn consisting of Amm Per- p 447
chlorate 75, ferrosilicon 16, wo,odpulp 6 & heavy
oil 3Y0, Its density was 1.05; Brisance lower Type 94M (Explosive) (Navy). A cream-yellow
thari that for TNT; Expln Temp 430°; Impact expl compn consisting of Trinitroanisole 60 &
Sensitivity 17cm (max for no explns with 5-kg RDX 40%. Its cast d was 1.64; Brisance by Cu
wt); Power higher than TNT; and Rate of Deton Cylinder Crusher Method 107% PA; Expln Temp
4400m/sec. Judged by its high Impact Sensiti- 2 16°; Friction Sensitivity 40–50 kg (max press-
vity and high Friction Sensitivity, 30 to 40 kg ure betw two rubbing surfaces for no explns);
(max pressure betw two rubbing surfaces for no Impact Sensitivity 13 cm (max for no explns
explns), instead of usual 60 kg, it was found un- with 5-kg wt); Power by Ballistic Mortar 112%
suitable for loading HE Shells, but was suitable PA; Rate of Deton by Dautriche Method 7700
for press-loading Navy Mines m/see. Originated as powerful expl for loading
Was used as an industrial expl by The Japan Torpedo Warheads but this use was discontinued
Carlit Co, Ltd, Tokyo (Ref 5, p 377 and Pam- due to its sensitivity to Sympathetic Detonation.
phlet of Carlit Co, Table listing properties) Later uses included Shaped Charge Grenades and
as a Booster Surround (Ref 1, p 32 as Type 94
Type 91 (Explosive) (Navy); Trinitroanisole & Ref 5, p 379 as Type 94M)
(TNAns); Methyl Picrate, or 2,4,6-Tnnitro-
phenylmethyl Ether, H3C .0.C6 H2 (N02 )3; mw Type 97H (Explosive) (Navy) is described here
243.13, N 17.28%; yel trysts, d 1.7 & 1.6 for as Seigata (Army)
cast; mp 68.4° (pure), 65–67° (coml); Brisance
by Cu Cylinder Crusher Test 92% PA or 100% Type 98 (Explosive) (Army & Navy) is de-
TNT; Expln Temp 279°; Friction Sensitivity scribed here asH2 Kongo
60 kg (max pressure betw two rubbing surfaces
for no expln); Impact Sensitivity with 5-kg wt Unknown Name Explosives are listed here
19cm; Power by Ballistic Mortar 101% PA; Rate under X-EXPLOSIVES and also under Japanese
of Deton 6660m/sec at d 1.59 Explosives and Related Items Described in
It was widely used straight for cast loading Journals &Patents Listed in Chemical A bstracts
After WWII
 J 58

Very Pistol. Verii shing6 kenjii X-7. A pressed mixture of PETN & wax. It was
used as Main Charge in some Incendiary Shells
Vomit Gas Projectile was 7cm (75-mm) in diam and as a Booster in 13-mm & 15-mm Shells
and contd 0.37 lb of crude diphenylcyanoarsine (Ref 5, p 379)
(See DC in Vol 2 of Encycl, p C 167-R) as a X-8. A brown expl compn consisting of Amm
vomit warfare agent and 1.02 lbs of TNT desen- chlorate 51.5, Ba Nitrate 34.5, Trinitronaphtha-
sitized with 30% ‘naphthalene as burster charge lene + oil 8.2, woodpulp 5.0 & other ingredients
(Ref 3, p 341, Fig 268) 0.8%. It was used in some Demolition Charges.
Dangerous to burn in large quantity (Ref 5, pp
War. Sens6 379–80)
X-9. A pressed mixture of RDX & AN (Am-
Warhead. Gyorai jitsuy5 t6bu monium Nitrate) used in Type 92 7-cm (70-mm)
HE Projectile described in Ref 3, p 304, Fig 236
Weapon. Heiki X-1 O. A pressed expl compn of RDX 90 & paraf-
fin 10%, coated with graphite and wrapped in
White Composition consisting of AN, RDX & Al foil. It was used in Type 1 47-mm and
GuN (Guanidine Nitrate) was used in conjunc- 7-cm (75-mm) Armor-Piercing Projectiles de-
tion with cast TNT in Type91 1O-cm ( 105-mm) scribed in Ref 3, pp 299 & 331
HE Long Pointed Projectile described in Ref 3,
p 352, Fig 278 Yasenho (Field Gun); Yiigekiteki jirai (Booby
Trap). See under MINES
White Phosphorus (WP) (Hakurin). It was used
as an Incendiary amd in Incendiary Mixtures in Yuenyaku (Black Powder). See Koko Shoku-
Bombs, Grenades and Projectiles, described here yaku
under “Incendiaries” and in Refs 2 & 3. WP was
also used in Smoke Compositions as described Yokosuka Depth Charge. This antisubmarine
here under Smoke Producing Materials, items d, weapon was not a depth charge in the accepted
e,handin Refs2&3 sense. It was towed under water by escort ships
and would explode upon contact with a sub-
X-EXPLOSIVES: merged enemy submarine. The charge was
X-1. A light gray to tan mixture of KC103 & cylindrical in shape, ca 5 ft long & 1 inch in
Sbz Ss of proportion not given in Ref 1, p 25, diam, fdled with 55 lbs of Type 88 Expl. Vertical
but it was the most common mixture for Fuze and horizontrd rudders were fitted on the tail,
Primers (See also Ref 5, p 378) and an impeller-armed Impact Firing Mechanism
X-2. A chalky-white mixture of PETN 58 & was located in the nose (Ref 1, p 65)
RDX 42% used as ffler for Army 7.92-mm and
12.7-mm Ammunition (Ref 1, p 27 & Ref 5, References on Japanese Explosives and Related
p 379) Items Used Before and During WWlI
X-3. A pressed mixture of RDX 83 & PETN 1) Anon, “Handbook of ’Japanese Explosive
17% used in 7.7-mm Ammunition (Ref 5, p Ordnance”, OPNAV 30-3M, USGovtPrintingOff,
379) Washington, DC, Aug 1945
X-4. A pressed mixture of RDX 92–95 & wax 2) Anon, “Japanese Explosive Ordnance”
8–5% used as a main charge in 20-mm Anti- (Bombs, Bomb Fuzes, Land Mines, Grenades,
aircraft Projectiles (Ref 5, p 379) and in Boosters Firing Devices and Sabotage Devices); Dept of
(Ref 3, p 388-R) the Army and the Air Force, TM 9-1985-4 and
X-5. A pressed mixture of RDX 85 & wax 15% TO 39 B-IA-I 1, March 1953
used as a Main Charge in 75-mm Armor-Piercing 3) Anon, “Japanese Explosive Ordnance”,
Projectiles (Ref 1, p 27 & Ref 5, p 379) (Army Ammunition, Navy Ammunition), Dept
X-6. A pressed mixture of RDX with Al pdr. of the Army and the Air Force, TM 9-1985-5
Al was evidently added for its incendiary effect and TO 39 B-lA-12, March 1953
(Ref5, p 379) 4) B.T. Fedoroff et al, “Japanese Ammunition,
 J 59

Explosives and Weapons”, Picattiy Arsen~ US Office of Tech Services PB Rept 53045
Manuscript, Unpublished (1955) J) Anon, “Allied and Enemy Explosives”,
5) O.E. Sheffield, “Handbook of Foreign Explo- Aberdeen Proving Ground, Maryland (1946)
sives”, FSTC 381-5042 (1966), pp 360–387,, K) G.C. Tibbitts et al, “Japanese Powder and
US Foreign Science Technology Center, Muni~ Explosives”, USOrdnanceTechIntelligence Rept
tions Building, Washington, DC 20315 6 (1946), US Office of Technical Services PB
6) Anon, “Military Explosives”, Dept of the Rept 50394
Army and of the Air Force TM 9-1300-214 and L) S. Nakahara & T. Hikita, “Studies of Delay
TO 11A-1-34, Nov 1967, Table 8-2 on pp 8-2 Powders”, K8gy6KayakuKy~kaishi 20, 275–79
& 8-3 for Explosives and Table 11-7 on p 11-4 (1958) [USDept of the Army Translation 1-1955,
for Propellants ID No 2203235 (October 1962), Report No 1
7) W.H. Tantum IV & E.J. Hoffschmidt, Editors, “Measurement of Combustion Temperature of
“Japanese Combat Weapons”, Vol 2 of Second Delay Powders”; Translation I-1957, ID No
World Combat Series, published in 1968 by WE 2203237 (Ott 1962), Rept No 3 “On Mechanism
Inc, Old Greenwich, Connecticut 06870 of Combustion of Delay Powders”; Translation
8) W.R. Tomlinson & O.E. Sheffield, “Pro- 1-1958, ID No 2203238 (Ott 1962), Rept No 6,
perties of Explosives of Military Interest”, “Theory of Burning Rate of Delay Powders”]
PATR 1740 (1958), reproduced as Anonymous M) Anon, “Manufacturing and Construction
AMC (Army Materiel Command) Pamphlet (Vehicles, Explosives, Arms and Ammunition)”,
706-177(1971) US OrdnTechIntelligenceRept OTIA 5801,
Chapter VI, Section 64, pp 64-1 ff (March 1960)
Additional References on Japanese Explosives N) R.P. Antonelli, “Encyclopedia of Explo-
and Related Items sives”, US OrdnTechIntelligenceAgency, Ordn
A) H.T. Creswell et al, “A Dictionary of Mili- Liaison Group, Durham, North Carolina (1960)
tary Terms: English-Japanese, Japanese-English”, O) M.H.B. Smith & J.E. Smith, “Small Arms
University of Chicago, Chicago, Ill (1942) of the World”, Stackpole, Harrisburg, Pennsyl-
B) M. Wiater, “Examination of Japanese vania (1960), pp 498–518
7.7-mm Ball Ammunition (Model 99)”, Frank- P) Anon, “Tests of M53 Fuze”, TechRes &
ford Arsenrd Rept R395 (1943) Development Inst, Japan Defense Agency (Sept
C) A. Suzuki, “Crystalline Structure and Ex- 1960) [Engl Translation, US Dept of Defense
plosibility of Fulminate of Mercury”, US Air Intelligence Rept 2220044563 (1963)]
Technical Branch Rept 0418 (1944) Q) Heizo Nambo, “Who, Invented Explosives”,
D) Anon, “Soldier’s Guide to the Japanese K6gy8KayakuKy!5kaishi 28, 322–29 & 403–23
Army”, Military Intelligence Service, War Dept, (1967). Engl translation obtainable for $15.00,
Washington, DC (1944) surface mail from Japan Publishers Trading Co,
E) Anon, “Data on Foreign Explosives”, US Ltd, PO Box 5030, Tokyo International, Tokyo,
Chemical Warfare Service Field Lab Memo Japan
4-6-2 (1944?) (US Office of Technical Services R) K. Sassa& 1. Ito, “Studies of Detonation
PB Rept 11544) Pressure by Aquarium Technique”, K&gy8-
F) J.O. Clements et al, “Japanese Methyl KayakuKy8kaishi (abbrd as KKK) 32, No 6,
Formate Munition”, US Office of Technical Nov-Dec 1971. Engl translation by Mrs Geti
Services, PB Rept 50950 (1944) in 1972 at the Bureau of Mines; available from
G) Anon, “Japanese Military Dictionary”, US US Dept of Commerce, NatlTechInfoService,
War Dept Tech Manual TM 30-541, US Govt- Springfield, Va 22151 (Compositions of Japan-
PtgOff, Washington, DC (1945) ese expls Akatsuki, Enoki Dynamite No 2 and
H) Anon, “Explosives and Demolitions”, US Geogel are given)
War Dept Tech Manual FM 5-25, US GovtPtg- S) Picatinny Arsenal Technical Reports (PATR)
Off, Washington, DC (1945), pp 133–34 (Japan- and other Reports:
ese Explosives) a) A.B. Schilling, “Grenade, Serrated, Cast
1) R.L. Cooley et al, “Japanese Explosives”, Iron (With PD Fuze for Japan Type 89
US Naval TechnicaJ Won to Japan Dec 1945, Grenade Discharger)”, PATR 149 (1943)
 J 60

b) Ibid, “Grenade, Serrated, Cast Iron Japanese Explosives and Related Items Described
(Hand Use or for Japan Type 10 Grenade in Jouranls & Patents Listed in Chemical Ab-
Discharger)”, PATR 150 (1943) stracts After WWlI
c) Ibid, “Unfired 20-mm HE Round of Following abbreviations are used for the
Japanese Ammunition”, PATR 1236 (1943) Japanese Joumrds and Japanese Patents listed
d) R.M. Dennis, “Drift Signal”, PATR 1203 in CA:
(1943) JP – JapanesePatent
e) W.R. Tomlinson, Jr, “Compilation of Japan Kokkai– JapaneseNational Diet
Data on the Composition of Foreign Explo- JapanSciRevEngrgScis – Japanese Science Re-
sives”, PATR 1311 (1943) ,’ view Series 1. Engineering Sciences – Changed
f.) A.B. Schilling, “Grenade, Hand, Stick to JapanSciRevMech&ElecEngrg (Printed in
Type”, PA Fragmentation Rept 193 (1944) Engl)
g) Ibid, “Land Mine and Type 93 Deto- KKK – K@yoKayakuKy6kaishi (Journal of the
nator”, PATR 1383 (1944) Industrial Explosives Society of Japan)
h) L.H. Eriksen, “Compilation of Data on KKZ – K6gyoKagakuZasshi (Journal of the
the Composition of Foreign Boosters and Chemical Society of Japan. Industrial Che-
High Explosives”, PATR 1446 (1944) mistry Section)
i) R.M. Dennis, “Unfired 25-mm HE Shell KKwZ – K@yoKwagakuZasshi (Journal of the
(Maroon Shell)”, PATR 1350 (1944) Society of Chefical Indust~, Japan, abbrd in
j) Ibid, “Unfired 25-mm HE Shell (Orange CA as JourSocChemInd, Japan)
Shell, Green Band), PATR 1351 (1944) KojinKwZ – K6jinKwagakuZasshi [Engineers
k) A.B. Schilling, “Unfired AP Rifle Gre- Chemical Journal, Japan, abbrd in CA as Eng-
nade”, PATR 1461 (1945) ChemJour(Japrm)]
1) W.G. Eppler, “Fragmentation of 8 l-mm TKShH – TokyoKogyoShikensho~okoku (Re-
HE Mortar Shell, Equipped with PD Fuie”, ports of the Government Chemical Industrial
PA Fragmentation Rept 214 (1945) Research Institute, Tokyo)
m) A.B. Schilling, “Unfired, Serrated Gre-
nade for Hand Use or for Type 10 Grenade
Discharger”, PATR 1491 (1945) Following are the titles of Japanese Patents
n) Ibid, “AP (ShapedCharge) Rifle Grenade and Papers, arranged in chronological order. A
with Special Pin Assembly”, PATR 1511 brief description of each subject is given in CA:
(1945) 1) T. Hikita, “Thermal Decomposition of
o) Ibid, “75-mm Hollow Charge HE Shell Some Explosive Compounds”, JapanSciRev,
Complete Round for Type 41 Mountain Series 1, EngrgScis 1 (2) 23–28 (1950)&CA
Gun”, PATR 1521 (1945) ,,. 45,2669 (1951)
p) Ibid, “50-mm Non-Serrated Grenade for 2) H. Tominaga & T. Kanno, “Combustion
Type 89 Grenade Discharger”, PATR 1544 of Aluminum Powder”, KKZ 53, 106–08 (1950)
(1945) &CA 46,8374 (1952)
q) Ibid, “Unfired 88-mm Complete Round 3) Y. Suzuki, “Explosive Tube from Liquid.
HE Shell, Less Fuze”, PATR 1557 (1945) Carbon Dioxide”, JP’s 3,4 & 5 (1950); CA 46,
r) Ibid, “Unfired 70-mm Complete Round 8376 (1952)
HE Shell”, PA Memorandum Rept 5 (1952) 4) Z. Akashi, “Gasless Fuse”, JP’s 3043 &
s) Ibid, “Unfired 70-mm HE Complete 3045 (1951 ); CA47(1953)
Round, Model 92 (Japanese Design, Chinese 5) T. Hikita, “Explosion of Perchloric Acid
Manufacture), PATR 1845 (1952) Mixtures”, KKZ 54, 253–55 (1951)&CA
t) B.T. Fedoroff & O.E. Sheffield, “Ency- 47,2987 (1953)
clopedia of Explosives and Related Items”, 6) K. Ogawa, “Protecting Cylinder for Mine
PATR 2700: Volume 1 (1960); Volume 2 Explosives”, JP 5046 (1951) & CA 47, 2988
(1962); Volume 3 (1966); Volume 5 (1972) (1953)
and Volume 6 (1974), various pages,under 7) S Ishiyama, “Ignition Apparatus of Elec-
Japanese names, which are also listed in tric Detonator Cap”, JP 7242 (1951)&CA 47,
this Section of Volume 7 5121 (1953)
 J 61

8) T. Hikita, “Progress in the Theory of De- 27) Y. Wakazono, “Delay Composition”, KKK
tonation”, KKK 13, 3–8 & 77–85 (1952) and 16, 214–18 (1955)&CA 50, 17453–54(1956)
CA 49,2736 (1955) 28) N. Tsumagari & F. Takada, “Use of Waste
9) T. Kikara & T. Hikita, “Molecular Theory Acid from the Manufacture of High-Brisance
of Detonation”, KKK 13, 106–13 (1952) and Explosives”, JP 4742 (1955) &CA 51, 18614
CA 49,5841 (1955) (1957)
10) T. Okawa, “Studies of the Muzzle Flashes 29) Sh. Kikuchi, “Priming Charges for Elec-
of Explosives by Means of High-Speed Cinema- tric Blasting Caps”, JP 6297 (1955) &CA 51,
tographic Camera”, KKK 13, 247–54 (1952) 18614 (1957)
&CA 49,5841 (1955) 30) K. Honma & H. Yoshitoni, “A Delay Com-
11) Y. Kate, “Lowering the Viscosity of Nitro- position”, JP 4743 (1955) & CA 51, 17170
cellulose”, JP 2292 (1952) & CA 47, 6658 (1957)
(1953) 31) T. Toshima & K. Honma, “A Delay Com-
12) T. Hikita & K. Yoneda, “A Method of position for Millisecond Delay Detonator”, JP
Measuring Detonation Velocity of Short 5098(1955)&CA 51, 17170(1957)
Charges”, KKK 14, 30–33 (1953) &CA 49, 32) Sh. Okubo & S. Ikunuma, “Blasting Caps”,
5841 (1955) JP 6898 (1955)&CA 51, 18614(1957)
13) K. Hino, “Gelatinous Dynamite”, JP 33) M. Shiunbi, T. Tahara & Sh. Miya, “Col-
2247 (1953) &CA 48,4840 (1954) loidal Explosives”, JP 8096 (1955) &CA 51,
14) S. Kinoshita & T. Sakamaki, “Detonator 181614 (1957)
for Electric Blastin~’,JP 2498 (1953)&CA 48, 34) T. Toshima et al, “Ignition Delay Compo-
6700 (1954) sition”, JP 8498 (1955) & CA 51, 181614 .
15) R. Kiyama et al, “Explosions under High (1957)
Pressures”, RevPhysChemJapan 23,43-48” 35) K. Shiino & S. Oinuma, “Preparation of
(1953) &CA 48,8544 (1954) Tetryl”, TKShH 51, 74–76 (1956) &CA 50,
16) K. Hino & J. Sate, “Colloidal Dynamite”, 11017(1956)
JP 6196 (1953)&CA 48, 11790 (1954) 36) T. Watanabe & O. Murata, “The Double
17) S. Takenaka, “Ignition Composition for Sympathetic Detonation”, KKK 17, 102– 11
Electric Detonators”, JP 6298 (1953)&CA 48, (1956) &CA 50,17454 (1956)
12410–11 (1954) 37) Y. Fukuyama, “Sensitive Ammonium Ni-
18) J. Sate, “Explosive Composition”, JP 296 trate”, KKK 18, 64–66 (1957) &CA 51,9159
(1954) &CA 48,13222 (1954) (1957)
19) Y. Tsurusaki, “Explosive”, JP 148 (1954) 38) M. Uretake & M. Hamasaki, “Limits of .
&CA 48, 13222 (1954) Explosion of the Systems Alcohol-Air and
20) A. Sate, “Explosive Composition”, JP Ether-Air”, KKK 18, 146–53 (1957) &CA 51,
988 (1954)&CA 48, 14210(1954) 17169 (1957)
21) T. Sakurai, “Explosive Composition”, JP 39) T. Ito, “The Liquid Viscosity of Picric
989 (1954) &CA 48, 14210 (1954) Acid, Trinitroanisole, and Trinitrotoluene”, KKK
22) N. Sakurai, “Explosive Composition”, JP 18, 153–56 (1957 & CA 51, 17169 (1957)
990(1954) &CA48, 14210(1954) 40) T. Sakurai, “Brisance of Explosives, Plastic
23) H. Teranishi, “Explosions under High Deformation Flow of Solid Produced by the De-
Pressures”, RevPhysChem, Japan 25, 58–63 tonation of Explosives”, KKK 18, 225–36
(1955) &CA 50,8207 (1956) (1957) &CA51, 17167 (1957)
24) W. Jono et al, “Explosion of Camphor”, 41) Sh. Okubo, K. Shindo & S. Oinuma,
KKZ 58, 673–75 (1955)&CA 50,8207 (1956) “Copper Azide Detonators. I. Preparation of
25) S. Hirose &K. Honma, “Ignition Ball for Copper Azide and Its Impact Sensitivity Test”,
Electric Detonator Compounded with a Non. TKShH52 , 311–14 (1957) & CA 52, 8559
combustible Product”, JP 6748 (1954) & CA (1958)
50,9022 (1956) 42) N. Nakashiro & K. Takizawa, “An Indus-
26) T. Sakurai, “The Brisance of Explosives”, trial EXI losive”, JP 5849 (1958) & CA 53,
KKK 16, 90–94 (1955 &CA 50, 17452 (1956) 16540 ( 958)
 J 62

43) K. Konoshita et al, “Waterproof Binder for 57) Ibid, “II. The Variation Under Pressure”,
Explosive Initiators”, JP 8797(1958)&CA 53, KKZ 63, 1883–86 (1960)&CA 57, 1140–41
4739 (1959) (1962)
44) 1. Ito, Y. Wakazono & Y. Fujinaka, “Delay 58) T. Murata & T. Fukuda, “NAP. Propellant”,
Composition. The Combustion Mechanism of KKZ 63, 1900–01 (1960) & CA57 , 1140
Minium-Silicon Delay Composition”, Suiyokaishi (1962) [A new type of solid proplnt prepd by
(Transactions of the Mining and Metallurgical treating NI-LIC104 + polyester resin composite
Alumni Assocn) 13, 653–59 (1958) &CA 53, proplnt with NC, .MeNOz or 0(CHZCH20N02)2]
12680 (1959) 59) K. Akimitsu et al, “Experimental Studies
45) Sh. Kinoshita & T. Yamazaka, “Delay of Composite Propellants”, KKZ 63, 1902–06
Composition for Electric Detonators”, JP 95 (1960) &CA 57, 1140 (1962) (Composite pro-
(1959) & CA53, 20807 (1959) plnt NH4C104 + epoxy. polysulfide resin was “
46) T. Soyarna, F. Shirnogori & N. Otake, found to be superior to proplnt NH4C104 +
“Ammonium Nitrate of Apparent Low Specific polyester resin in both its phys & burning props)
Density”, JP 2153 (1959) & CA53 , 22956 60) Sh. Tsuchiya, “Chemical Equilibrium Lag
(1959) During Rapid Expansion Through Rocket
47) S. Nakata &M. Yamada, “Apparatus to Nozzle”, BullChemSocJapan 34, 854–59 (1961)
Manufacture Percussion Caps”, JP 2445-9(1959) &CA56, 11871 (1962)
&CA53, 16541 (1959) 61) N. Nakajo et al, “Gelati~zation Properties
48) K. Hino & S. Hasegawa, “Theory of of Nitrocellulose, Nitroglycerol-Nitro~ycol
the Variable Reaction Zones in the. Detonation Gels”, KKK 22, 254–58 (1961) &CA 58,2318
of Industrial Explosives”, KKK 20, 2-1 (1959) (1963)
&CA ~ 20205 (1960) 62) L Fukuyama & H. Yoshitomi, “Effects
49) Y. Wakazono, “Preparation of Delay Com- of Sensitive Ammonium Nitrate on Explo-
position in Millisecond Detonator”, KKK 20, sibility of Gelatin Dynamite”, KKK 23 (l),
46–50 (1959) &CA 54,20206 (1960) 23–27 (1962) &CA 59,8538 (1963)
50) I. Fakuda, “Explosive Properties of Am- 63) S. Tsuchiya, “Flame Temperature of Am-
monium Nitrate”, KKK 20, 119–35 (1959) & monium Perchlorate Propellants”, KKZ 65,
CA 54,20205 (1960) 84347 (1962) &CA 5? 16949 (1962)
51) Sh. Nakahara & T. Hikita, “Delay Powders. 64) K. Namba, “Calculation of the Heat of
III. The Mechanism of Combustion of Delay Reaction in the Nitration of Glycerol”, KKK
Powders”, KKK 21,2-8 (1960) &CA 55, 11847 23, 76–77 (1962) &CA 63,9735 (1965)
(1961) 65) Y.N. Tsuchiya, “Crystal Habit Modifi-
52) K. Okazaki et al, “Properties of Silver cation of Ammonium Nitrate. III. Application
Nitrocyanamide”, KKK 21, 12-15 (1960)&CA to Ammonium Nitrate-Fuel Oil Explosives”,
55, 11848 (1961) KKK 23, 78–83 (1962) (in Engl) & CA 58,
53) Sh. Nakahara & T. Hikita, “Delay Powders. 3262 (1963)
IV. The oscillatory Bth-rring of Delay Powders”, 66) T. Fakuda”& M. Yamada, “Rocket Pro-
= 21, 86–92 (1960) &CA 55, 11847 (1961) pellants”, JP 395 (1962) & CA 59, 13763
54) K. .Hino & M. Yokogawa, “Ammonium (1963)
Nitrate-Fuel-Surfactant Explosives”, KKK 21, 67) E. Matsumura et al, “Double-Base Rocket
218–26(1960)&CA 55, 11849 (1961) Propellants”, JP 2797 (1962) &CA 60, 2719
55) Sh. Nakahara, “Delay Powders. V. Effects (1964)
of Pressure on the Burning Velocity of Delay 68) S. Hirose & N. Higashijirnima, “Simul-
Powders”, KKK 21, 238–43 &CA 55, 11847 (1961) taneous Purification and Granulation of Pen-
56) A. Iwama & K. Yamazaki, “Effect of Some tnte” (PETN), JP 4443(1962)& CA 62,5270
Parameters on the Ignition Delay of Hyper- (1964)
bolic Bipropellanis. 1. The Variation With Liquid 69) M. Aoki & Sh. Motoya, “Free-Flowing
Temperature, Oxidant Concentration, Subatmos- Explosive Compositions”, JP 4444 (1962) &
pheric Pressure and Fuel Composition”, KKZ CA 60,6695 (1964)
63, 1879–83 (1960) &CA 57, 1140 (1962) 70) M. Inagaki, “Rocket Propellants”, JP
 J63

4445 (1962) &CA 6Q 5269 (1964) 87) K. SUZU@, ‘~Properti?s of polyether-

71) T. Tosabayashi, “Powdered Explosive for Epoxy Type Propellrmts’” 5th InternSymp on
Slow-Burning Fuses”, JP4446 (1962)&CA 60, Space Technology & Science, Tokyo, Japan
5270 (1964) (2-7 Sept 1963), 61–64. IAA Accession No
72) K. Hino & T. Arakawa, “Composite Rock- A65-14296, 3pp (1964) (Engl) & CA 60,9735
et Propellants Containing Lithium Perchlorate”, (1965)
JP 10747 (1962)& CA60 ,6695 (1964) 87a) M. Uetake & H. Sate, “Ignition of Pro-
73) Y. Matsuda et al, “Solid Rocket Propel- pellants by Electrostatic Discharge”, KKK 24
lants”, JP 15796 (1962)&CA 60,6695 (1964) (2), 67-72 (1963) & CA 60, 11835 (1964)
74) K. Tsujihashi, “Coal Mine Explosives”, 88) 1. Fukuyama & T. Kai, “Srdt Pair Explo-
JP 15798 (1962)& CA60, 5270 (1964) sive for Coal Mining”, KKK 24 (3), 140–47
75) K. Nava & H. Honda, “Experimental (1963) &CA 63,6777 (1965) (Two types NC
Studies on Coyote Blasting. III. Time of Scab- contg expls with salt pairs NH4C1/KN03 and
bing of Free Surface Layer in Coyote Blasting”, NH4C1/NaN0 ~ were investigated. Both types
KKK23 (5), 226–29 (1962) &CA 60, 2715 offered greater safety than the usual mining
(1964) expls. The salt pair NH4C1/NaN03 made the
76) T. Uemura,” “Mechanism of Ignition of expl hydroscopic and gave poorer transmission
Methane-Air Mixtures by Electric Detonators”, than NW C1/KN03 )
KKK 23 (5), 229–41 (1962 &CA 60, 5269 Note: Same paper is listed in CA 60, 11836
(1964) (1964) under the title “Ion-Exchange Type
77) T. Suzuki&K. Nakai, “Delay Electric De- Coal Mine Explosives”
tonators”, JP 942 (1963)&CA 60,9093 (1964) 89) K. Nawa, “Blasting for Seismic Prospect-
78) K. Yamazaki et al, “Polyerethane-Am- ing”, A Review with 58 references, KKK 24 (3),
monium Perchlorate-Base Propellants Having 160–65 (1963) &CA60, 2715 (1964)
High Specific Impulse and Slow Burning Rate”, 90) K. Yamrnoto, “Primary Explosives. H.
TokyoDaigakuKokuKenkyushoShuho (Bulletin Therrnrd Decomposition of Diazodinitrophenol
of the Aeronautical Research Institute, Univ of and Other Primary Explosives”, KKK 25 (l),
Tokyo)3 (6), 381–89 (1963) &CA 60, 359 10–19 (1964)&CA 6Q 15673 (1964)
(1964) 91) E. Yoshikawa, “AN-FO Explosives in
79) N. Tomoishi & M. Masui, “Commercial Europe”, KKK 25 (l), 33–38 (1964) &CA
Explosives”, JP 9590 (1963) &CA 60, 9094 60, 15674 (1964) (A review)
(1964) 92) Y. Wakazono & Ch. Sate, “Granular Ex-
80) T. Watanabe & M. Inagaki, “Rocket Pro- plosives. 1. AN-FO Blasting Agents”, KKK 25
pellants”, JP 9594 (1963)&CA 60,7864 (1964) (2), 63-69 (1964) &CA 61,9397 (1964)
81) 1. Hayashi & T. Sate, “Explosive Compo- 93) T. Yoshida et al, “AN-FO Explosives.
sitions”, JP 16147(1963)&CA 60,9094 (1964) I“, KKK 25 (2), 76–84 (1964) & CA 61,
82) N. Tomoishi & K. Oishi, “Dynamite Ex- 11838 (1964)
plosives”, JP 16146 (1963) & CA 60, 7865 94) Sh Okubo & Y. Mizushima, “Tests of AN-
(1964) FO Blasting AGents”, KKK 25 (2), 85–90
83) Sh. Nakahara & Y. Honda, “Priming Com- (1964) &CA61, 11838(1964)
position for Electric Detonators”, JP 16149 95) K. Yarnarnoto, “Primary Explosives. III.
(1963) &CA 60,15676 (1964) Thermal Decomposition and Initiation of Pri.
84) K. Ito & Y. Inumaru, “Waterproof Com- mary Explosive-Potassium Chlorate Initiating
mercial Explosives”, JP 20394 (1963)&CA 60, Compositions”, KKK 25 (3), 126–34 (1964)
10472 (1964) &CA 61, 11839(1964)
85) T. Murata & T. Fukuda, “Rocket Propel- 96) Ibid, IV. “Initiation of Lead Thiocyanate-
lants”, JP 20398(1963)&CA 60, 10471 (1964) Potassium Chlorate”, KKK 25 (3), 134-44
86) T. Kakutani et al, “Solid Rocket Propel- (1964) &CA61 ,11839(1964)
lants Containing Binder, Plasticizer, and Sur- 97) M. Yokogawa, “Combustibility of Am-
factant”, JP 23798 (1963)&CA 60, 14327 monium Nitrate Explosives”, KKK 25 (3),
(1964) 156–59 (1964) &CA 62,8924 (1965)
 J64

98) H. Fukuda, “Burning of Ammonium 26 (4), 190–92 (1965) &CA 64 ; 3273 (1966)
Nitrate E~pl~~ive~”, KKK25 (3), 159–60 113) H, Osada & N. Kakinouchi, “Initiation of
(1964) &CA 62,8924 (1965) Ignition of Solid Rocket Propellants”, KKK
99) N. Machida et al, “Combustion of CO.~ 26 (4), 200–11 (1965) &CA 64, 3273 (1966)
Mine Powdered Explosives”, KKK25 (3), 164= 114) M. Mochizuki, “High-Altitude Combustion
68(1964) &CA61, 11837(1964) of Solid Propellant Rockets”, KKK26 (4),
100) K. Namba, “Developmen.ts in the Syn- 211–15 (1965 )& CA64,6392 (1966)
thesis of Explosive Substances”, KKK 25 (4), 115) H. Sakai, “Inflammable Resins”, JP
206–1 5 (1964) & CA 62, 8924 (1965) (A re- 16154 (1965)&CA 64,521 (1966)
view with 26 references) 116) AsaAi Chemical Industry Co, Ltd, “Auto-
101) K. Otsubo, “Chemical Engineering in matic Manufacture of Dynamite”, BelgP 669299
the Explosive Industry”, KKK 25 (4), 2 16–24 (1965) &CA 65,10420 (1966)
(1964) &CA 62,8924 (1965) 117) M. Nimi, “The Sensitivity of Explosives”,
102) K. Yamamoto, “Primary Explosives. V. KKK 27 (2), 71–72 (1966) &CA 65, 6987
Ignition of Primary Explosives When Heated (1966) (A review with 6 refs)
in an Electric Furnace”, KKK 25 (5), 258–70 118) K. Yamazaki & H. Tokui, “Composite
(1964) &CA 62,8923 (1965) Propellants Containing Epoxidized Polybuta-
103) K. Shiino & S. Oinuma, “Nitration Product diene as Fuel Binder”, KKZ 69 (3), 575–78
of Monomethylurea Nitrate”, KKK 25 (5), (1966) &CA65, 10415 (1966)
283–90 (1964) &CA 62,8923 (1965) 119) K. Sassa& G. Larocque, “Measurement
104) K. Kimura, “Slurry Explosives”, KKK 25 of Detonation Velocity in Bore Holes by Re-
(5), 293-97 (1964) &CA 62,8924 (1965) (A sistance Probe”, KKK 27 (4), 223–28 (1966)
review with 10 refs) &CA 66, 6374.(1967)
105) K. Yamamoto, “Primary Explosives. VII. 120) K. Sasa & 1, Ito, “Measurement of Deto-
Sensitivity of Piimary Explosives to Mechanical nation Pressure of Explosives by Modified Aquar-
Action”, KKK 25 (6), 330–42 (1964)&CA 64, ium Technique”, KKK 27 (4), 228–33 (1966)
3273 (1966) &CA 66,6374 (1967)
106) K. Yamazaki & H. Tokui, “The Cross- 121) M. Shinohara & M. Sakaguchi, “Some Ex-
Linking Reaction of Polybutadiene Binder for periments on Sensitivity of Nitroglycerol”,
Composite Propellants”, BullChemSocJapan 38 KKK 27 (5), 303–05 (1966) & CA 66, 6373
(12), 2774-78 (1965) (English) &“CA 64,6391 (1967)
(1966) 122) J. Sate, “Mechanical Properties of PETN-
107) K. Kiyota, “How We Use Explosive Fo”rm- Epikote 871 Composite Explosives”, KKK 27
ing Technology”, KKK 26 (l), 3539 (1965) (5), 306-08 (1966) &CA 66,6373 (1967)
&CA 64,3274 (1966) (A Review) 123) K. Yamazaki & H. Tokui, “On the Com-
108) K. Yarnamoto, “Primary Explosives. X. posite Solid Propellant Impregnated with Metal-
Hazardous Properties of Pb(CNS~ –KC103 Mix-” lic Foil”, Bullr2hemSo~ietyJapan 40 (5), 1249–
tures”, KKK 26 (2) 66–73 (1965) & CA 64, 53 (1967)&CA 67,5261 (1967)
6394 (1966) 124) K. Yamazaki, “Solid Rocket Propellants
109) K. Yamamoto, “Primary Explosives. XI. Burning Characteristics”, KKK 28 (5), 356–63
Sensitivity of DDNP” (Diazodinitrophenol)– (1967) &CA 68,9401 (1968) (A review)
KC103 Mixtures and Effects of S in DDNP”, 125) H, Shimizu et al, “Acetylenic Propellants. :
KKK 26 (2)? 74–82 (1965)&CA 64, 6394 I. Synthesis of Acetylenic Propellants”, KKK
(1966) 28 (5), 386–90 (1967)&CA 68,9401 (1968)
11O) Y. Mizushima, “Gap Test in Hard Poly- 126) H. Yoshitomi, “Nitric Oxide and Nitrogen
vinyl Chloride Tubes”, KKK 26 (2), 96–97 Dioxide in Blasting Gas”, KKK 28 (6), 447-51
(1965) &CA 64,6393 (1966) (1967) &CA 68,9402 (1968)
111) Y, Mizushima, “Measurement of, Blast 127) T. Wakabaishi, “Liquid Oxygen Explo-
Wave Pressure”, KKK 26 (3), 142–55 (1965) sives”, Koalsu Gasu 1967, 4 (2), 87–89 (Japan)
&CA 64,3274 (1966) (A review with 42 refs) &CA 69,68687 (1968)
112) T. Mataki, “Rocket Propell&ts”, KKK 128) H. Kimura & H. Tamada, “Slurry Explo-
 J 65

sives”, JP 19239 (1968)&CA 70, 105 (1970) 145) H. Wakamiya et al, “Electric Detonators
129) K. Suzuki et al, “Combustion Stabiliza- or Delayed Explosives”, JP 10118 (1969)&CA
tion of Composite Propellants”, JP 19240 (1968) 71, 143 (1969)
&CA 70, 105 (1970) 146) K. Yamazaki & K. Kishi, “Composite
130) Y. Namura & J. Sate, “TNT (Trinitro- Solid Propellant Containing Preshaped Oxidizer
toluene)-Based Explosive Compositions Contain- Salt-Metallic Fuel-Burning Rate Controller Par-
ing Acrylamide Polymer Gel as Gelatinize. I. ticles”, USP 3454437 (1969) & CA71 , 161
Preliminary Experiments, KKK 29 (5), 300–07 (1969)
(1968)&CA 71,141 (1969) 147) K. Ito et al, “Ammonium Nitrate Explo-
131) Y. Nomura & J. Sate, “TNT-Based Explo- sives for Coal Mines”, JP 17518 (1969)&CA 72,
sive Compositions Containing Acrylamide Poly- 110(1970)
mer Gel as Plasticizer. 11. Detonation Velocity 148) Y. Nomura, “Explosive Compositions Con-
in the Closed State”, KKK 29 (6), 427–31 taining Acrylamide Gels as Plasticizers”, JP
(1968)&CA 71,141 (1969) 17519 (1969) &CA72, 125 (1970)
132) T. Suzuki et al, “Small-Arms Single-Base 149) T. Yamagi et al, “Porous Granular Am-
Propellant Charge”, USP 3442213 (1969) & monium Nitrate Production”, JP 18573 (1969)
CA71, 118(1969) &CA 71, 142 (1969)
133) S. Minekawa et al, “Flexible Explosive 150) 1. Hayakawa, “Composite Rocket Propel-
Compositions Containing Block Copolymers”, lants”, JP 27318 (1969)&CA 72,96 (1970)
USP 3449179(1969)& CA71 ,92 (1969) 151) T. Kakuda et al, “Propellants”, JP 28396
134) 1. Hayakawa & T. Harada, “Oxidants for (1969) &CA 72,133 (1970)
Composite Rocket Propellants”, JP 05717 152) A. Iwama, “Solid Propellants Containing
(1969) & CA72, 125 (1970) Titanium Dihydride”, JP 28397 (1969)&CA
135) H. Nagato et al, “Solid Rocket Propel- 72, 158 (1970)
lants’’, JP05718 (1969) &CA71 , 172 (1969) 153) T. Harada & I. Omura, “Composite Rocket
136) T. Yokoyama et al, “Solid Rocket Pro- Propellants with Carboxy-Terminated Binders”,
pellants”, JP 05719 (1969)& CA71 , 172 (1969) USP 2476622 (1969) & CA 72, 158 (1970)
137) K. Takata et al, “Preventing the Caking of 154) T. Yamashita et al, “Fluorine Containing
Ammonium Nitrate for Use in Explosives”, Polymers as Propellant Binders”, KKK 30 (3),
GerOffen 1906776 (1969)&CA 71, 172 (1969) 157–61 (1969) &CA72, 153 (1970)
138) K. Tsujihashi et al, “Continuous Mixing of 155) J. Okabe et al, “Slurry Explosives Con-
Nitroglycerol with Guncotton”, JP 10109 (1969) taining Lignin-Chromium Complexes Having
&CA71, 173 (1969) Plastic Characteristics and High Density”, Ger-
139) K. Tsujihashi et al, “Continuous Gelation Offen 1915456 (1969)&CA 72, 110 (1970)
of a Mixture of Nitroglycerol imd Guncotton”, 156) K. Tanaka et al, “Underwater Explosion
JP 10111 (1969)&CA 71, 173 (1969) in a Closed Vessel”, KKK 30 (4), 333–40
140) T. Kashimura et al, “Fuel and Binder for (1969) &CA78, 109 (1973)
Rocket Propellants”, JP 10114 (1969)& CA71, 157) Y. Wakazono & Y. Otsuka, “Slurry Explo-
172 (1969) sives Containing an Improved Thickening
141) Y. Ishitani & S. Akimaru, “Explosive Agent”, USP 3524777 (1970) & CA 73, 112
Compositions Useful for Metal Processing”, (1970)
JP 10115 (1969)&CA 71, 143 (1969) 158) T. Takei & S. Fujihira, “Explosive Com-
142) M. Shimohara et al, “Waste Molasses for positions”, JP 08676 &08677 (1970) &CA
Stabilizing Industrial Liquid Explosives”, JP 73,95 (1970)
10116 (1969)&CA 71, 173 (1969) 159) T. Fukuda et al, “Cellulose Acetate Coated
143) N. Nakashima, “Igniter Composition for Propellants”, JP 09279 (1970)& CA 73, 111
Solid Rocket Propellants”, JP 10 I 17 (1969)& (1970)
CA71, 172 (1969) 160) N. Tomoishi, “Low Density Colloidal
144) A. Tanaka et al, “Polybutadiene Mixed Dynamite”, JP09280 (1970) & CA 73, 111
Solid Propellants”, JP 10118 (1969) & CA 71, (1970)
142 (1969) 161) K. Kishi & T. Yamazaki, “Mixed Solid
 J 66

Propellants”, JP20188 (1970) & CA74, 138 Compositions for Blasting Concrete”, JP 27397
(1971) (1971 )& CA78, 129(1973)
162) H. Sato & F. Yoshida, “Propellant Blocks”, 179) I. Araki & T. Nakayama, “Application
JP 20199 (1970) &.CA74 ,98(1971) “ of Liners for Solid Propellants”, JP 06236
163) H. Sato & F. Yoshida, “Propellant Blocks”, (1972) &CA 7~ 147 (1973)
JP 20200(1970)&CA 74,98 (1971) 180) T. Ishimoto et al, “Aluminum-Magnesium
164) M. Hamasaki & N. Nakashima, “Method Alloys as Priming Compositions”, JP 14359’
of Cracking Concrete for Demolition Purposes”, (1972) &CA79, 148 (1973)
BritP 1205378 (1970) & CA .74, 98 (1971) 181) J. Kaneko & J. Nomura, “Propellant
165) K. Kishi & T. Yamazaki, “Solid Propel- Compositions”, JP 14360 (1972)&CA 79, 147
lant Mixtures”, JP 28318 (1970)&CA 74, 179 (1973)
(1970) 182) Y. Matsuguma et al, “Combustion Pre-
166) T. Maeda, “Composite Propellants Con- ventive Chemicals for C oalrnine Explosives.
taining Resin Binder”, JP 34959 (1970)&CA II. Inorganic Compounds”, KKK 33 (4), 214–
75, 146 (1971) 22 (1972) &CA78 , 108 (1973)
167) K. Kishi & Sh. Yarnazaki, “Priming Com- 183) S. Minekawa et al, “Self-Supporting Ex-
positions for Solid Rocket Propellants”, JP plosives”, GerP 1646268(1972)&CA 78, 129
34960 (1970) &CA75, 130(1971) (1973)
168) K. Tanaka, “Electric Signals Accompanied 184) T. Ohmori & E. Tane, “Ignition Agent
with Detonation of Explosives. II. Signals Origi- for Solid Fuel, Jl? 51202 (1972)&CA 80, 147
nated from the Product Gas”, KKK 31 (l), (1974)
28–31 (1970) &CA 78, 109 (1973) 185) Sh. Azaka et al, “Glue-Like Dynamite”,
169) O. Katsuki Preventive
et al, “Combustion JP 15480(1972)& CA79, 66 (1973) and CA
Chemicals for Coahnine Explosives. 1. Organic 81, 141 (1974)
Compounds”, KKK 31 (3), 131–37 (1970) & 186) M Takeda, “Moisture-Resistant Match
CA 78,108 (1973) Tips Containing Glyoxal”, JapanKokai 23909
170) Y. Hara & H. Osada, “Thermal Decom- (1973) &CA 79,89 (1973)
position of Ammonium Nitrate and a Mixture 187) H. Hijikata, “Sulfur-Free Match Tip Com-
of Ammonium Chloride and Sodium Nitrate”, position with High Porosity”, JapanKokai
KKK 31 (4), 236–43 (1970) &CA 78, 109 23910(1973) &CA 79,89 (1973)
(1973) 188) M. Takeda, “Match Striker Composition
171) H. Sakai & K. Tsutsui, “Industrial Explo- Containing Urea Resin as Adhesive”, Japan-
sives Containing Polyethyleneglycol Esters”, Kokai 23911 (1973)&CA 79,89 (1973)
JP 01600 (1971 )& CA76, 101 (1972) 189) D. Fakuma et al, “Stretchable Composite
172) Z. Meisek, “Sensitive Ammonium Nitrate Propellants”, JapanKokai 23912 (1973)&CA
Explosives”, JP 15798 (1971) & CA 76, 133 79, 115 (1973)
(1972) 190) D. Fakuma et al, “Powder Propellants
173) M. Hamasaki et al, “Gas Producing Com- with, Good Uniformity”, JapanKokai 23913
positions”, GerOffen 2063580 (1971)&CA 75, (1973) &CA 79,89 (1973)
80(1971) 191) A. Iwama, “Annual Review of Fuels for
174) Y. Nomura, “Plastic Explosives” JP 1973. Rocket Fuels”, Nenryo Kyokai Shi 52 (6),
22760 (1971 )& CA77, 196(1972) 390–94 (1973) &CA 79,65 (1973)
175) Y. Wakazono et al, “Slurry Explosives 192) M. Shinohara & K. Ohishi, “Industrial
Containing Aluminum Powder”, S. AfricanP Explosives”, Japan 05838 (1973) &CA 79,76
6907340(1971)&CA75, 104(1971) (1973)
176) T. Harata & T. Maetaj “Solid Propellants”, 193) K, Inoue et al, “Isocyanate Additive for
JP 26119(1971)&CA 79, 147(1973) Propellant”, JapanKokai 67415 (1973)& CA80,
177) T. Maeta, “Composite Propellants Con- 123 (1974)
194) K. Inoue et al, “Diketone Stabilizers for
taining Adhesive and Combustion Retardants,
Propellants”, GerOffen 2263037 (1973)& CA
JP26120 (1971)&CA 7~ 147(1973) 79, 147 (1973)
178) M. Hamazaki & N. Nakajima, “Explosive 195) A. Asano, “Smoke-Controlling Oily Agent
 J 67

for Ammonium Nitrate-Fuel Oil Explosives”, naphtha, triethylamine & iso-hexylamine

JapanKokai85712 (1973)&CA 80, 112 (1974) Refs: 1) H. Gartmann, Weltraumfahrt No 6,
196) U. Krone, “Pyrotechnic Compositions”, 134 (1951) &CA 46,4233 (1952) 2) O.E.
JapanKokai 2164437 (1973) & CA 80, 121 Lancaster, Edit, “Jet Propulsion Engines”,
(1974) Princeton Univ Press, Princeton, NJ (1959), p
197) A. Yokoyama, “Solid Propellants with 528 3) J.W. Herrick & E. Burgess, “Rocket
Improved Combustibility”, JapanKokai 98007
Encyclopedia Illustrated”, Aero Publ, Los”
(1973) &cA80, 34(1974)
198) Sh. Yamaguchi et al, “Solid Rocket Fuel”, Angeles, Calif (1959), pp 240-42
JapanKokai 99311 (1973)& CA80, 71 (1973)
199) T. Yamazaki et al, “Electric Igniter JB-2 Bomb. The American copy of the Ger
Charges”, Japan 08848 (1974) & CA 81, 144 “buzz bomb”. The chge consisted of a per-
(1974) forated cylinder, 8.5 inches OD, 2.5 inches ID,
200) H. Misashi & Y. Hori, “Waterproof Binders
36.5 inches long, and weighed 120 lbs. It de-
for Explosives”, Japan 09733 (1974) &CA 81,
145 (1974) veloped at 70”F a thrust of 11000 lbs for a
period of 1.85 sees. Four of these chges, each
encased in a suitable motor, were attached to
Jarrett, G. Burling, Col, US Army (1902–1974).
a launching sled, which ran on a heavy non-
Founder and curator emeritus of the world- portable rail system. By an ingenious develop-
famous US Army Ordnance Museum at Aberdeen ment of the US Air Forces, the bomb, sled &
Proving Ground, Maryland. His knowledge of rocket motors were converted to what amounted
armaments not only of the USA but also of to a free flight rocket. This light, highly port-
foreign countries helped US Government in able launching system had a great advantage
selecting new weapons, thus saving many dollars. over the heavy & rigid German launchers
He retired from the Army in 1966, but stayed The JB-2 Bomb did not come into combat
on as a voluntary researcher with the APG use, although a requirement for 500 launching
Museum, with the title of Curator Emeritus units a month existed at the end of WWII. The
Refi Anon, “In Memoriam. G. Burling Jarrett”, construction of a production plant with a capa-
National Defense, Sept-Ott, 1974, p 135 city of 600000 lbs of proplnt a month (suffi-
cient for 1200 launchings) was nearing comple-
JATO. Abbreviation for Jet Assisted Take Off tion. Interest in the JB-2 Bomb remained suf-
which refers to the use of an auxiliary rocket ficiently high so that the pilot plant was con-
motor for added thrust in the take-off of an verted to a small production plant for peacetime
aircraft. The usual JATO units are solid propel- operation
lants (Ref 2): Refi Summary Technical Rept of Div 8, NDRC,
“The Preparation and Testing of Explosives”,
Rocket description 12 AS-1OOOD-1 Vol 1 (1946), pp. 98–99
Charge type End-burning
Purpose Assisted take-off of aircraft
Thrust, lb 1000 (rated) JB Powders. Smokeless proplnts, patented ori-
Burning time, sec 12 (rated) ginally in 1888 by Johnson & Borland, and
Impulse, Ib-sec 16,000 (actual) manufd for many years by the EC Powder Co
Propellant Asphaltic composite Ltd, Greenhite, England (See EC Powders in
Outside tube diam, in 9.6 Vol 5 of Encycl, p E6-R). The milita~ proplnt
Length, in 36 contd NC 50, KN03 40 & roasted starch (partly
Gross weight, lb 205 burned) or lampblack 10%. A sporting proplnt
Propellant weight, lb 90 contd NC 50, KN03 22, Ba(N03)2 25 & roasted
However JATO units based on liq propellants starch or lampblack 3Y0. These powders are
,have also been used for example the “Tonka” no longer manufactured
fuels used with white fuming nitric acid (Ref 1). Rejl Daniel (1902), pp 386–87
Tonka fuels are mixtures of aniline,
monomethylaniline, dimethylaniline,
 J 68

JCP Powder. One of the varieties of plasto- Typical Jetcord comes in a veriety of sizes
menites. It is a sporting smokeless proplnt for special applications. The powerful linear-
contg NC, DNT & Ba nitrate shaped’ chage permits demolition contractors to
Refl Daniel (1902), pp 387 & 634 cut supporting steel structures with a few ounces
of expl rather than depend on the blast effect
of large quantities of expls. Jetcord has been
JellyBag Method of Mixing. See under Drums, used successfully to demolish buildings & bridges
Rotary (Rotating) for Blending (Mixing) of Refi Industrial Research Magazine (April 1974),
Explosives and Their Components in Vol 5 pp 67–70
of Encycl, p D1556-R

Jet Formation in Shaped Charges. See Detona-

Jelly, Mineral. Same as vaseline tion; BMT (Birkhoff-MacDougall-Pugh-Taylor)
Theory of Jet Formation in Shaped Charges in
Vol 4 of Encycl, p D226-R; and Detonation,
Jensen’s Test (For Stability of Explosives). Munroe-Neumann Effect (or Shaped.Charge
Test tubes, each contg O.lg of a NC expl, are Effect) and Lined-Cavity Effect in on””pp
suspended in a bath of mineral jelly preheated D442-Rff
to 1000. A strip of KI-starch paper is suspended
above the sample. Heating of the bath is con-
tinued, by raising the temp 5° per rein, until JET FUELS. hrtroduction. These are fuels for
the point is reached at which the test paper air-flow jet propulsion systems (See Jet Propul-
begins to color. This point is taken as an indi- sion in this Vol). Fuels for rockets are described,
cation of the stability of the NC proplnt. in part, under Hyperbolic Propellants in this Vol,
Jensen’s Test is a combination of the deflagra- pp H254ff. Air-flow jet propulsion systems are
tion test of Sy and the Abel Heat Test divided generally into two categories: those
Refi Reilly (1938), pp 80 & 83 needing an extemrd source of ignition “imd those
that are self-igniting or hyperbolic
Recent literature on jet fuels is very extensive,
Jetcord. An Explosives Technology (Fairfield, eg between 1957 & 1971 there are some seven
Calif) development which is special expl chge pages of Refs to jet fuels in CA indexes and these
similar to we military shaped, or “hollow probably do not include all contract research
chge”. It consists of a metrd-sheathed, expl- reports and certainly not classified literature.
ffled, linear-shaped chge, having an approx What follows is a summary of the props & re-
chevron-shaped cross section. Jetcord is quirements of the most common jet-aircraft
available in a size range (1000, 2000 & 4000 fuels (JP series) and a list of recent review
grains/ft expl chge) that permits the cutting of articles on these and other jet fuels of special
a few roils of Al up to 3 inches of steel. Ini- interest
tiating the expl device raised a problem. The . Jet Fuels (Grades JP-3, JP-4, JP-5 & JP-6).
use of conventional, highly sensitive electric Specifications for early aircraft jet fuels were
blasting caps would not be feasible in the vici- based primarily on manufg considerations, since
nity of high-powered elec machinery. An alter- it was believed that aircraft could burn almost
native was to use a very insensitive device known anything of the nature of kerosene fuels (Ref
as Exploding Bridgewire (EBW) detonators de- 1). Later improvements in aircraft, particularly
veloped during WWH (See in Vol 4 of Encycl, in high-speed jets, made it necessary to pay more
p D807-L and in Vol 6, p E353-R). EBW de- attention to fuel characteristics and less attn to
tonators differ from conventioml types in that ease of manuf. The most important of these
they require currents of thousands of amps de- fuel characteristics is fuel stability at high temps.
livered in a few microseconds before they will Other problems associated with jet aviation fuels,
detonate. Under such elec impulses, the deto- both for military & civilian use, are minor corn-”
nator bridgewire literally explodes, and the re- pared to stability at high temps. Such problems
sulting high temp shock adequately initiates include availability, handling & physical property
Jetcord specifications
 J 69

The need for thermal stability of jet fuels is tion of jet fuels under defined conditions. The
based on the following facts. In supersonic apparatus selected was called the Erdco Jet
flight, the aircraft is subjected to high tempera- Fuel Coker. Data correlation was undertaken
tures. This heat must be removed. Most con- by the Coordinating Research Council, an or-
venient solution, in many types of jet aircraft, ganization sustained jointly by the Society of
would be to use the fuel as a heat sink for Automotive Engineers, and the American Pe-
cooling vital aircraft components, such as engine troleum Institute
oil With this Erdco coking unit, the test fuel
Theoretically, use of fuel as a coolant is under consideration is pumped thru an amular
convenient. But, it is we~ known that heating heat exchanger. Hot fuel then passesthru a
oils for even short periods of time accelerates heated sintered steel filter. Fuel, flow rate,
gum and sediment formation. (In fact, “this is fuel temperature, and filter temperature can be
the basis for many stability prediction tests in varied over a wide range to control test severity.
the petroleum industry.) It was not unexpected Insoluble sediment which is formed during the
then, that when fuels are heated in aircraft heating operation deposits on the filter. The
fuel systems, temperatures would be high enough time required to achieve a given pressure drop
to cause some fuel degradation across the filter is a measure of fuel stability.
Mechanism studies of this disintegration have Visual observations of the heated tubes are
been resolved into three thoughts: made to estimate heat exchanger fouling ten-
a) fuel is cracked dencies
“b) fuel is oxidized More specifically, typical operating condi-
c) fuel is polymerized tions are: a flow rate of 4 pounds per hour, a
Most workers in this field believe polymeriza- fuel temperature from the heat exchanger of
tion to be the cause of sediment which plugs 400”F, a falter temperature of 500”F, and a
fflters and deposits lacquers on such vital parts fuel pressure of 150 pounds per square inch
as heat exchanger surfaces gage. Fuel stability is then determined by
Although petroleum refiners are not unfamiliar operating until a pressure drop of 25 inches of
with questions of thermal stability of petroleum mercury is obtained across the fiiter or until
products, jet fuel stability requirements (stable 300 minutes have elapsed. No heater tube
in the range 400–500°F) presented a new set appearance requirements have been designated
of problems. One of the first things to be done Some characteristics and requirements of the
was to define limits of acceptable stability. Such JP Series of fuels is given below (Ref 1) (more
limits naturally would depend upon individual detailed characteristics are presented later):
engine design and the environment to which the JP-3 (Used by Military). A mixture of about
fuel is exposed. Fuels meeting one set of con- 70% gasoline and 30% light distillate. Specifi-
ditions could conceivably fail to meet another cations limiting boiling range are a 5 to 7 pound
set. The solution: devise some sort of labora- Reid vapor pressure and a maximum 9~o eva-
to~ test that would correlate with actual engine porated point of 470”F
performance JP-4 (Used by Military and Commercial). A
Pioneering efforts in this were carried out by mixture of about 65% gasoline and 35% light
Pratt & Whitney and Du Pent. Working with a distillate. Reid vapor pressure specification is
scaled down fuel system, they were able to obtain 2 to 3 pounds. Product was developed as a re-
some degree of correlation with engine perfor- placement for JP-3 because of excessive fuel
mance. But, around the same time, others losses encountered at high altitudes with JP-3
interested in this problem – refiners, engine JP-4 referee (Used by Military). A special
manufacturers, and air frame designers – began grade of JP4 having rigidly specified character-
to build test rigs. Soon there were as many istics. Fuel is designed to be typical of lower
devices as there were groups involved in the quality JP4 fuel which would be available in
thermal stability problem. Consequently, a wartime. Used in developing and testing of
meeting was arranged to suggest a suitable piece military jet engines
of equipment and set up a program for evalua- JP–5 (Military). Essentially a specially fraction-
 J 70

ated kerosine. Flash point is higher (140”F) Again citing the laboratory example above, the
and freezing point (–40°F)” lower than most same JP-5 fuel hydrotreated shows improved
kerosines stability to 300 plus minutes
Kerosine (Used by Commercial) has essentially Use of hydrogen is effective in removing
the same requirements as burning kerosine with trace constituents, often times the bad actors,
the exception of freezing point. Commercial such as nitrogen and sdfur. Also, hydrogen
airlines usually require freezing point of –40°F saturates previously unsaturated olefiris or aro-
maximum because of the low temperatures en- matics which may be present. The amount of
countered at altitude. Many, but not all, hydrogenation depends again, upon the source
burning kerosines will meet this requirement of crude oil. Good cfides may only need mild
Attempts have been made to increase the hydrogenation, other cases,heavy
stability of the above fuels by: Another possible solution to the problem of
a) use of processing or treating techniques high temperature stability is the use of additives.
b) incorporation of additives Not exactly a stranger to petroleum people (as
c) segregation of stable stocks evidenced by use in gasoline and lubricants) they
Use of conventional treating processes was generally fall into two classes: metallic and non-
the logical starting point for improving thermal metallic. The former, for the most part are
stability since refiners already have these faci- metal salts of sulfonates or naphthemtes, whereas
lities. One of the first treating’ processes con- the latter are either aminei or amine derivatives
sidered was sulfur dioxide treatment, although (later other organics may prove more effective)
current capacity would possibly be insufficient Use of additives in jet fuels, however, must
in an all-out war. In tests carried out at one of necessity be approached with ‘caution. As
petroleum laboratory, a JP-5 fuel stability was surface active “materials, many have a variety of
increased twofold: Untreated fuel had a stabi- uses and properties. Hence, they must not in-
lity rating of 57 minutes. After sulfur dioxide troduce new problems such as foaming at high
extraction, the time was increased to 119 mi- altitudes, emulsification, or interference with
nutes. However, for all intent and purpose, this low temperature flow. These could easily lie
is not considered to offer any benefits since severe Mnitations, but additives are under serious
the test defines acceptable stability as 300 mi- consideration thruout the industry
nutes Additives can be most effective when con-
Another refinery treating procedure is acid taminants causing instability have been mini-
treatment. This method is somewhat success- mized by refinery processes such as hydrogena-
ful. In further test on a JP-5 fuel at the above tion. In general, however, the prime ‘purpose of
mentioned laboratory, the improvement fact or an additive is either to dissolve or prevent for-
was 2.5 or 157 minutes. Actually, effectiveness mation of sludge or else to disperse sediment
of treating depends upon the crude oil supply in fine particles which enables passing thru
and its appearance after original refining, that filters and other vital engine parts. The problem
is, first separation from the crude. What would is of prime concern in the case of metallictype
be described as mild treatment is good for one additives which can build up ash deposits, which
refiner, but another, because of crude supply, can seriously affect jet engine operation. An
would need mucli higher treats, say to the order appreciable slug of ash can do extensive damage
of 25 to 50 pounds per 42-gallon barrel, before if suddenly tossed thru a jet engine
a stable product is obtained. Acid treating is Studies have been made thruout the refining
not favorable from ~e processing side, but it industry in an effort to utilize selected stocks
is possible to produce high quality fuels with for the production of jet fuels. Basically, this
the process would amount to determining the stability of
A better, approach to achieving thermal many stocks, for example, straight run gasolines,
stability is’ thru hy’tlrogenation. Hydrogen is now distillates, kerosines, #kylate bottoms, and what-
readily available in most refineries because of ever else is available from refinery streams. Those
catalytic reforming developments. Hydrogena- with best heat stability, by laboratory “test, could
tion produces fuels of excellent thermrd stability. then be blended into jet fuels meeting required
 J 71

specifications Recent Review Articles on Jet Fuels.

To meet military supply and demand it Hibbard & Olson (Ref 10) discuss turbojet
often becomes necessary to maintain large supplies & rarnjet fuels and their relation to fuel systems
of jet fuels at various locations thruout the world. Carney (Ref 11) reviews the props of “slush”
This fuel must be stable so it can be available hydrogen and points out its desirability as a
for immediate use. While fiel can be kept re- space vehicle proplnt firel because of wt savings
latively new in some areas by means of stock on long-term storage. “Slush” hydrogen is a
‘rotation, this may not be possible in others. This fluid mixt cont( solid Hz (by wt) 50% in liq Hz
brings up the problem of stability in standing F-O mixts (Flex) with light hydrocarbon (HC)
storage fuels as rocket proplnts for upper-stage applica-
Jet fuels carr be made from a very broad tions show the unique ability to provide high
hydrocarbon range, in fact, anywhere from 150°F performance, space storability, hypergolicity,
to 600°F depending upon specifications. Fuels current availabilityy, high d, and capability for
consist of certain quantities of straight run, cata- both transpiration & regenerative cooling.
lytically cracked, and thermal cracked material. Methane, (CH4), gives the highest theoretical
Stability-wise, straight run is most stable; ther- specific impulse of an HC fuel with Flex, but
mrd cracked least stable. Hence, most blends others show advantages in handling, bulk d,
end up intermediate and regenerative & cooling capability. Blending
Standing storage stability can usually be im- of HC fuels may further improve space stora-
proved by the same general procedures being bility, fuel d, and fuel cooling ability. Methane
explored for thermal stability, that is, acid is the best HC fuel with Flex in a transpiration-
treatment and/or hydrogenation, where improve- cooled engine or in a regeneratively cooled en-
ment is gained by removal of nitrogen and sulfur gine operating at supercritical pressure in the heat
compounds, olefins and diolefins. Hence, the exchanger. 1-Butene and a eutectic blend of
problem today is actually a corolla~ of thermal pentane & iso-pentane are the most promising
stability fuels for regenerative cooled thrust chambers at
Another problem encountered with jet fuels subcritical pres&rres, An F/O ratio of ca 82/1 8
is due to contaminants and the consequent gives a sharp max specific impulse with methane
plug@g of filter systems in the jet aircraft. as the fuel. Such high concns give hypergolicit y
Handling and distribution systems for jet fuels (ignition on contact with fuel) almost like F
are usually underground. Fuel is pumped out rdone. Data are given on ignition delay times
of the tank by water displacement. Understand- using Flex with several light HC fuels and with ‘
ably, when fuel is moved, there is some agitation. H. AU give satisfactory short ignition times for
If an additive is present, emulsification is possible. ambient sea-level start and during cold-rdtitude
Also, there may be many contaminants such as starts (Ref 12)
rust, dirt, and water. The rate of settling, na- Lo (Ref 14) predicts that “triergol” or
turally is a function of viscosity and density. “tribrid” proplnts will provide max thrust in
This is important since jet en@es camot future rockets & space vehicles. These systems
tolerate too much foreign matter contain a metal (or metal oxide) in addn to Hz
For the most part, -fdtration systems can as fuel. Examples are: 03/Be/H2, 02/Be/H2
remove the contaminants. However, aside from & F2 /Li/H2. They give a much greater specific
foreign matter there is the case of insoluble impulse (See Isp in this Vol,’ p 163-R), than the
formed from the fuel in the nature of gums. corresponding “diergols” 03/Hz, 02 /H2 & ‘‘
In this. respect fdterability behavior is apparently F2 /H2 by increasing the reaction temp. In
related to the character of the deposits formed. practice, 3 tanks ,ue required for the ‘triergol”
The more crystalline the deposit the less ten- system, but one of them can also serve as the
dency to plug fflters combustion chamber
Zabetakis et rd (Ref 6) reported that mixts Zrelov (Ref 15) reviews the development of
of JP-4 & UDMH (unsym-Dimethyl Hydrazine, jet fuel technology with emphasis on production
See in this Vol, pp H203-R to H204-L) are methods, composition, ener~ content, combustion
insensitive to shock
 J72 \

Table I
Chemical and Physical Requirements and Test Methods

., Fuel I Test method

Rcqllircmcut.s Federaltest
GradeJP-3 NATO GradeJP-4 NATO GradeJP-5 NATO method ASTM
symbolnone symbolF-40 symbolF-42 standsrd st&ndards
No. 791

Distillation:
Initial boiling poi[,t.--. -.-,. - . . . ..-. ----- (1)-------
“ . . . . . . . . . . (’)----------------- (’)-----------------
Fuel evaporated,10percentmin. at------ (9----------------- (9----------------- 400°F. (204.4”C.)-.
Fuel evapwaterf,20 percentmin. at------ 240°F. (115.6°C.)-- 290”F. (143.3°C.). - (9--.-------..-----
Fuel evaporated,50 percentmin. at------ 350°F. (176.7°C.)- - 370” F. (1S7.S0C.).. (9-----------------
Fuel evaporated,90 percentmin. at. - ..-, 470”F. (243.3°C.). - 470” F. (243.3”C.)-. (1)----------------- ~ 1001 D86
Endpoint, max---.. --.. -.. --------- .-, (1)----------------- (1)--.---------.---- 550” F. (287.8”C.) --
Percentevaporated,at 400”F. (204.4°C.). (9----------------- (’)----------------- --------------------
Residue,vol. percentmox-.--.--l------. l}4------.--_------ W&---.------------ l)L--.---.-.---.---
Distillation loss,vol. percentmax-------- 15__--.-_-.----- l%-.--.--.-------.- l)i----------------
Gravity OAPI—min.(specificgravity, max.)--- 50.0 (o.780)--------- 45.0 (0.802) --------- 36.0 (0.845) --------- - 401 D287
Gravity “API—max.(specificgravity, min.)-.. 60.0 (0.739) -,----- 57.0 (oc751)-------- 4S.0 (0.7S8)--------- 401 D287
Existent gum,mg/100ml, Max--.---. -.--,--- 7------------------ 7-.--.-.--------.-- 7------------------ 3302 D3S1
Potentir#gum, 16hr. agifig,mg/160ml, max-. 14----------------- 14----------------- 14----------------- 3354 z DSi3
Sulfur, total, percentwt. Max---------------- 0.4----------------- 0.4----------------- 0.4----------------- 5201 D1266
Mercaptan-sulfur,percentwt. mns.s---..--.-. 0.005 --------------- 0.001 --------------- o.ool -------------- 5204 D1219or D1323
Reid vapor pressure,100° F. psi, min. (gin/ 5.0 (351.6) -------- 2.0 (140.6) -------- -------------------- 1201 D323
cmZ,min.).
Reid vapor pressure,100° F. psi, ma... (gin/, 7.0 (492.2)-------- 3.0 (210.9)--------- ---:---------------- 1201 D323
cmt,max.).
Frwzing ~int, °F.,msx-------------------- –76° (-60° C.)---- –76° (-60° C.)---- –55”(–4s” c.)---- 1411 D1477
Thermal value (see3.2.2) Heat of combust. ll3,400------------- ls,400:------------ 18,300-------------- 2502 -------------- -
(loweror net) BTU/ilJ min.
or Aniline-~avity product,rein ---------- 5,250-------------- 5,250----___----- 4,500-------------- 3601and 401 D611and D2S7
Viscosity,centistokeeat –30° F. (–34.4° C.), ------- ------------ -------------------- 16.5---------------- 305 D445
max.
ArOnlMiCS, w>!,perCCnt max----------------- 25.0. . . ------------- 25.0---------------- 25.0---------------- 3703 D131!I
Olefin, vol. p{wcut mlix.~-.-----..------.---. 5.o---------------- 5.0---: ------------- 5.0----------------- 3703 D1319
Smokepoint, mm mill ---------------------- (9----------------- (’)----------------- 1~.o---------------- 2107 D1322
Explosivm,cw,percentmnx.-.--------.--.-.. ---------.- -------- -------------------- -------------------do-----------------1151 ---------------
Smokevolatility index,miri. (see3.2.3)------- 52.0---------------- 52.0---.--_-.---:-- -------------------- ------------- ------------- --
Cepperstrip corrosiou,ASTM classification, No. 1-------------- No. 1-------------- No. 1-.--.-----.-.- --------.---- ~D130
max.
Water re8cti0n, vol. change,ml, max. (see 1.----------------- 1-.---------.--.--- 1------------------ 03251 --------------- I
3.2.1).
l%.+ point, niin----- .--------- .----- .---.: ..:----------------- -------------------- 140°F. (60.0”C.)--- 1102 D93
Thermalstability--------------------------- -------------------- (t).------------.--- (’)----------------- 13464 ----------------
Changein pressuredrop in 5 hr, in. Hg---- -------------------- (’)----------------- (’)----------------- 73464 ----------------
Prcl,euterdc~sit- .------------” -------- -------------------- (1)----------------- (1)----------------- 73464 ---.--..----.---

1 To be rep,orted ,– not limited 5 To be performed in accordance with paragraph titled

2 Use steam jet method of D381 after oxidation “Tests at 2 12°F for Aircraft Engiqe Fuels” of
3 The mercaptan-sulfur determination may be waived at ASTM, D 130,56. Earlier ASTM methods are not ap-
the option of the Inspector, if the fuel is considered plicable since they require a dry sample
“Doctor sweet” when tested ‘h accordance with Method 6 See 4.5.1 for exception to Method 3251
5203 of Federal Test Method Standard No 791 7 See 4.5.2 for test conditions under Method 3464
4 May be reported as Bromine No when specified
by the armed service for whom the material is approved
 J 73

characteristics, scale formation & corrosion ten- Beatty & Gluckstein (Ref 8) propose a mixt
dencies, volatility, thermal & oxidation stability, of Me3Al 5–40 & Et3Ai 95–60% as a jetfuel
low temp props, and expln & fire hazards igniter in jet aircraft engines
Giacco (Ref 16) reviews solid proplnts for Becker (Ref 9) claims that wetting the com-
use in rockets bustor surface of a jet engine with di-methyl-
Koecker (Ref 17) reviews specification re- silicone or Si(OEt)4 prevents decompn of
quirements of fuels for industrird gas turbines, Bez 03, on the engine walls, from Be contg
conventional jet turbines (kerosine & gas oils), fuels, such as a 4/1 mixt of trimethoxyboroxime-
supersonic jet engines (JP-5 & JP-6), and future acetone
hypersonic jets (endothermic fuels) Because of the importance of these fuels,
Back (Ref 18) discusses proplnt toxicology, the Military Specifications for Jet Fuels, JP-3,
including toxicological effects on blood pres- .JP-4& JP-5 (Ref 4) are listed:
sure, heart rate, and effects on autonomical & 1. SCOPE
central nervous systems caused by N2H4 & 1.1 Scope. This specification covers fuel”
derivs, penta- & decaboranes, F compds. and Be for aircraft turbine engines, ramjet engines, and
compds rocket engines
The handling of hazardous fuels & oxidizers 1.2 Classification. Jet fuels shall be of ,the
is reviewed by Cloyd & Murphy (Ref 13). Data following grades, as specified:
are presented on some highly reactive materials
that have been studied in the search for fuels Grade NATO symbol Description
& oxidizers for space work, including liq H, JP-3__ None ___ High vapor pressure type
pentaborane, F, C1F3, 03, N 204 & N2H4 and
Low vapor pressure type
its derivs. Both the hazards that restricted the JP4__ F40
“n (NATO description:
use of these materials and the procedures by
wide-cut, gasoline type)
which they were handled & stored safely are
described. Refs are given to work done by High flash point,
JP-5__ I F42 I
NASA & other investigators kerosene type
Jet Fuel Patents. 3. REQUIREMENTS
The patent literature on jet fuels is very ex- 3.1 Materrizls. The fuel shall consist com-
tensive. Some examples of patents granted on pletely of hydrocarbon compounds, except as
jet fuels are as follows: Fox & Britton (Ref 2) otherwise specified herein
claim the incorporation of viscosity-index im- 3.2 Chemical and physical requirements.
provers in jet fuels to improve engine start-up The chemical and physical requirements of the
& combustion efficiency over a wide range of fuel shall conform to those listed in Table I,
temps. Materials claimed to be effective are when tested in accordance with the applicable
ethyl glycol, Acryloid & Sanotex tests. Requirements contained herein are abso-
Maisner (Ref 3) claims that incorporating lute and are not subject to correction for tol-
nitroparaffin gel improves jet fuels erance of test methods. However, if multiple
Burkhardt (Ref 4) proposes proplnts, for re- determinations are made, average results shall
action engines, with compns which contain be used
finely divided metals such as Zn, Cd, Mn, Fe, 3.2.1 Water reaction. The fuel shall sepa-
Pb&W rate sharply from the water layer with only a
Thomas (Ref 5) claims system: useful for few small bubbles around the periphery of the
propulsion of rocket shells, JATO &, airborne interface and no shreds of lace or film at the
vehicles, consisting of a mixt of finely divided interface. Neither layer shall have changed in
MeN03 with fuels which are nitro compds, volume by more than 1 milliliter
such as NGu, Amm Picrate, etc. The addn of 3.2.2 Heating value. The heat of combus-
Al can modify burning characteristics. Binders tion determination may be waived at the option
are, chlorinated polyphenyls or urea resins. The of the Inspector if the aniline-gravity product
ingredients are milled on rolls just hot enough to of the fuel is not less than the numerical values
soften the resin and then the mixt is pelleted specified in Table The aniline-gravity product
 J 74

is defined as the product of the gravity of the from undissolved water, sediment, and suspended
fuel in degreesAPI and the aniline point of matter. No substances of known dangerous
the fuel in degrees Fahrenheit. If the aniline- toxicity under usual conditions of handling
gravity product of the fuel is less than the and use shall be added
value specified, the fuel shall be accepted or 4. QUALITY ASSURANCE PROVISIONS
rejected on the basis of the heat of combus- 4.1 General. AU the tests required herein
tion requirement for the testing of fuel are classified as accept-
3.2.3 Smoke volatili~ index. The smoke ance tests, for which necessary sampling tech- ‘
volatility index shall be computed from the niques and methods of testing are specified in
following equation: this section
S.V.I. = S.P. + [0.42 x volume percent boiling 4.2 Inspection. Unless otherwise specified
under 400°F (204.4°C)] by the procuring activity, inspection shall be in
where: S.V.I. = Smoke volatility index accordance with Federal Test Method Standard
S.P. = Smoke point in millimeters as No 791, Method 9601
determined by ASTM Method 4.3 Sampling. Sampling shall be in accord-
D1322 ance with ASTM Method D270 titled Sampling
3.3 Additives. The additives listed herein of Petroleum and Petroleum Products
may be used singly or in combination “in amts 4.3.1 When required, a 10-gallon sample,
not to exceed those specified taken in accordance with ASTM Method D270,
3.3.1 Antioxidant. The following active shall be forwarded to the laboratory designated
inhibitors may be added separately or in com- by the procuring activity for testing as specified
bination to the fuel in total concentration not herein
in excess of 8.4 pounds of inhibitor (not in- 4.4 Examination of product. Each container
cluding weight of solvent) per 1000 barrels of of fuel may be examined to determine confor-
fuel (9.lgm/100 US gal, 24mg/liter or 109 mance with this specification
mg/imp gal) in order to prevent the formation 4.5 Test methods. Tests as specified in 3.2
of gum: to determine conformance to chemical and
a) 2 ,6-ditertiary butyl-4-methyl ‘phenol physical requirements shall be conducted in ac-
b) NM’-Diiecondary butyl paraphenylene- cordance with Federal Test Method Standard
diamine No 791 or ASTM standards, using applicable
c) 2,4-dimethyl-6-teritiary-but ylphenol methods as listed in Table I, except for the
d) 2,6-ditertiary-butylphenol following
3:3.2 Metal deactivator. A metal deactivator, 4.5.1 Water reaction. The water reaction
N~’-disalicylidene- 1, 2-propane-diamine, or test shall be conducted in accordance with
NJN’-disalicylidene 1,2-ethylene diamine may Method 3251 of Federal Test Method Standard
be added in w amount not to exceed 2 pounds No 791, except that the water used for the test
of active ingredient per 1000 barrels of fuel shall be a buffer solution consisting of 1. 15g
(2.2gm/100 US gal, 5.8mg/liter or 26mg/imp ~ HP04 (anhydrous, reagent grade) plus 0.46g
gal) KH2P04 (anhydrous, reagent grade) per 100rnl
3.3.3 Corrosion inhibitor. An approved of distilled water. This” solution shall have a
corrosion inhibitor sJ-@lbe added. The cor- pH of 7
rosion inhibitor furnished under this speci- 4.5.2 Thermal stabili~. A manual, semi-
fication shall be product which has been automatic or automatic CFR fuel coker shall
approved under Specification MIL-I-25017. be used. The equipment and operating pro-
The amount’ added shall be listed in QPL-25017 cedures shall be in strict accordance with
(latest revision). The, coritractor “shall maintain Method 3464 of Federal Test Method Stan-
and, upon request, shall make available to the dard No 791. No deviation from this method
Government, evidence that all inhibitor product; is allowed
used are equal h every respect to the product 4.512.1 Test conditions. The tei conditions,
qualified under Specification MIL-I-25017 as applicable, shall be in accordance with Table
3.4 Workmanship. The fuel shall be free II
 J 75

Table II. Thermal Stability Test Conditions Hibbard & W.I. Olson, CombustPropellenti-
Nuovi, AttiConvMilan 1963, 217 (Engl) & CA
61, 15904 (1961) 11) R.R. Camey, Adv-
CryogEng 9, 529 (1964) &CA 61, 13115
(1964) 12) A.I. Masters, JSpacecraftRockets
Preheater temperature (0 F.)------ 300 400 3 (6), 905 (1966) &CA 65, 10415 (1966)
Filter temperature (0 F.)---------- 400 500
Fuel flow (lb/hr)----------------- 6 6 13) D.R. Cloyd & W.J. Murphy, NASA Rept
Test time (minutes) -------------- 390 300 SP-5032 (1965), AEC Accession No 1727 &
CA 65, 10415 (1966) 14) R. Lo, ChemIng-
Tech 39 (15), 923 (1967) &CA 67, 92451
4.5.2.2 Reported data. The following data (1967) 15) V.N. Zrelov, ItogiNaukiTekhnol-
shall be reported: OrgVeshchestv 1966, 5 (Publ 1968)&CA 72,
a) Differential pressure in inches of mercury 4854 (1970) 16) M. Giacco, QuadMerceol
at 300 minutes or time to a differential 7 (l), 63 (1968) (Ital) &CA 71, 83156 (1969)
pressure of25inches ofmercury, which- 17) M.H. Koecker, BrennstChem 50 (4), 105
ever comes first (1969) &CA 71, 5038u (1969) 18) K.C.
b) Preheater deposits at the end of the test Back, FedProcFedAmerSocExpBiol 29 (6),
4.6 Rejection and retest. Material not con- 2000 (1970) &CA 74, 11530 (1971)
forming totherequirements of this specifica- 19) US Specification Ml L-T-5624J, “Turbine
tionshall be rejected. Rejected material shall Fuel, Aviation, Grades JP-4 & JP-5° (Ott 1973)
not be resubmitted without furnishing full par-
ticulars concerning previous rejection and mea-
sures taken to overcome defects Jet Perforators & Jet Tappers. Two commercial
6. NOTES applications of the Shaped Charge Effect,
6.1 Intended use. The fuel covered by this marketed by the duPont Co, are described in
specification is intended for use in aircraft tur- the Blasters Handbook (Ref 1). The principle
bine engines, ramjet engines, and rocket engines upon which they are based is as follows:
6.3 Precaution for mixing inhibitors. To “The jet principle is simply the focusing of
prevent any possible reaction between the con- a greater than normal amount of the heat and
centrated forms of different corrosion inhibi- energy of an explosion against a very small
tors, the fuel supplier is cautioned not to com- area, This is accomplished by using a high
mingle corrosion inhibitors prior to their ad- density, high strength explosive formed around
dition to the fuels a conical liner of metal or glass. When the ex-
written by J. ROTH plosive is detonated, the cone is collapsed and,
vaporized, forming a small high temperature -
jet containing particles of liner material moving
at velocities of 10000 to 30000 feet per second.
Refs: 1) Staff, C&EN 33, 4502 (24 Ott 1955) This strikes the target with such heat and force
2) H.M. Fox & S.C. Britton, USP 2712726 that the target simply flows radially from the
(1955) &CA 49, 14298 (1956) 3) H. Maisner, point of impact leaving a deep nearly round hole.
USP 2712989 (1955)& Ordn 40,476 (1955) The principal factors that control the performance
4) W. Burkhardt, GerP 1021238 (1957) & CA of jet charges are the type and weight of explo-
54, 10328 (1960) 5) C.A. Thomas, USP sive, the diameter, material, and shape of the
2857258 (1958) &CA 53,2580 (1959) cone, and the stand-off or, distance to the target”
6) M.J. Zabetakis et al, US BurMines RI 5635 DuPont let Perforators are explosive shaped
(1960) &CA 54; 21763 (1960) 7) J. Kofen- charges specifically designed for perforating oil-
bach & T. Wasserbach, USP 2938779 (1960) well casing and penetrating far into the surround-
&CA 54, 17851 (1960) 8) H.A. Beatty & ing formation. ‘fhgse charges consist of a copper
M.E. Gluckstein, USP 2935839 (1960) &CA cone and explosive charge contained in plastic
54, 17889 (1960) 9) E. Becker, USP 2986876 or metal bodies of different sizes depending upon
(1961) & CA55, 26448 (1961) 10) R.R. the specific well to be perforated
 J 76

When detonated, duPont Jet Perforators emit and other causes of accidental detonation as
a high velocity jet of tiny copper fragments compared to most commercial explosives. If
which penetrate the oil-well casing and formation heated to a high enough temperature it will
leaving a deep, large diameter hole through which burn without detonating. In one test a case
the oil can flow into the well ‘ of Jet Tappers was completely burned in a
Perforators for both “carrier” and “through: bonefire of kerosene-soaked wood without
tubing” type oil well completions are available. detonating. In another test, six Jet Tappers
In “carrier” type guns ranging from 2 5/8 to were laid side by side between steel plates and
5 inches OD, the Jet Perforators are threaded a 150 pound weight was dropped nine feet
on a strarid of “Primacord” and loaded into onto the upper plate. The charges were com-
the gun, a steel’ tube which is sealed at both pletely crushed but there was no detonation
ends. The gun serves to control the standoff The special Jet Tapper Blasting Caps have
distance and prevents the well fluid from been designed to withstand prolonged exposure
interfering with the jet formation. For through- to high temperatures. Experience ha: shown
tubing completion a smaller version of the that they will stay in a hot tap hole for from
carrier-type perforator can be supplied three to eight minutes before detonating when
duPont pioneered the development of shaped they are used as part of the Jet Tapper assembly
charges for oil well use and these perforators The only phase of open hearth furnace
and auxiliary devices have been used depend- tapping, as it is now practiced, thatis replaced
ably for several years in the oil well industry by the-use of the Jet Tapper is the lancing
duPont Jet Tappers are designed for tapping operation or the burning through of the tap
open hearth steel furnaces. They consist of a hole facing with an oxygen lance. The tap
two ounce charge of a very powerful explo- hole must be dug out to the facing as is the
sive in a plastic case with a copper cone. The present practice. The Jet Tapper is then slid
charge is contained in a bullet-shaped insu- into the tap hole until the nose of the insu-
lating jacket. When the Jet Tapper is assembled lating jacket touches the facing, as shownin
for use, a special high temperature Jet Tapper the diagram. The person placing the Jet Tapper
Blasting Cap is threaded through a hollow then retires to the firing point and the Tapper
fiberboard pole eight feet in. length, the cap is detonated
is inserted in the charge, and the insulating Field experience indicates that over-a~-a 90
jacket is slipped onto the end of the loading to 95 percent average of successful taps is being
pole obtained using duPont Jet Tappers, and that
The explosive used in the Jet Tapper is the unsuccessful taps are very easy to lance. The
relatively insensitive to impact, friction, heat, unsuccessful taps can usually be traced to: (1)
.,

,.. ,,!

,,, ,,

t
JET TAPPER
Cross Section of Open Hearth Furnace Tap Hole Showing Jet Tapper
in Position for Firing
 J 77

a poorly dug out tap hole, (2) steel which has brevity, we include all these propellants
leaked through the facing, or (3) excessively under the single term fuel”
high furnace bottoms “For propulsion in the atmosphere, where
The use of Jet Tappers has proved to have ambient air is available, this air may be in-
the following advantages over the conventionrd ducted by the jet engire in order to partici-
method of tapping: pate essentially in the chemical transformation
(1) No one is at the runner when the metal of the fuel: the engine is then properly called
flow starts an air “flow jet engine in contrast to the
(2) The danger of burns from faulty con- rocket, which does not use any air and is the
nections on oxygen lances is eliminated only jet engine which can be used for pro-
(3) Heats can be tapped at exactly the de- pulsion in vacuum”
sired time, avoiding off-specification steel These quotations are from Sec B of a classic
resulting from loss of volatile additives during book on Jet Propulsion entitled Jet Propulsion
delayed or slow taps Engines (Ref 1). The contents of this excellent
(4) Taps start out at full flow rate, thus treatise are summarized in its preface:
reducing the over-all tapping time and ladle “This. volume considers those principles and
skull problems encountered in combining components
(5) Tap hole maintenance is reduced and to form a complete engine. It relies heavily
perfect alignment of the tap hole is insured upon the other volumes which deal with basic
(6) The need for bars to knock down principles or principles and problems related
ridges in front of the tap hole is practically to components of an engine
eliminated Section A gives a concise history of the
Because of these major advantages, it is development of rockets and air flow jet engines.
exycted that Jet Tappers will eventually replace Section B gives definitions of thrust and various
the oxygen lance method of tapping entirely. efficiencies and” derives relationships for the
In fact they have already been adopted for performance of the different jet propulsion
more than two-thirds of all the open hearth systems. Section C gives the performance analysis
furnaces in this country of turbojets based on the internal solution of
Cook (Ref 2) states that further commercial matching the compressor, combustor, turbine,
use of the Jet Effect is hindered by the high and nozzle. It includes a discussion of off-design
cost of well-made lined-cavity charges performance and describes the problems of
Refs: 1) Blasters Hdb (1958), pp 91-96 2) control and testing which are unique to a
Cook (1958) p 259 complete unit. Section D treats the turboprop
in a somewhat similar manner. It gives the logic
JET PROPULSION for interest in a turboprop and discusses the
introduction. “In the absence of all contact additional complications. Section E is dev’oted
with an external solid, a prime mover placed to the ramjet, its performance, controls, and
in a fluid of finite or even zero density can methods of testing. Section F discusses the
propel itself by ejecting a fluid or solid mass wave engines in general, and in particular the
toward the rear. By convention we say that pulse jet and the comprex. Section G treats
this mover is propelled by jet propulsion, the liquid rocket engine, from the consideration
although the propulsive thrust really results of appropriate fuels (both monopropellant and
from the effects of pressure and friction bipropellant) to the designing and testing of
exerted on the wall of the hollow interior of the motor. Section H gives a similar treatment
the mover by the solids or fluids moving in for solid propelled rockets; with special stress
the interior toward the exhaust nozzle” on the stability and characteristics of burning.
“In all jet propulsion engines, just as for The possibility of a variety of hybrid engines,
all propulsion of thermal origin, the source part rocket, part turbine, or more generally
of available energy is an exothermic chemi- part jet and part rotating machinery, is intro-
cal transformation of solids, liquids, or gases, duced in Sections I and J which treat two
carried on board and called propellants. For such cases—the ram-rocket and the jet rotor.
 J 78

Each section derives. the possible performance of the reaction products through the nozzle
and outlines the possible use of these engines. contributes .to the total thrust
Section K deals with the problems in making If compression and expansion of the internal
a nuclear jet power plant suitable for air- flow is not produced by rotating or reciprocating
craft. It gives the theory related to the machinery but by oscillatory motion of the
shielding, heat transfer, and ithe production flow, ie wave motion, the jet engine is called a
arid control of a smrdl lightweight reactor. pulse jet .!
The final section does not quite give a peek If, in a continuous flow jet, only the compres-
into the future, but it gives a systematic sion resulting from ram effect in the inlet
procedure for exploring the many possibilities diffuser is utilized, the compression and expansion
of the types of jet engines” machinery is eliminated, and the turbojet be-
In what follows we will briefly describe comes a ramjet
the various types of jet propulsion systems Types of Jet I%opulsion” Engines. The basic
and give a list of references to the voluminous jet propulsion engines are illustrated
literature that has appeared on this subject schematically in Fig 1:
since the publication of the above book
(1959). The reader is also referred to the N —
—
—+
following Encyclopedia articles: Combustion;
Rocket
Hyperbolic Propellants; Ignition; Propellants n (liquid prcpelbmts)

and Rockets 1
In general, in all jet propulsion engines, the
-
driving energy source is the exothermic chemi-
cal transformation of solids, liquids or gases
(propellants) carried on board the engine
For propulsion in the atmosphere, where Turbopropjet or turboprop
(thrustougrnentor by external dilution)
ambient air is available, this air may be induced L

by the jet engine in order to participate essen-

tially in the chemical transformation of the - 4

fuel: the engine is then properly crdled an air -

flow jet engine (in Fig 1 the Turboprop, — I
- -
Turbojet, Ramjet & Pulse Jet are examples of Turbojet
air flow jet engines) in contrast to the rocket,
which does not use any air and is the only
jet engine which can be used for propulsion
in vacuum
A flow of ambient air may also be inducted
exclusively for augmenting the thrust by in-
creasing the mass flow of the discharged gases:
thus we can conceive of an air flow jet engine
with two flows, an example of which is a
turbojet with a ducted fan
Whereas the internal flow of a rocket is
usually continuous, and even quasi-steady, that
of an air flow jet engine can be continuous
or discontinuous, ie intermittent. The machines Fig 1. Types of Jet Propulsion Engines
which work on the internal flow of a jet
engine and have a continuous flow require In these diagrams, D is the intake duct, C
purely rotating machines, ie turbo machines; is the compressor, B is the burner, T is the
the engine is called a turbojet turbine and N is the exhaust nozzle. The
In the turboprop, the exothermic reaction mode of operation of these engines will be
not only drives the propeller but the exhaust described in the next section
 J 79

Modes of Operation of Various Jet Engines. each produces available energy stored in a
1) Rockets. As clearly stated a rocket is gaseous medium at a high temperature and
differentiated from a fluid flow engine in that pressure
a rocket generates its thrust entirely from
reacting material carried within it, while a
fluid flow system takes in material (air) from
the outside. The subject of rockets will be
described in more detail under Rockets and
some material pertaining to rockets has
already been described under Hyperbolic
fiopellants and under Ignition. Here we just
outline the type of rockets in use or under
development:
1) Solid propellant rocket motor
a) Constant volume combustion
b) Constant pressure combustion
(i) Restricted burning
(ii) Unrestricted burning Propelling
I nozzle -
2) Liquid propellant rocket engine Turboprop
a) Gas pressure feed system I
propulsive system
b) Turbopump feed system v
3) Gas or vapor propellant rocket engine ..— .- .. ..
4) Ionic rockets
Turboprop & Turbojet. The basic principles in- >‘ ‘- “
volved in generating the potential power of a
turbojet and a turboprop are identical. They
each have a compressor, a burner, and a turbine
u
-r,+ &&4
which runs the compressor. This common part Fig 2. Comparison of Turbojet & Turboprop
of each produces energy in the form of a hot Engines
gas at a high pressure. The only difference in
the engines is the manner in which the avail- Note: The power generator system for the
able energy is converted to useful thrust. In turboprop is essentially the same as in the
a turbojet the energy is converted to thrust turbojet
by expanding the gases through a nozzle to The advantages of a turboprop are in its
form a jet at high velocity. By directing this greater efficiency, ie more of the gas ‘generator
jet backward the reaction gives a forward com- energy is converted into useful work than in
ponent of thrust. In a turboprop, part of the the turbojet. Its main disadvantages lie in the
potential energy is removed by additional
heavier and more cumbersome machinery that
turbine stages that drive a propeller. Any resid-
it requires
ual energy is then used to produce a jet stream
similar to that of a turbojet, but because of the Ramjet. We quote from Sect E of Ref 1:
lower energy level the jet velocity is much “The ramjet engine, in common with all
lower (See Fig 2 below) jet engines, produces propulsive power by in-
For convenience of thought in comparing creasing the momentum of the working fluid
the two engines, the part that is common to through some form of heat release so that the
the turbojet and the turboprop is usually momentum of the exiting jet exceeds the
referred to as the hot gas generator, or power momentum of the entering air stream. In con-
generator, and the means for converting the trast to other air-breathing jet engines the ,
energy to thrust power is called the propul- working cycle is accomplished without mechani-
sive system. The hot gas generator is analogous cal compression of the working fluid and ~th-
to the steam boiler on a steam engine, in that out intermittent semiclosed combustion cycles;
 J 80

Flaw hieher ~ressure than the free stream air

“fk’+w:~’v--””=’e-r’e’~
i
“ ‘ surrounding the engine. The exhaust nozzle
is used to expand the flow and thereby to
convert the pressure into velocity. The flow
I
velocities after combustion are subsonic; hence
~“ ~ “~1.1 I
b~ ‘ 1~ an initial contraction of the flow area is
~ ~jj~j ~ necessary. This contraction must be sufficient
m
to either reduce the internal pressure to the
Fig 3. Schematic of ramjet engine ambient value or to accelerate the internal
flow to sonic velocity. At low design flight
conseqtiently the ramjet is mechanically the speeds, ambient pressure is achieved with un-
least complicated air-breathing engine yet choked flow and the nozzle terminates with
devised the convergence. At high flight speeds the
fie basic elements of the engine can be internal flow chokes at pressures above
represented schematically as in Fig 3. The ambient and for maximum thrust realization
charge air is inducted to the combustion or a diverging passage is added downstream of
heat release chamber through a diffuser, so- the throat in which the flow continues to
called because the entering air stream is gener- expand to supersonic velocity until ambient
ally decelerated from the forward speed of pressure is attained”
the engine to a lower combustion entrance The fundamental limitation of’ the ramjet
velocity. in engines employing liquid or gaseous is its requirement of sufficiently rapid motion
fuels for the energy addition to the charge air, for the engine to become operative. “The
the fuel is injected through orifices or nozzles engine will not yield an internal thrust force
“at some point .in the diffuser process. The until the flight speed is high enough to
location of the point of fuel injection depends produce a diffuser pressure rise that is sufficiently
upon the desired degree of atomization and great to exceed the pressure losses in the flame
vaporization of the fuel and the desired holder, combustion chamber, and exhaust nozzle.
mixture pattern of the fuel and charge air at An effective propulsive thrust force will not be
the entrance to the combustion chamber obtained until the flight speed is enough greater
At the end of the diffuser passage is lo- than this minimum value for the internal thrust
cated a flame holder, a turbulence-generating to compensate the drag directly chargeable to the
device offering shelter to the subsequent com- engine installation. A yet higher speed must be
bustion flame. The fuel-air mixture entering obtained before the propulsive thrust is great
the combustion chamber is ignited in the enough to overcome the drag of the vehicle in
sheltered regions of the flame holder by some which the engine is installed and thus to qualify
independent ignition source. In most engines the engine as a useful propulsive device
this igniter. is only required to function at The minimum flight speed at which the ram-
the onset of combustion, the combustion jet can qualify as a propulsion system for air-
process being self-propagating for continuous craft depends upon the degree to which the’
operation internal pressure losses and the installation drag
The combustion of the fuel-air mixture is are minimized and upon the drag of the pro-
ideally completed in the combustion chamber, pelled airframe. In general it has been found
normally a constant area passage. (In ramjets that the minimum speed application of the
utilizing an external heat source such as a’ ramjet is not less than about 400 mph. (This
nuclear reactor, the fuel-injection, flame- speed is the relative speed of the engine and
holding combustion process is replaced by a not necessarily of the airframe. Thus, ramjet
heat exchanger from which the uncontaniinated engines, tip-mounted on the rotors of heli-
charge air is discharged at an elevated copters, have proved to be adequate propulsive
temperature) devices at zero forward airplane speed.) The
The products of combustion leaving the efficiency of the engine is very low at these
combustion chamber are, in general, at a minimum speeds, however, and applications of
 J 81

interest at subsonic speeds are confined to Pulse Jet. We quote from Sect F, Chapter
installations in which the attractions of light 4of Refl:
weight, mechanical simplicity, and low cost “In its standard form the pulse jet consists
outweigh considerations of fuel consumption of a shaped tube fitted with flow-check valves
As the engine flight speed is increased the at the front end (Fig 4). The air flowing
thrust increases as a function of the square of into the engine .through the valves is mixed
the flight speed in the same order as the with a continuously sprayed fuel. The mixture
airframe drag. Thus a ramjet engine, properly is then fired. As a result of the pressure rise
designed, is capable of producing the very high which accompanies the explosion, the inlet
thrusts necessary for supersonic propulsion. The valves close and the exhaust gases are forced
engine efficiency, and hence the specific fuel out through the tailpipe. Expansion waves
consumption, ideally improve as flight speed which are generated in the discharge reduce
increases so that the principal range of the pressure behind the check valves until
application of the ramjet as a competitive they open again to admit a fresh charge of
power plant appears to lie in the propulsion air, and the cycle is repeated. A spark. is
of supersonic vehicles needed ordy for starting; once a regular cycle
The inability of the engine to produce a is established, each fresh charge of mixture
useful propulsive force at zero or low flight is ignited by the hot gases from the preceding
speeds necessitates the use of an auxiliary explosion and operation proceeds without
power plant to initially accelerate the vehicle further use of the spark plug
to the required take-over speed of the ram- Despite the mechanical simplicity of the
jet. Such auxiliary power is also required for pulse jet, a great deal of information is still
controlled landing of the vehicle. As a con- lacking about such important details ,as “its
sequence the ramjet engine is not well-suited operating cycle as the flow behavior through
for conventional aircraft applications (with the intake valves and at the discharge end, the
the exception of the helicopter) and the timing and mechanism of ignition, and, above
principal application of the engine appears all, the process of combustion. This lack of
to be further restricted to missiles or other basic information has necessitated the use of
similar vehicles of a one-flight expendable quite arbitrary assumptions in all theoretical
nature” investigations of the pulse jet cycle”

Air
bet Flopper p[otes
r

Combustion chomber
Toilpipe

\L Entrance diffuser

Fig 4
 $.

J 82

Comparison of Performance Parameters of Jet

Engines. The excellent diagram below is taken
from pp. 96 & 97 of Ref 1

Thrust F Efficiency n,
Propulsion MOSS of oir or proportional to of converting Ielotive weight %oboble rans
method Picture gas handled moss hondled fuel energy to of fuel for 0 of maximum
m and change in mechanical qiven duration flight speeds
momentum energy

*L,OL:e
1. Above 600
mph
, ,,,.~ L %~~f in
Rocket ..,. ,,,.,:lf
@ ). For flying
Velocity, mph Veltxity, mph Velwity, mph bombs
Velocity, mph Velocity, mph

Romiet
-= .~,o
p----,~’,,o:[$;
-
I I I 20000F

y-. ,~o: () ,., ,

.+.
1. Above
mph
2. FwJng
500

@
Velocity, mph Velocity, mph V— mph
V- mph V- mph

0.,.?,-+
1. 300 to 60
mph
Pulse jet 2. ~m::”ng

Turbojet
-~ ~lzoo
czo~!!i!i
k’
~ko)L%:o 800 0
0
400 to 1500
mph

Velocity, mph Velocity, mph 0

V – mnh V – moh V-muh

300mt;h600
Turbcprop
@

IF---i~E$~~s
uperchorge

‘::g: ~= J35;0 ,&: 150 to 450

mph
@
exhaust jet V-mph
V - mph V - mph

mentals of Rocket Propulsion,” Reinhold, ,NY

Note that overall efficiency of all the above
(1960) &CA 56,13152(1962) 4)M.
engines is primarily controlled by the cycle
fuel efficiency & the propulsive efficiency Barrere et al, “Rocket Propulsion,” Elsevier
Pub Co, Amsterdam (1960) & CA 58, 7780
Written by J. ROTH (1963) 5) S.S. Penner, “Chemical Rocket
Propulsion & Combustion Research,” Gordon
& Breach, NY (1962) & CA 58, 5447 (1963)
Refs: 1) O.E. hncaster, Ed, “High Speed Aero- 6) W.H. Jones, “Recent advances in the
dy~amics & Jet Propulsion,” Vol XII, “Jet chemistry of liquid & solid propellants,”
Propulsion Engines,” Princeton, NJ, Princeton Combust Propellenti Nuovi, AttiConv, Milan,
Univ Press (1959) 2) N.A. Ragozin, “Jet 1963, 249 (Pub 1964) & CA 62, 1505 (1965)
Propulsion Fuels,” Pergamon Press, NY (1961) 7) M. Barrere, “Research in the field of
3) R.E. Weich, Jr & R.F. Strauss, “Funda- chemical propulsion,” NASA Accession No
 J 83

N65-21452, Rept No CPIA-67, 4-6 (1964). c 100 BC Hero built a steam jet engine, called
From SciTechAerospRept 3 (1 1), 1889 (i 965) an aeolipi[e, in Alexandria, Egypt
& CA 65, 12054 (1966) 8) D.L. Turcotte, 1232 Chinese used rockets to frighten enemy
“Space Propulsion,” Blaisdell, NY (1965) & soldiers
CA 65, 13449 (1966) 9) L.E. Maher, “Aero- c 1500 Leonardo da Vinci proposed using up-
space applications of rocket engines,” JBrit- ward movement of hot gas in fireplace
InterplanetSoc 19 (1 1), 490 (1964) 10) J. chimney to turn a spit for cooking meat
Szabo, “Principles & physicrd possibilities of 1629 Italian engineer Giovanni Branca built a
space travel~’ NedTijdschrNatuurk 32 (5-6), crude steam turbine which drove a machine
191 (1966) &CA 66, 6747K (1967) 11) 1678 Ferdinand Verbiest, a Jesuit in China,
D. Genthe, “Oxy compounds of fluorine & built a model carriage, using a jet of steam
their applicability in rocket propulsion,” for power
NASA Accession No N66-I 2486, Rept No 1687 Sir Isaac Newton stated the law of
DLR-FB-65-29; avail CFSTI (1965). From action and reaction
SciTechAerospRept 4 (3), 480 (1966) & CA 1791 John Barber, an Englishman, patented
66, 97055 (1967) 12) E. Ungerer, “Prob- a gas turbine that was an ancestor of the
Iem of propulsion by hot-water jets,” NASA tubojet
Accession No N6638349, Rept No DLR- 1908 Rene Lorin, a French engineer, made
FB-66-43, avail CFSTI (1966) (in Ger). detailed drawings of a proposed ramjet
From SciTechAerospRept 4 (23), 4611 (1966) engine
& CA 66, 10638 (1967) 13) Ya. B. Zeldovich 1926 A. A. Griffith in Great Britain described
et al, “Impulse of Reactive Force of Solid theories of using gas turbines in aircraft
Propellant Rockets,” (AD-632233), CFSTI, 1930 Frank Whittle of Great Britain patented
Springfield, VA (1966) & CA 67, 4513 (1967) design for a jet-aircraft engine
14) C.A. Vansant, “Aeroenergy; a new frontier;’ 1939 Heinkel Company in Germany built and
IAA Accession No A66-3443; avail AIAA (1966). flew the first jet-engine airplane
From Intern Aerospace Abstr 6 (18), 3162 (1966) 1941 First successful turbojet airplane was
& CA 67, 23624 (1967) 15) G.A. Marxman, flown in Great Britain. Engine designed by
“Boundary-layer combustion in propulsion,” Whittle
SympCombust 11, 269 (1966; pub 1967) & CA 1944 First jet-propelled fighters used in WWH
68, 41776 (1968) 16) R. Cockburn, “Rocket by Germans
propulsion & space research:’ Endeavour 26 1947 First supersonic (faster than speed of
(97), 21 (1967) &CA 66, 77884 (1967) 17) sound) rocket-powered airplane was flown
L.S. Billman, Ed, “Advanced Propulsion Con- in the US by Charles Yeager
cepts:’ Gordon & Breach, NY (1967) & CA 1952 First scheduled airline flights by jet
70, 21461 (1969) 18) W.H.T. Lob, Editor, transports begun by Great Britain
“Jet Rocket; Nuclear, Ion and Electric Pro- 1955 First jet-engined convertiplane that takes
pulsion: ‘Theory and Design,”, Applied Physics off and lands straight up and down was
& Engineering, Vol 7, Springer-Verlag (1968) tested in the US
19) R.W. Jenkins & R.E. Elbel, “Performance 1957 High-energy fuels that increase jet ranges
potential of the bipropellant pulsed turbine rdmost 50% were put into commercial
space power system:’ AdvEner~ConservEng, production
PapCritSumIntersocEnergy ConversEngCont 1958 First commercial jet passenger service
1967, 493, AmSocMechEng, NY & CA 71, between New York and London
103725 (1969) 1960 Turbofan engines using fans for added
thrust in place of afterburners came into
commercial use
Jet Propulsion, History of. Early uses of the More detailed, fairly recent historical data
principles of jet propulsion and their evolution on Air Flow Jet Engines are given in Ref 1,
into modern jet aircraft are summarized in the pp 29-53 (including 201 refs). The subjects
tabulation below (Ref 2) covered in this excellent review are: Piston
 ,

J 84

Engine Jet Development; Turbojet Develop- for boiler feed or similar services, in which
ment; Ramjet Development; Development of the fluid being pumped is discharged into a
Intermittent Jets; Other Forms of Air Flow space under the same pressure as that of the
Jet steam that is used to operate the injector
A.D. Baxter, the author of this chapt of Rejl Perry (1950), 1439; (1963), pp 5-17
Ref 1 summarizes his review as follows: & 6-13
“In conclusion, it may be observed that in
the ten years following the 1939-1945 war, Jewel Powder. One of the early American
air flow jet engines supplanted piston engines smokeless proplnts “of the Ballistite type (See
in almost all high performance military air- Vol 2 of Encycl, p B8-L) proposed by Monroe
craft, they made large inroads on the civil Refi Daniel (1902), pp 387 & 447
aviation field including the first regular turbo-
jet passenger setiice in 1951, they made super-
sonic flight a commonplace, and finally they Jewler Explosives. See Ievler Explosives in
doubled the world air speed record” this Vol, p 14-R
Refs: 1) O.E. Lancaster, Edit, Jet Propulsion
Engines, Princeton Univ Press (1959) Chapt 3
(by A.D. Baxter) 2) S.S. Stillwell, World Johnite Explosives. See Jahnite Powders in
Book Encyclopedia Vol II (1965) p 92-R this Vol

Jet Propulsion Unit “Decipede”. A jet pro- Johnson & Alexander Priming Composition.
pulsion unit, whcih develops 1000 pounds thrust These inventors were issued British patents
for 43 sees, was developed at the request of in 1856–57 for a priming compn containing
the Engineer Board Field Station. The unit amorphous P 8.3 & lead nitrate, [Pb(N03 ~ ],
is the motor power of an amphibious “Snake” 91.7%
employed in Marine & Army land operations. Refi Daniel (1902), pp 8 & 388
It burns ten 8%-inch diam grains of CP 401
proplnt simultaneously in a single motor tube.
The proplnt gasescome out of five pairs of Jolt & Jumble Tests. These tests have been
nozzles spaced along the side of the motor used for many years to establish the safety and
tube. This unit, informally known as the general ruggedness of fuze & booster designs
“Decipede” was developed to the point of under the application of repeated shocks in
satisfactory operation several directions. Both tests were designed
Refi Central Res Lab, Monsanto Chemical originally as a simulation of shocks received
Co, “The ‘Decipede’, a 1000 Pound Thrust, during transportation of US Army caissons
43 Second Burning Time, Jet Propulsion over rough terrain. In present applications
Unit”, OSRD 5704 (Nov 1945) the tests are intended to accurately represent
actual conditions which may be encountered
in transportation, handling or use of fuzes.
Jet Pumps are devices for transferring liquids They are rather a deliberate exaggeration of
from one point to another, using the fluid severe conditions to which an item might be
pressure as an operating medium. They also exposed during transportation or use. As a
may be used for mixing liquids. Two types of result of the long use of these tests, much in-
jet pumps are of interest to the chemical engi- formation has been accumulated regarding the
neer. One of them is the ejector (siphon, ex- behavior of a wide variety of fuzes in the
hauster or eductor), which is designed for use tests. Although it is not a requirement that
in operations where the head pumped is low the fuzes be operable afterward, some fuze
and is less than the head of the fluid used for designers do require that their fuzes remain
pumping by pressure. Another device is the operable. In such cases, operability is judged
injector. It is operated by steam and used by examination only, although firings may be
 J 85

conducted in addn where considered appropri- Jones Detonator Loader. An automatic loading
ate by the designer machine developed in 1943 by R.A. Jones of
Jolt Test.. It consists of assembling the test Ohio in cooperation with engineers at Picatinny
item into the end of a pivoted arm which Arsenal. This machine proved to be a great
under cam action falls by gravity thru 4 inches success during WWll and saved about 175000
on a heavy bed plate, giving a considerable man hours per year
jolt. Each item is tested for 1750 jolts, at a Refi E. Cox, ArmyOrdn 29, No 152, 282–84
std speed of 35 jars per rein, in each of three (1945)
positions: vertically up, vertically down&
horizontal. All fuzeexpl elements shall be
present in the fuze during the test. The jolt Jones Blasting Explosives. Jones patented the
testing machine is shown on US Ordnance following compn: chlorates such as NaCIOs
Corps Drawing 81-3-30. It takes 50 reins to are used with finely divided carbonaceous sub-
test a sample in each of the three positions, stances & the o-isomer of nitrotoluene, which
or ca 21%hrs for a complete test keeps the mixt plastic. The chlorate may be
The criteria by which samples are judged mixed with a powdered carbonaceous absorbent
to have withstood this test are: 1) no element material such as sawdust & a liq mixt of o-
shall explode and 2) no parts shall be broken, nitrotoluene & melted TNT
deformed, be displaced, come apart, or arm Ref L.T.W. Jones, USP 1820567 & 1820568
in such a manner as to make the assembly (1931) & CA25, 5771 (1931)
unsafe to handle, or dangerous to use. Break-
down & inspection, together with engineering
judgment, are usually the basis for the decision Jones Dynamite: An Australian Dynamite con-
Jumble Test. It consists of placing the test sisting of NC 30–35% absorbed by a mixt of
item in a std steel ftiture which completely Ca sulfate & kieselguhr 70–65%
encloses the item, then putting the fixture Ref: Daniel (1902), p 388
inside a rectangular hardwood maple box,
which is rotated about its diagonal corners. Jones Smokeless Powder. One of the first
The f~ture containing the item rolls inside the progressive-burning smokeless proplnts patented
box, receiving bumps at random. The box ro- in 1897 in Austria. It was prepd by coating
tates at 35 rpm and the test consists of 3600 grains of proplnt with a thin layer of resin,
revolutions. It takes about 2!4 hrs. The fatty acids or carnauba wax. About % part of
jumble test machine is shown on US .Ordnaqce coating per 100 parts smokeless prophit was
Corps Drawing 81-3-35. The criteria for pass- used. This method retarded combustion, es-
ing the test are the same as given under Jolt pecially at the start, and allowed attainment
Test ““ of a fairly progressive increase in the rate of
Note: Particular care should be exerciied in burning without increasing the pressure in ,the,
handling test “items after the jolt & jumble gun barrel
tests; a safety shield should be used. The Ref Daniel (190,2), p 388 ,
articles’ may become armed or the expl chge
may have sifted out. In these cases, a slight
jar may initiate a defective fuze. The jolt Jordan Pulping Machine. It is used in preparing
test is always run first. Total time for both cotton for nitration. The machine operates on
tests is ca 5% hrs the centrifugal principle, by means of which
Refs: 1) Ohart (1946), pp 135–37 2) us the entering cotton is thrown from the large
Military Standard, “Fuze’ and Fuze Compo- end of the beater to the small tapered end, and”
nents, Environmental and Performance Tests thence to a storage tank above the machine.
for”, Ml L-sTD-331 (Jan 1966) with Change The more efficient way to operate these units
Notice 2 (Dee 1967) is to have them adjusted in such a manner that

,. ,’
 J 86

the cotton is given successive cuts. In other in Cook (1958), p 8 2) Daniel (1902), p
words, the first treatment in the Jordan machine 389 3) Marshall 1 (1917), p 363 4) Davis
will give only a fairly coarse cut, the next a (1943), p 334 5) Giua, Trattato VI (1)
little freer, and so on, until the cotton has (1959), p 340
finally been pulped to the necessary degree of
freeness
Juinite. See Ethylenebisurethane and Deriva-
tives in Vol 6 of Encycl, p E234-L
Jouguet, (Jacques-Charles) Emile (187 1 –1943).
French physicist, generq inspector of mines and
professor of mechanics Ecole des Mine, ficole Jump Firing Test. In tabulating the elevations
Polytechnique, member French Academy of & azimuths required to obtain a given range and
Science (1930). He was the author of “M6- deflection of a gun, account is taken of the fact
canique des Explosifs” (1917) and conducted that usually the direction of the target to the
research on wave diffusion, movement of fluids, trajectory at the origin differs from that of
explosives; and fundamental work on the hydro- the axis of the bore of the gun before it is
dynamic theory of detonation. His name is fired. This difference in direction is called
associated with that of Chapman” in the famous jump. The jump may be in any direction,
Chapman-Jouguet condition. In their honor but as a matter of convenience it is described
parameters of a steady detonation wave are by two coordinates, vertical & horizontal
usually designated by the subscript CJ The jump firing test is described in US
See Detonation, Chapman-Jouguet in’ Vol 4 Ordnance Proof Manual 40-11 (1942)
of Encycl, pp D230–37 and Jouguet’s Rule,
p D607-L
Ref A.G. Debus, Edit, “World Who’s Who in Jumping Detonation. See Detonation, Jumping
Science”, Marquis Co, Chicago (1968), p 896-L in Vol 4 of Encycl, p D421 -L

I
Jouguet’s Rule. See in Vol 4 of Encycl, p Junk Test. Bergmann-Junk Test in Vol
See
D607-L 2 of Encycl, p B102-R

JP, JPH and JPN Propellants. See under Bal- Juno 1. A space research vehicle which is a
listite in Vol 2 of Encycl, p B9-R four-stage version of the Juniper C (qv). The
first stage burns a high energy hydrazine fuel,
called Hydyne (developed by the North Ameri-
Judson Dynamite or Powders. American expls can Aviation Co), and liq oxygen. The 2nd,
patented by E. Judson in 1876 and manufd in 3rd & 4th stage thrusts are solid propellants.
Drakesville, NJ. These expls were, in fact, a Characteristics of Juno 1 are length 68.6’,
combimtion of Black Powder & NC *d were diam 70”,. wt loaded 64000 lbs, useful pay I
much more powerful than. straight BlkPdr, al- load 10–1 5 lbs, altitude 2000 miles, and ve-
though some of them contained only a small locity 19000 miles/hr. The rocket was used
amt of NC. For example, one compn con- to launch several of the Explorer satellites
tained: NC 5, NaN03 64, sulfur 16 & bitu- Rejl F.I. Ordway & R.C. Wakefield, “Inter-
minous coal (cannel coal) 15%. Judson’s mtional Missile and Spacecraft Guide”, McGraw-
expls were also called RRP (meaning Railroad Hill, NY (1960), United States of America, pp
Powders) 73–74
Judson’s patent may have been pre-dated
by Nobel’s patent (Ref 1) for a mixt of NC Juno 2. A space research vehicle having 4
& Black Powder stages of thrust. The fiist stage burns a hydro-
Refs: 1) A. Nobel, BritP 2359 (1864) quoted carbon, RP-1, and liq oxygen. The other three
 .
J 87

stages burn solid propellants. Length of the Jute, Cl 2HI 809; mw 306.26, 0 47.02%;
rocket is 76’, diam 105’~ wt loaded 121000 fibers of East Indian, South American& Chi-
lbs, and pay load 13–80 lbs. The vehicle was nese plants, such as Corchorus, Olitorius, Cap-
used to orbit Explorer 7 sularis & Abutilon Avicenna. It is used ex-”
Refl F.I. Ordway & R.C. Wakefield, “lnter- tensively in the. manuf of gumy sacks, bags
mtional Missile and Spacecraft Guide”, McGraw- & twine (Ref 6). On nitration it yields:
Hill, NY (1960), United States of America, p 74 Nitrojutes, Cl 2H1 S06(N03)3, N 9.52% to
cl zH~qO@Os)Q, N 11.52%; expl compds
prepd in 1889 by Cross& Bevan (Ref 1) by
nitrating jute with mixed acid contg about
Juniper C. A space research vehicle having 3
equal vols of coned nitric & sulfuric acids.
stages of thrust. The first stage burns either The authors do not state the ratio of acid to
liq oxygen & ethyl alcohol or liq oxygen & jute. Temp of nitration was 18°, time 30
Hydyne (See under Juno 1, above). The se- reins, N content 10.5% which corresponds to
cond & third stages are solid proplnts. The a compn between the above formulas
rocket is 66.6’ in length, diam 70”, wt loaded Miihlhaeuser (Ref 2) nitrated jute previously
64200 lbs, pay load 300 lbs, range 1600 miles,
purified by boiling in a 1% Na2C03 scdn fol-
altitude 400 miles, and velocity 14700 miles/hr
lowed by a wat6r rinse. By using 1P dry jute
Refi F.I. Ordway & R.C. Wakeford, “Inter-
& 15 parts of acid, 2/1 coned H2S04/coned
national Missile arid Spacecraft Guide”, McGraw-
HN03, a product with 12.26% N and 132%
Hill, NY (1960), United States of America, pp
4445 yield was obtd. The props of Nitrojute are
similar to those of nitrated lignocelhdosses
(See Lignin Nitrate in this Vol)
Since the cost of jute is higher than that
Jupiter Dynamite or Powder. One of the older “of cotton or wood pulp, and since Nitrojutes
American type No 2 Dynamites, similar in are no better than ordinary NC, there is no
compn to Neptune or Vulcan powders advantage in manufg .Nitrojutes. They were
Refi Daniel (1902), p 389 ; , never used in expls, except for experimental
purposes
Refs: 1) C.F. Cross & E.J. Bevan, JChem-
SOC 55, 199 (1889) 2) O. Miihlhaeuser,
JusticePowder. Justice patented in 1888 an ChemZtg 16, 163 (1892); JSCI 11, 546 &
expl mixt consisting of a nitrate & a chlorate, 937 (1892); and DinglersPolyJour 28388 &
such as KC103, consolidated by means of 137 (1892) 3) P.G. Sanford, “Nitroexplo-
molten paraffin or naphthrdene sives”, Crosby Lockwood & Son, London
Refs: 1) Cundill (1889) in MP 6, 19 (1893) “ (1896), pp 125-27 4) Daniel (1902), pp
2) Daniel (1902),” p 389 3) Giua, Trattato 557–58 5) Marshall 1 (1917), p 149
6 (1959), p 394 6) Hackh’s (1944), p 463; (1972), p 367
 KI

K (Pulver). See under Erosion of Gun Barrels materials 4%. Daniel (Ref 1) uses the name
in Vo15, pEl16-L Kadmite for the same compn
Refs: 1) Daniel (1902), 390 2) M. Guia,
Trattato 6 (1) (1959), 388
KI and K2 (of Muraour). For a proplnt whose
burning rate, V, may be expressed by V=a+bp,
where a and b are constants and p is the ambient Kaipinites. Expls resembling Cheddites (See
pressure, Muraour defines a constant, KI, which Vol 2 of Encycl, p C 155-L) developed in Fr
is the total area under an ideal pressure-time based on the study of the Belg Yonckites.
curve, and not the real pressure-time curve. Kaipinite O No 12 contains Amm perchlorate
The ideal combustion rate Vi is given by 38, Na nitrate 28 & TNT 34%; Kaipinite O
Vi=bp. At low ambient press, the real fpdt, No 13 consists of Amm perchlorate 38, Na
based on V, is always less than the “ideal” nitrate 31 & TNT 28Y0. They are used for de-
fpdt which is obtained from Vi. ThUS K1 = molition and mining purposes
fpdt (based on Vl) ‘is always greater than the Refs: 1) Venrrin, Burlot & L6corch6 (1932),
real Jpdt (based on V). The constant K2 is 546 2) O.E. Sheffield, “Handbook of
obtained by dividing ~ by the proplnt thick- Foreign Explosives”, US Army Foreign Science
ness, and is inversely proportional to the rate & Technology Center, FSTC 381-5042 (Ott
of diminution of proplnt thickness for a pro- 1965), 225
plnt ignited on two opposite faces
Refs: 1) H. Muraour et al, MAF 22, 517
(1948) 2) P. Prache, MP 32, 350 (1950) Kaliialmatrit No 55. See under Almatrites in
Vol 1, p A140-L

K-1 Explosive (Russ K-1 Splav, K-1 Fusion,

Mixture K-l). Mixture consisting of TNT 70 Kallenites. Dynamites patented in Australia
and DNB 30%, used during WWII for filling in 1899 by Callaghan & Fraser, recommended
some land mines made of cast iron. Although for underground work because they did not
this mixt was less brisant than TNT, it was produce poisonous gases. They contained NG,
nevertheless too brisant for a container made absorbed by finely ground eucrdyptus leaves
of cast iron material, and sometimes broke it and tree bark. Some varieties contained K
into fragments too small to be effective nitrate and NC
against personnel. For this reason, the bri- See Fraser & Callaghan in Vol 5, p F186-L
sance of K-1 was reduced by the insertion in Rejl Daniel (1902), 390
its mass of long blocks of a less brisant expl,
such as Schneiderite. Because of the toxicity
of K-1, it was preferable to use K-2, described Kamikaze Bomb. See under Baka Bomb in
below Vol 2, p B4-R
Refs: 1) Shilling (1946), 240 2) PATR
2145 (1955), RUSS10
Kanite. A US AN expl containing a substance
akin to oxidized (blown) oil
K-2 Explosive (Russ K-2, Splav, K-2 Fusion, Rejl W.H. Blumenstein, Interstate Corn Com-
Mixture K-2). Mixture containing TNT 80 mission Opinion No 1557 (1 June 1911) &
and DNN 20%, used for loading 82mm Land CA 5, 2949 (1911)
Mines made from cast iron. It was less toxic
than K-1, described above
Refs: 1) Shilling (1946), 240+1 2) PATR Kanone. Ger or Swiss for Cannon
2145 (1955), Russ 10

Kapsiul’. Russ for blasting cap, detonator or

Kadinite. A Dynamite containing NG 26, igniter
Na nitrate 56, sulfur 10, carbon 4 & ligneous Refi B.T. Fedoroff et al, PATR 2145 (1955),
p Russ 28
 K2

Kapsiul’ Detonator. Russ blasting cap containing

the following expl compns (Ref 1)

Composition (grams)
Type MF Stab Lead LA Base Charge Use
Mixt Styphnate
No8&No8M 0.5 – — — 1.02 Tetryl or Blasting
1.00 PETN or
RDx
No 8A — — 0.10 0.20 same Blasting
TAT-1 & TAT-2 – – 0.06 0.21 0.11 Tetryl Fuze
M-1 . 0.1 – 0.20 0.10 Tetryl Fuze

Kapsiul’ Vosplamenitel’. Igniter cap, usually Karl Fischer Method for Determination of
referred to as squib. If followed by “udarnykh Moisture. See under Dynamites in Vol 5,p
sostavov”, it refers to percussion igniters. The D1 622-L and under Ethanol in Vol 6, p El 58-R
formulation used in rifle (C’vintovochnyi”)
percussion caps is MF 16.7, K chlorate 55.5
& Sb trisultide 27.8%; for pistol (“revol’vernyi”) Karman, Theodor von (1881–1963). Hungarian
percussion caps, MF 25.0, K chlorate 37.5 & scientist who worked in Germany & the US on
Sb trisr.dfide 37.5%; and for mine throwers aeronautical problems, on rockets, and on com-
(“minomFtnyi”), MF 35.0, K chlorate 40.0& bustion phenomena
Sb trisulfide 25.0% (Ref 2) Refi Anon, Explosivst 1963, 134
Igniter caps containing non-corrosive (“ne-
korrodiruyou-shchikh”) percussion compns:
MF 67.8, Ba nitrate 29.6 & Sb trisulfide KA-Salz. One of several for RDX.
Ger names
2.6% (for rifles); Czeck “Oksid”: Lead Styph- See under Cyclotrimethylenetrinitramine,
nate 45.0, Tetracene 5.0, Ba nitrate 30.0 & Cyclonite or RDX in Vol 3, pp C61 1-L to
Sb trisulfide 20.0% (for pistols) (Ref 3) C626-L

Kapsiul’ Vosplamenitel’, Trubochnye. Tubular

igniter caps containing the following percussion Kast Brisance Meter. See Brisance in Vol 1,
mixts: a) KTM cap — MF 25.0, K chlorate p IX; Compression Tests in Vol 1, p X; also
37.5 & Sb trisulfide 37.5%; and b) RGM cap – see under Brisance or Shattering Effect in
MF 50.0, K chlorate 25.0 & Sb trisulfide Vol 2, pp B265-L to B297-L, and Brisance
25.0% (Ref 4) Test Methods in Vol 2, pp B299-L to B300-R
Refs: 1) Gorst (1957), 126 2) Ibid, 115
& 120 3) Ibid, 116 4) Ibid, 120
Kast, H (1869–1927). A Ger scientist who
specialized in expls,and was for many years
Kardox Cartridge. See under Cardox in Vol 2, associated with the Chemisch-Technische
P C67-R Reichsaustalt. He designed an apparatus for
the detn of brisance of expls (brisance meter),
and developed a formula for theoretical calcu-
Karitto, See under Carlit in Vol 2, p C68-R lations of brisance. Kast also developed an
and under Japanese Explosives in this Vol impact machine (Kast Stauchapparat) that was
 K3

for many yetis the “standard” impact test for Kelbar Powder Company Explosive. The
expls. He was the author of several books and Kelbar Powder Co of Avondale, Pa developed
articles on expls an expl contg Amm Nitrate 93.37, resin 6.57
Ref: F. Lenze, SS 22, 305 (1927) & CA 22, & moisture O.osyo. It had satisfactory brisance
1238 (1927) and stability was comparable to TNT &
80/20 Amatol, but was sensitive to bullet im-
pact and was rendered very insensitive by com-
Katiusha (Katyusha or Kostikov’s Gun). Russ pression. Its high mp (about 160°) made
132mm rocket launcher M-13. It consisted loading of shells or bombs by casting or ex-
of a truck-mounted system for firing 16 rockets trusion impracticable, therefore the expl was
from eight rails. The M-1 3 weighed 7.1 tons thought to offer no particular promise
and fired 94-lb rockets to a max range of Ref: J.D. Hopper, “Study Ammonium Nitrate
9846 yards Explosive Received from Kelbar Powder Com-
Refs: 1) Anon, FieldArtilJ (NOV 1943), 816 pany”, PATR 1009 (Ott 1939)
2) G. Underhill, InfantryJ (May 1945), 44–49
3) J. Quick, Dictionary of Weapons and Mili-
tary Terms, McGraw-Hill (1973), 256 Kelbetz Explosives. Expls patented in England
in 1896 by an Austrian, Kelbetz. They con-
sisted of AN mixed with oxalates of aromatic
KDNBF. Acronym for the K salt of Dinitro- amines, such as aniline and toluidine, and some-
benzofuroxan, See Vol 2, p B68-R times also contained small quantities of charcoal.
Other Kelbetz expls contained about 95% AN,
fatty acids such as stearic, palmitic, oleic, etc
Keeping Test. One of the tests used in England (with or without their metallic soaps, such as
to determine the exudation of Dynamites; other Ca), and small quantities of charcoal
methods include press and centrifugal tests. In Refi Daniel (1902), 391
this procedure, a previously weighed cartridge
of Dynamite is stored in a verticaJ position for
6 days at 40°, and then reweighed. If leakage Kellow and Short. Patented in 1862 in England
exceeds 5Y0,the expl is considered unsatisfactory an expl mixt consisting of K nitrate, Na
With straight Dynamites, this test correlates nitrate, K chlorate, sulfur, barkmeal or sawdust
well with the pressure test; for other Dynamites, Ref: Daniel (1902), 391
agreement is not as good
Ret Marshall 2 (1917), 421
Kelly, Bell and Kirk Explosive. Australian Dy-
namite patented ‘in 1899, containing NC, K
Keil Explosive. A mixt of nitrodextroglucose nitrate, cork and calcined eucalyptus leaves
(prepd from starch) with K nitrate or chlorate Ref: Daniel (1902), 391
& vegetable fibers
Refi Daniel (1902), 391
Kent, Robert H (1886–1956). American
ballistician at Aberdeen Proving Ground, Mary-
Kekule Oil. A liq expl (d=l .47g/cc) prepd in land from 1922. His achievements are de-
1869 by passing ethylene gasinto mixed nitric- scribed in a series of articles in Ordnance 40,
sulfuric acid. The oil consisted of a mixt 769–81 (1956)
(about 50/50) of Nitroglycol, CH2(ON02)-
CH2(ON02), and beta-Nitroethyl Nitrate,
cH~(oNo~)cH2N02 Kent Powder. A Brit coal mine expl no longer
Refs: 1) Naofim (1928), “220–21 2) Davis on the “permitted” list. It contained NG 24,
(1943), 228
 K4

K nitrate 32.5, wood meal 33.5 & Amm oxa- Kessen Explosives (Kessensprengstoffe in Ger).
late 10%. [t had a charge limit of 32 OZ, and Several expl mixts were proposed by W. Kessen
power by ballistic pendulum of 2.01” of WASA-G (Wastfdisch-ArAaltische Spreng-
Ref Marshall, Diet (1920), 53 stoff Aktiengesellschaft). One of such compns,
patented in 1938 (Ref 1), consisted of BlkPdr
used for blasting mixed with NG and/or nitro-
Kentite. A Brit “permitted” coal mine expl glycol and a large amt of Na bicarbonate. It
of the Favier type. It contained AN 34, K was intended for use in gaseous coal mines
nitrate 34, TNT 15 & Amm chloride 17Y0. Another patent issued to Kessen (Ref 2)
It had a charge limit of 18 OZ; power by bal- dealt with the manuf of moist AN expls contg
listic pendulum 2.64’: compared with 3.27” large amounts of carbonaceous materials
for Brit standard 60% Celignite (See Vol 5 Refs: 1) W. Kessen & WASA-G, BritP 493984
of Encycl, pp G57-Rff) (1938) &CA 33,2719 (1939) 2) Ibid, GerP
Refs: 1) Barnett (1919), 132 2) Marshall, 679511 (1939)&CA 33, 9647 (1939)
Diet (1920), 53 3) Marshall 3 (1932), 119 3) PATR 2510 (1958), Ger 1OI-L

Kerosene (Kerosine, Coal Oil, Astral Oil). A Ketocyclopentane. See Cyclopentanone in

mixt of petroleum hydrocarbons, chiefly of the Vol 3, pp C603-R to C603-L
methane series having from 10 to 16 carbon
atoms per molecule. It constitutes the fifth
fraction in the distn of petroleum, after the Ketohexamethylene. See Cyclohexanone in
petroleum ethers and before the oils. PaIe Vol 3, p C597-L
yel or w-white, mobile liq; characteristic, not
altogether disagreeable odor; bp 175–325°,
flash pt 150–185°F, d about 0.80g/cc. Insol ‘ Ketone Peroxides. Bjorklund and Hatcher
in w, mist with other petroleum solvents. Be- (Ref 1) prepd several expl compds by treating
sides uses as a fuel, illuminant and cleansing ketones with hydrogen peroxide–nitric acid
agent, it is used as a rocket and jet engine fuel mixts. The probable compns of these compounds
(Refs 1,3 &4) are as follows:
An underground storage tank, partially filled 1) (C3H602)3; white solid; mp 95–97°; was
with kerosene, exploded, killing 29 people. obtained by adding acetone to a mixt of H202
The expln occurred after C02 was pumped into and 70 HN03; it exploded violently on impact,
the tank to test a fire-extinguishing installation sudden heating or treatment with coned H 2S04
(Ref 2) 2) (C3H602)2; white solid; mp 131–32°; was
Refs: 1) Davis (1943), 66 2) K. Nabert & obtained by adding a mixt of H 20 2–70% HN03
G, Schon, Erdi51 u Kohle 8, 809 (1955) &CA to acetone; it is a violent explosive
50, 8207 (1956) 3) Merck (1968), 599-R 3) (C5H802)3; white solid; mp (decomp
4) CondChemDict (1971), 496-R 166–67 0 and explodes violently at higher
temps); was prepd from cyclopentanone, H202
and HN03
Kerosene Nitrate. Fiala claims the nitration of 4) (C6HI ~02)2; white solid; mp 126–27°;
kerosene by adding 3–5cc of coned nitric acid was prepd from cyclohexanone, H 202 and
per liter of kerosene with vigorous stirring, and HN03; it is a violent explosive
allowing it to stand for severzil days 5) Explosive oils of unknown compn obtained
Refi F. Fiala, USP 2511433 (1950) & CA by treating methylethylketone, ethylethyl-
44, 8103 (1950) ketone and 3-methylcyclohexanone with a
HzOZ–HN03 mixt
Refi G.H. Bjorklund & W.H. Hatcher, Trans-
Kerr Cell. See under Cameras, High-Speed RoySocCanad 44, Sect III, 25 (1950) & CA
Photographic in Vol 2, p C 15-L 45, 7952 (1951)
 K5

2-Ketotrimethyleneimine. See 2-Azetidinone in The wrapped charges are dried at 60–70° and
Vol 1, p A519-L then dipped in paraffin. They were used as
bursting charges in mines
Refs: 1) Anon,, PB Rept No 925 (1945),
Ketoximes and Derivatives. The Dow Corning 48 2) PATR 2510 (1958), Ger 101-L
Corp reported an expl hazard inherent to
ketoximes and many of their derivatives. In
manufg ketoximosilanes, Kickless or Recoilless Weapons. Weapons where
Rsi C)-N.C ‘Et )two potentially de- the recoil effect is reduced and counteracted
+ \Me ~’ by vents in the breech which deflect up to
vastating explosions were experienced. An analy- 80% of the expansion gases to the rear. Re-
sis of the incidents strongly su~ests that coilless weapons can therefore fire artillery-
acidic conditions were inadvertently generated sized ammo without generating artillery-sized
which markedly lowered the threshold temps re- recoil, or any recoil at all. Thus, the heavy
quired for expl decompn of these materials. It mountings and recoil- absorbing devides needed
is suspected that conditions were unintention- with artillery weapons are not required; with
ally produced under which the highly exother- internal stress and muzzle energies low, the
mic Beckman rearrangement preceded, and that barrel can be much thinner and lighter than
the resulting high temps resulted in the explo- that of a full-recoil gun firing the same weight
sively rapid formation of huge volumes of of shell. Naturally, the effective range is also
gaseous degradation products much smaller than with full-recoil weapons.
Subsequent expts led to the following For calibers of about 100mm, a recoilless rifle
findings: 1) Methylethylketoxime can be dis- (RR) will have a max range of 1000–2000
tilled at atmos press ( 152°) ordy if highly puri. yards, as opposed to a full-recoil gun range
fied; 2) The presence of impurities, especially of about 25000 yards. But the ratio of wea-
acidic impurities, drastically lowers the temp pon weights is also of the order of 1 to 20
at which degradation occurs; the hydrochloride even counting the wheeled mounts used with
salt of rnethylethylketoxime undergoes violent some RR’s, and cost ratios are also in this
degradation when heated to 50–70°; 3) Al- range. Recoilless weapons are used whenever
though the derived ketoximosilanes can be distd the range is secondary to the size of tiell de-
without difficulty at reduced press, here again livered, and where high velocities are not re-
the presence of acidic impurities drastically quired. RR’s are primarily intended for anti-
lowers their thermal stability. FeCl ~ at 10ppm tank use where their “hollow charge” (HEAT)
did not trigger the degradation even at 250°, shells penetrate armor without needing the
but 500ppm yielded an expln at 150°, and 2% kinetic energy required by conventional solid
lowers the onset of violent degradation to 50°. shot fired from full-recoil artillery
As with the ketoxime itself, the presence of The US 106mm RR and two earlier US
HC1 salts can cause expl degradation at rela- models which can be fired from the shoulder,
tively low temps the 75 and 57mm, are widely used, as is the
Ref L.J. Tyler, “Ketoxime Dangers”, C&EN Russ B-1 1 107mm RR and the older B-10
52 (35), 2 (2 Sept 1974) 82mm RR. Another widely used type is the
one-man 84mm Carl Gustav, manufd in Sweden
and used by, among others, the Brit army.
Keystonite. See under Alkalies, Action on The alrgest recoilless weapon, the Brit Wombat
Aromatic Nitrocompounds in Vol 1, p A126-R 120mm, is not widely used. These are all pro-
perly called recoilless rifles since their barrels
are rifled as in the case of conventional artil-
KH-Charge (KH-Ladung in Ger). The designa- lery. Some light recoilless weapons hale smooth
tion for a compressed charge consisting of 4–8 barrels and project a HEAT charge attached to
pellets of TNT, wrapped in paper and glued on a reduced caliber “stick” which fits into the
the inside with an acid-free glue such as dextrin. barrel. The West Ger Panzerfaust and ,the Russ
(

I
 K6

RPG both consist of a small caliber tube (about Kieselguhr or Guhr (Diatomite, Tripoli Powder).
40mm) within which the charge and “stick” Soft bulky solid material, 88% silica, composed
are set. When the weapon is fired, the “stick” of skeletons of small prehistoric aquatic plants
and the much alrger HEAT charge. affixed to related to algae (diatoms). It has the property
its end are projected out. These are short- of absorbing up to three times its weight of
range, one-man weapons fired from the shoul- NC and other liquids. It was formerly used
der (Ref 1) extensively in the manuf of Guhr Dynamites,
A novel approach to reducing recoil in con- invented by Nobel in 1866 (See under Dyna-
ventional artillery is the US XM-204 Soft Re- mite in Vol 5, pp D1595-L to D1 596-R).
coil Gun, still in an early stage of development. Present-day straight Dynamites have various
The barrel and recoining parts are held in a proportions of active constituents substituted
firing position against a spring; when released for kieselguhr wi~ resulting higher perfor-
they move forward. At their maximum for- mance (Ref 3)
ward velocity, the charge is fired. Much of Kieselguhr has also been used as a coating
the recoil energy is expended in checking the agent for porous pn”lled AN in Nitro-carboni-
forward momentum of the barrel, the remainder trate (NCN) blasting agents, where it aids in
is absorbed conventionally and “recocks” the the absorption of fuel oil (Ref 3)
spring used for the first part of the sequence. Refs: 1) Hackh’s (1969), 372-L 2) Cond-
Recoil forces transmitted to the carriage are ChemDict (1971), 274-R (under diatomaceous
reported to have been halved (Ref 2) earth) 3) C.E. Gregory, “Explosives for
Note: See also under Cannon in Vol 2, p North American Engineers”, TransTechPubli-
C28-R cations, Cleveland (1973), 42 & 55
Refs: 1) E. Luttwak, “A ,Dictionary of
Modern War”, Harper & Row, NY (1971),
162-R 2) Anon, “RUSI and Brassey’s De- Kinenite. AN expl containing DNB, somewhat
fence Yearbook 1974”, Praeger, NY (1974), 325 similar in compn to Bellite (Vol 2, p B32-R),
Roburite, Sekurite & Tonite
Refi Colver (1918), 141
Kier or Keir. A large vat in which cotton,
textile goods etc are boiled, bleached, etc
KINETICS IN EXPLOSION PHENOMENA
Introduction. In a very broad sense, kinetics
Kiering. Digestion of raw cotton, or other ma- (often called chemical kinetics) may be defined
terials, in kettles called Kiers. For instance, as the study of the rate of change of chemical
raw cotton may be purified by digesting it in reactions under non-equilibrium conditions.
a kier with a solution of caustic soda This incomplete definition will be augmented
Refi Marshall 3 (1932), p 29 below, but first we must consider why kinetics
are such an important facet in the practical
and theoretic~ understanding of explosion phe-
Kiernan and Bowen Explosive. An expl mixt nomena
developed by Kiernan & Bowen of New Orleans, There is general agreement that the energy “
La, contg Na chlorate 75, turpentine 10, bone- sources for detonations, deflagrations, thermal
meal 10 & dried blood 5%. It was concluded explosions and various transition phenomena
that this expl had no value from a military are exothermic chemical reactions. Thus, it
standpoint because of its low brisance, high is immediately clear that the rate of energy
degree of sensitivity to impact, and the ease supply, ie, the rate of the chemical reactions,
with which it lost turpentine, which resulted will have a most important bearing on the ini-
in decreased sensitivity to initiating agents tiation, growth and propagation of the above
Ref A.J. Phillips, “Study of Sodium Chlor- processes. Obviously, the influence of kinetics
ate Explosive Developed by Kiernan and on explosion phenomena is an immensely broad
Bowen”, PATR 1277 (April 1943) subject. Consequently, we must arbitrarily limit
 K7

ourselves to a description of only a relatively concentration of species A at time t; f is

few of its most important aspects, namely, A/Ao, the fraction of A. reacted in time t.
detonations and’ thermal explosions, to the ex- The rate constants k. and kl have the units
tent that the latter are required for a descrip- of moles/liter-see and see-*, respectively, if
tion of detonation effects. The kinetics of in- the concentrations are expressed in moles/
dividual explosives, if known, will be described liter. Obviously, the above definitions could
under the ind~vidwd explosives, and, as already have been made in terms of B or M or N, ex-
stated, we will be primarily concerned with cept that in accordance with Eq 1, the minus
the rate of energy supply, ie, the rate of the signs of the differential equations for M and N
thermal decomposition of explosives and the (Eqs 2 & 3) must be replaced by plus signs.
resulting exothermic reactions. The kinetics An excellent review of higher order reactions,
involved in the synthesis of explosive com- opposing reactions, consecutive reactions, etc,
pounds, eg, nitration kinetics, will be described is given in Chapts H & III of Ref.10 and in
elsewhere in this Encycl Ref 11
A Cursory Review of Chemical Kinetics. In Rate constants are “constant” only at a
what follows we will employ certain concepts fixed temp and vary strongly as the temp of
and terms widely used in the extensive literature the system changes. The following empirical
on chemical kinetics. These concepts and terms dependence of the rate constant k on the ab-
will now be reviewed briefly. For details, the solute temp T is known as the Arrhenius
reader is directed to the general references equation
listed at the end of this section
dlnk . ~ or ~ = ~e-E/RT (4)
For a generalized chemical reaction whose
dt RT2
stoichiometric (overall) equation is
where the Arrhenius parameters E and Z are
aA+bB=mM+nN,
called activation ene~ and frequency factor
the reaction rate R is defined b or pre-exponential factor, respectively. The usual
dimensions of E are cal/mole. The dimensions
‘=-:&):-~c+)=:t+)=+t:) ‘1) of Z are the same as those of k; thus for a
where a, b, etc are the number of moles of zero-order reaction Z is in moles/liter-see, and
chemical species A, B, etc, and (dA/dt), (dB/dt) for a first-order reaction Z is in see-l. The term
etc, are the rate of change of species A, B, etc. E/RT is dimensionless. Based on kinetic theory,
If experiments show that the reaction rate is Z is interpreted (Refs 1, 2, 6, 10 & 11) as the
independent of reactant A, the reaction is number of collisions per unit volume per second
called zero-order in A; if the rate depends on of molecules A+A or A+B, and the term e-E/RT
the instantaneous value of A, the reaction is is a measure of the fraction of colliding molecules
termed first-order in xl; if the rate depends that result in reaction. Thus, if E=O, then
on the instantaneous value of AZ, the reaction e-~/RT =1, and all colliding molecules react;
is called second-order in A, and so on. In conversely, if E/RT >> 1, almost none of the
most explosion phenomena we will deal only colliding molecules react
with zero-order and first-order reactions. The An alternate approach, the so-called transi-
rate equations for zero-order and first-order tion state or activated complex theory, is based
reactions are, respectively “on quantum mechanics and thermodynamics.
dA It postulates that the necessary condition for
=koor Ao– A=kot=l–f (2) reaction is the crossing of a potential energy
‘d~
and barrier. The initial configuration (reactants)
passesover by continuous changes of coordi-
dA
-—..-= nates to the final configuration (products),
klA or
dt and there is always an intermediate configura-
ln[*J “k’’= in(+)(3)
where k. and k, are ~he zero-~rder and first- tion (the transition state or activated complex)
order rate constants, respectively; A. is con- which is critical for the process. Once this
centration of species A at zero time; A is the critical configuration is attained there is a high
 K8

probability that the reaction will go to com- trols the overall reaction rate. For obvious
pletion (Refs 5, 6, 10 & 11). In terms of this reasons such a reaction is called rate-controlling,
theory E= AH*+RT, where AH* is the differ- and the overall rate constant is essentially that
ence in enthrdpies between the activated com- of this rate-controlling step
plex and the iriitial state, and For complex reactions, some of whose ele-
Z = !!# eAs*’R where kB mentary steps are of comparable rates, but
others are slower, the so-called stbdy state
and h are the Bol tzmann and Planck constants, hypothesis (Refs 4, 6, 10 & 11) can occasion-
respectively, and AS* is the entropy change ally lead to a simple theoretical description
in passing from the initial state to the activated (mechanism) of the complex reaction. A
complex famous example of this is the thermal decompn
Both the collision and activated complex of N205, where the observed kinetics for this
theories predict a mild dependence of Z on T, reaction are accurately first-order, even though
and the latter also predicts a mild dependence the reaction is complex (Ref 1O)
of E on T. In practice, over the limited temp For overall Arrhenius parameters (based on
ranges of the usual exptl conditions, these measurements of the overall rate constant as
mild dependencies are rarely observed. Both a function of temp), there are no “normal”
theories also predict that “normal” values of Z values if the reaction involves several elementary
should be 1013 to 1014 see-l for unimolecular steps of comparable rates. Indiscriminate use
processes. This agrees with many exptl ob- of such parameters in assessingdetonation phe-
servations. In many cases,however, because nomena (eg, hot spots) can lead to gross errors.
of steric effects, Z can be much smaller than The reader is reminded that much of the
“normal”. Benson (Ref 12) presents evidence existing kinetic data for explosives are based
that Z for certain unimolecular gas reactions on the measurement of the overall pressure
producing two free radicals, or for reactions changes in the system under study. Unless
involving the opening of a “small” carbon fing, the detailed reaction sequence, usually called
is larger than “normrd” and is of the order the reaction mechanism, is known, Arrhenius
1016 xc-l parameters based on pressure change measure-
All of the above discussion is strictly appli- ment can be most unreliable
cable only to homogeneous gas phase reactions. Refs for this section: 1) R.C. Tolman, “Sta-
Usually the above considerations do apply rea- tistical Mechanics”, NYChemCatrdogCo, NY
sonably well’ to non-polar liquids and non- (1928) 2) L.S. Kassel, “Kinetics of Homo-
polar solutions, although “normal” Z values geneous Gas Reactions”, ReinholdPublCorp,
may be an order of magnitude less than for NY (1932) 3) N. Semenoff, “Chemical
gas reactions. Reactions in solids are often Kinetics and Chain Reactions”, ClarendonPress,
much more complex, since they are usually Oxford (1935) 4) G.K. Rollefson & M.
heterogeneous, involve catalytic effects, re- Burton, “Photochemistry and the Mechanism
actions at preferential sites (dislocations, etc), of Chemical Reactions”, Prentice-Hall Inc,
and nucleation phenomena. These complicated Englewood Cliffs, NJ (1939) 5) S. Glass-
processes are quite beyond the scope of the tone, K.J. Laidler & H. Eyring, “The Theory
present article. For some description of these of Rate Processes”, McGraw-Hill, NY (1941)
phenomena, and further references, the reader 6) W.A. Noyes, Jr & P.A. Leighton, “The
should consult Refs 9, 10 & 11 Photochemistry of Gases”, ReinholdPublCorp,
Another important aspect that we have so NY (1941) 7) E.W.R. Steacie, “Atomic
far ignored is that reactions almost never ac- and Free Radical Reactions”, 2nd Edit, Rein-
tually proceed as represented by a stoichio- holdPublCorp, NY (1954) 8) D.A. Frank-
metric equation (eg, Eq 1). Usually a stoi- Kamenetskii, “Diffusion and Heat Exchange
chiometric equation is the algebraic sum of a in Chemical Reactions”, Princeton Univ Press,
number of steps called elementa~ reactions. Princeton, NJ (1955) 9) F.P. Bowden &
Frequently one of these elementa~ reactions A.D. Yoffe, “Fast Reactions in Solids”, Aca-
is much slower than the others, and thus con- demic Press, London (1958) 10) S.w.
 K9

Benson, “The Foundations of Chemical Kinetics”, Table I

McGraw Hill, NY (1960) 11) H. Eyring & Isothermal, Decomposition of Explosives
E.M. Eyring, “Modern Chemical Kinetics”, at CJ Conditions
ReinholdPublCorp, NY (1963) 12) S.w. Explosive Arrhe.nius Fraction
‘CJ
Benson, “Thermochemical Kinetics”, J. Wiley Parameters * (nan~sec) (“K) Reacted (f)
& Sons, NY (1968)
TNT Zinn & Rogers 10 2250 1
Application of Kinetics to Explosion Phenomena.
TNT Zim & Rogers 1 2250 0.70
Brief mention was made earlier of the various NMe Makovsky & 1 3000 1
explosion phenomena that are strongly de- Gruenwald
pendent on the kinetics of the exothermic NMe Makovsky & 0.1 3000 0.74
chemicrd processes involved in explosions and Gr-uenwald
detonations. This matter will now be con- PETN Robertson 0.1 2550 1
sidered in more detail as follows: PETN Roth 1 2550 1
1) Steady Detonation, 2) Initiation Processes, PETN Roth 0.1 2550 0.99
3) Stability and Storage, and 4) The “Ideal”
Explosive *See Table 111
In what follows, the experimental Arrhenius Initiation Processes. For an adiabatic thermal
parameters E and Z may be for the overall explosion, the delay T is given by (See Vol 4,
exothermic process and may not always refer p D620 and this Vol, under Hot Spots, p H170ff)
to the E and Z of a simple elementary reaction
~ = CRT2
in that process ~ exp (E/RT) (5)
Steady Detonation. The thermo-hydrodynamic
theory of detonation is very successful in de- where Q is the heat of explosion and c is the
scribing ideal detonation parameters (CJ states) specific heat. The controlling variable in this
without any reference to chemical kinetics. equation is the activation energy E obtained
This is so because reaction rates at CJ conditi- from kinetic studies. This is shown in Table II
tions are extremely fast – at least for military Table II
explosives. Based primarily on the dependence Influence of Kinetics on Adiabatic
of detonation velocity on explosive charge dia- Explosion Times of PETN
meter, Jones, Eyring and others (Refs 2, 3,
Arrhenius
10 & 11) have estimated that reaction times for
Parameters* T(”K) 7 (see)
ideal detonations of military explosives are the
order of 0.1 to 1 psec. Thus for ideal deto- Robertson 2550 8.8 x 10-18
mtion conditions, f, the fraction of explosive hdrew & Kaydimov 2550 4.7 x 10-14
reacted, must approach unity in times that are Roth 2550 1.7 x 10-12
appreciably less than 0.1 to 1 psec. In Table Robertson 1000 2.7 X 10-12
I we show that this is indeed the case. The Andrew & Kaydimov 1000 8.6 x“lo-10 ‘
calculations of f were made under the assump- Roth 1000 5 x 10-9
tion of isothermal first-order decomposition at Robertson 750 4 x 10-9
TCJ (conservatively estimated in the tabulation), Andrew & Kaydimov 750 3.3 x 10-7
and the kinetic parameters of Table III of a Roth 750 5.1 x 10-7
following section Robertson 600 7.8 X 10-6
Andrew & Kaydimov 600 1.5 x 10-4
Roth 600 7.5 x 10+
Robertson 500 1.3 x 10-2
Andrew & Kaydimov 500 1.1 x 10-1
Roth 500 1.0 x 10-2
*See Table III
 K 10

Note that variation hi Arrhenius parameters strongly for a particular explosive in its vapor or li-
influences ~ at high temperatures, but regardless quid state and then used to estimate its stor-
of the source of the kinetic data, the conclusion age life, could give very misleading results.
that chemical reaction is exceedingly fast at CJ Furthermore, most explosives decompose auto-
temperatures is still valid. At lower temperatures catalytically, ie, they produce decomposition
(the region where initiation processes pre- products that accelerate further decomposition.
sumably occur) considerable compensating Also, impurities not removed during manufac-
effects are evident and the computed explo- ture can greatly shorten storage life. All of
sion times are much less dependent on data these facts must be taken into account
source than they are at high temperatures As an example, let us consider the storage
Campbell et al (Ref 7) have successfully characteristics of liquid NC at 21° (294°K).
used Eq 5 to interpret their observations on Unfortunately, the Arrhenius parameters for
the shock initiation of homogeneous explo- NC given in the literature (Table III) vary
sives such as NM, Iiq TNT & single crystal widely. An average of the Serbinov-Roth
PETN parameters (Tables 111& IV) gives an adia-
Heterogeneous initiation phenomena, batic explosion time of 32 years at 21°, while
generally interpreted in terms of hot-spot the Robertson parameters (Table 111)give a
mechanisms, are also strongly influenced by time of 2500 years! Since conditions will
the kinetics of exothermic decompn of the not be adiabatic over long periods of time, the
explosive being initiated. The general relations calculations show that pure NC has good stor-
between hot spot parameters and decompn age life — certainly longer than 32 years. How-
kinetics parameters are given in Eqs 1 thru 5 ever, Gorbunov & Svetlov (Ref 8) have shown
of the article on Hot Spots in this Vol, pp that induction periods at 400, to the onset of
HI 70ff. Of special interest is a recent inter- rapid gas production, are approximately in the
pretation of the initiation of explosives by ratio 7:3.5:1 for pure NC, NG with 0.16% w,
impact presented by Afanasev & Bobolev and NG with O.17% nitric acid. Thus, the
(Ref 12), described under Impact, Initiation storage life of NG containing minor amounts
of Explosion by in this Vol, pp 135ff. In of nitric acid can be expected to be at least
Ref 12, the relation between the variables seven-fold less than that of pure NG. Nitric
controlling impact initiation and the kinetic acid in NG can be an impurity not totally
parameters of the explosive impacted are given removed during manuf, and it can also be a
by their Eqs 11 thru 14. A rather different decompn product (3N02 + H20 = 2HN03 + NO)
treatment of impact initiation, based on adia- The “Ideal” Explosive. From a kinetics point
batic compression of small occluded gas bubbles of view the “ideal” explosive is readily identi-
in explosives, and the dependence of these pro- fiable, but to find such an explosive is quite
cesseson chemical kinetics are presented by another matter. To possessgood storage life
Bowden and Yoffe (Refs 5 & 6) and be impervious to moderate energy stimuli,
The large uncertainty in the quantitative the ideal explosive should have a large E, small
interpretation of heterogeneous initiation phe- Z, be readily purifiable, non-hydroscopic, and
nomena results not only from the uncertainty produce no decompn products that accelerate
of the kinetic parameters used (See section further decompn. It will explode only upon
on Kinetic Data), but also from the large un- being wbjected to large, externally applied,
certainty of the temps of the initiation sites stimuli, such as the nearby detonation of an-
(hot spots) other explosive. At present, theory offers
Storage and Stabili~. It is obvious that prac- little guidance as to what type of compounds
tical explosives must possesslong storage life. have a large E for decompn, yet produce ap-
Kinetic data are most useful in evaluating preciable heat once they start to decomp (large
the storage characteristics of an explosive, Q). For a low vrdue of Z, th~ activated com-
but they must be the right kind of data. plex theory indicates that AS (See Cursory
Most explosives are solids under normal stor- Review of Chemical Kinetics section) should
age conditions. Thus, kinetic data obtained be negative. In terms of molecular structure,
 K 11

this suggests that the activated complex has a extensive use of the Arrhenius parameters E
very rigid molecular structure, while the un- and Z, and to a lesser extent of Q, the net
decomposed explosive has a very “floppy” heat of decomposition reactions. A compila-
molecular structure tion of this data is given in Table 111. Unfor-
tunately, many of these data are wildly dis-
Kinetic Data. In a previous section we made cordant, eg, for PETN, E and logz range from

Table Ill

Kinetic & Thermochemical Parameters for the Decomposition

of Molten and Liquid Explosives
Explosive Temp Range Q E(kcal/ log Z Experimental Refs
(“C) (cd/g) mole) (see-’ ) Method
Amm Nitrate 217–267 — 38.3 12.3 Weight loss Cook & Abegg (7)
Amm Nitrate 243–361 — 40.5 13.8 Pressure Robertson (2)
Diaminotrinitro- ? — 46.3 15.1 DSC (a) Rogers (18)
benzene (DATB)
DINA 150–170 680–720 45.0 18.6 Weight loss; Dubovitsky et al (1 O)
Pressure &
Heat Evoln
DINA 130–175 — 35.5 13.4 Adiabatic furnace Gross & Wster (14)
EDNA 184–254 — 30.5 12.8 Pressure Robertson (2)
EDNA 144-167 — 30.8 11.1 Weight loss Cook & Abe% (7)
EGDN 95–105 —. 39.0 15.9 Pressure Phillips (1)
EGDN (vap) 140–170 — 35.7 14.3 Pressure Andreev & Belyaev (9)
HMx 270–295 — 52.7 19.7 Pressure Robertson (5)
HMX ? 560 57.3 18.8 DSC (a) Rogers (17)
(Ref 17)
Hydrazine Nitrate 189–200 — 38.1 12.2 Weight loss Cook & Abegg (7)
Hexanitrostilbene ? — 30.3 9.2 DSC (a) Rogers (18)
(HNS)
NG 75–105 — 40.3 17.1 Pressure Phillips (1)
NG 115–282 — -35 -14 Thermal explosion Serbinov (8)
NG (vap) , 150–160 — 36 15.5 Pressure Andreev & Belyaev (9)
PETN 160–225 — 47.0 19.8 Pressure Robertson (2)
PETN 145–171 — 39.0 15.6 Pressure Andreev & Kaydimov (13)
PETN 177–222 — 46.5 19.4 DSC (a) Rogers (18)
PETN 149–201 — 31.8 13.4 Chemical analysis Roth (6)
RDx 213–299 — 47.5 18.5 Pressure Robertson (4)
RDx ? — 43.1 16.4 DSC (a) Rogers (18)
RDx ? 615 45.2 — DSC (a) Hall (16)
Tetryl 211–260 — 38.4 15.4 Pressure Rideal & Robertson (3)
Tetryl 140–165 — 40.0 16.0 Pressure Dubovitsky et rd (12)
Tetryl 145–155 340 36.0 15.6 Heat Evoln Dubovits@ et al (11)
Tetryl ? 330 — — DSC (a) Hall (16)
Tetryl 132–164 — 34.9 12.9 Weight loss Cook & Abe= (7)
TNT 257–310 — 34.4 11.4 Pressure Robertson (4)
TNT 237–277 — 43.4 12.2 Weight loss Cook & Abe% (7)
TNT 288 (b) — 41.1 13.2 Thermal explosion Zinn & Rogers (15)
TNT 220–260 300 (c) 37.0 11.2 Adiabatic furnace Gross & Amster (14)
a) Differential Scanning Calorimeter
b) Min temp at which explosions were observed in 1-mm thick samples
c) Assumed
 K 12

a high of 47. Okcal/mole and 1019”8see-l to a . lne restuts m 1awe IV show agreement with
low of 3 1.8kcaJ/mole and 101s”4sec-1, respec- the lower values of E and Z of Table III, ex-
tively. Moreover, the temp ranges over which cept for TNT, for which “Wenograd” data
the kinetic parameters were measured are re- are not reliable
latively low. Thus, there is no assurance that
Writterr by J. ROTH
the parameters hold at considerably higher temps,
eg, detonation temps Refs: 1) L: Phillips, Nature 160,753 (1947)
Some insight into what are the “best” para- 2) A.J.B. Robertson, JSocChemInd(London)
meters, and how valid they are at higher temps, 61, 221 (1948) 3) E.K. Rideal & A.J.B.
may be gained by examining the results of the Robertson, ProcRoySoc A195, 135 (1948)
so-called Wenograd test. In this test liq or 4) A.J.B. Robertson, TransFaradSoc 44, 977
molten expl is loaded into a hypodermic needle (1948) 5) Ibid, 45,85 (1949) 6) J.
which is then heated rapidly to a controlled Roth, Addendum to Bulletin Sixth Army-Navy
temp by condenser discharge, and the explo- Solid Propellant Group Meeting (1950), p 41
sion time of the test explosive at that temp 7) M.A. Cook & M.T. Abegg, IEC 48, 1090
is measured. Roth (Ref 9) obtained “Weno- (1956) 8) A.I. Serbinov, ZhFizKh 33,
grad” kinetic parameters for NC, EGDN, 2641 (1959) 9) K.K. Andreev & A.F.
TNT and Petrin. He analyzed the results in Belyaev, “Theory of Explosive Substances”,
terms of Eq (5) and the following Eq based FTD-MT-64-242 (1966), p 149 (Russ original
on Frank-Kamenetskii (Ref 1) and Chambr6 published in 1960) 10) F.I. Dubovitsky,
(Ref 4) TranslIzvAkadNauk(Chem) No 6, 1126 (1960)
—
E-
T min
= 4.57 log
[
pQZE
~ AR
r2
T~h 1 (6) 11) Ibid, 1763 (1960) 12) F.I. Dubovitsky
et al, Russ JPhysChem 35 (3), 255 (1961)
13) K.K. Andreev & B.I. Kaydimov, Ibid, 1324
where: d is a geometric factor =2 for cylinders (1961) 14) D. Gross & A.B. Amster, 8th
A is the heat conductivity of the expl 15) J. Zinn &
SympCombustn (1962), 729
r is the radius of the expl cylinder
R.N. Rogers, JPhysChem 66, 2646 (1962)
‘m in is the lowest temp at which explo- 16) P.G. Hall, TransFaradSoc 67 (2), 556
sions are recorded (1971) 17) R.N. Rogers, Thermochimica-
Acta 187, 1 (1972) 18) R.N. Rogers, Pri-
vate Communication (1974)

Table IV

Arrhenius Parameters Based on the Wenograd Test

(0.018cm inner diameter tubes)
“Direct”*
Explosive Temp Range Min Tube Min HE Z**
“K (kcal~mole) (se~-l ) Temp ‘K Temp “K (WC”’)
NG 555–650 35 2.3 X 1014 555 515 -2x 1015
EGDN 570–645 35 2.8 X 1014 570 530 -9x 1014 ,
TNT . — 700 650 -4x 1014(a) ~
Petrin 550–630 28 12 x 1011 , 540 510 -4x 1012
(PE-trinitrate)
*From slope of explosion time vs 1/0.93 T’tube data and Eq (5), with Q E 500 cal/g for NG, EGDN &
Petrin and Q q 300 cal/g for TNT
**From Eq (6) us~g min HE Temp and “direct” E
(a) Assumed E = 41.1 kcal/mole
 K 13

Refs: 1) D.A. Frank-Kamenetskii, ActaPhys- Kirsanov Explosive. A Sprengel-type expl prepd

Chim URSS 10, 365 (1939) 2) H. Jones, by mixing just before use, a mixt of K chlorate
ProcRoySoc(London) A189, 415 (1947) 80 and Mn dioxide 20%, with a tit of tur-
3) H. Eyring et rd, ChemRevs 45 (l), 69 pentine 90 and phenol 10%. The solid oxidiz-
(1949) 4) P.L. Chambr6, JChemPhys 20, ing mixt acts as an absorbent for the liq fuel
1705 (1952) 5) Bowden & Yoffe (1952) Refs: 1) Davis (1943), 355 2) A. P&ez
6) Bowden & Yoffe (1958) 7) A.W. Camp- Ara (1945), 231
bell et al, PhysFluids 4 (4), 498 (1961)
8) V.V. Gorbunov & B.S. Svetlov article in
K.K. Andreev et al, “Teoriya Vzryvchatykh K1-Starch Test. See Abel’s Test in Vol 1, p A2-L
Veshesto” (Theory of Explosive Substances),
translation FTD-MT-63-254 (1964), (Russ
Oligifld 1963), 274-291 9) J. Roth, Stan- Kittitas. Conditioning agents commonly used
fordResInst Finrd Rept, Contract Now 65- for reducing the tendency of ~ to cake are
0283~d (1966) 10) L.G. Bolkhovitinov et Kaolin or other forms of clay, and various
al, 12th SympCombustn (1969), 776 types of Kieselguhr (qv), such as Kittitas,
11) P.A. Persson & T. Sj6hn, 5th DetonSymp Celite & Dicalite
(1970), 153-67 12) G.T. Afanas’ev & V.K. Refs: 1) Anon, lEC 36, 1088 (1944)
Bobolev, “Initiation of Solid Explosives by 2) Not found in CA
Impact”, NASA translation TTF-623 (1971)

Kiwit. A Ger chlorate expl introduced during

Kinetite (Kinetit or Kin6nite-Swiss). One of WWI. It contains not more than 77% Na or
the earliest gelatinous (plastic) expls which K chlorate, carbon carriers such as paraffin,
contd no NG. It was patented in 1884 by naphthalene, vaseline, meal or oil, and not
Petry and Fallenstein and was used extensively more than 15% DNT. It may contain DNT,
at the end of the last century in Ger and other Dinitronaphthalene, NaCl and not more than
European countries. It was prepd by gelatiniz- 4% Guncotton
ing Nitrobenzene or Nitrotoluene with Col- Refi Marshall, Diet (1920), 54
lodion Cotton, and impre@ting this plastic
mass with sulfur, K chlorate and other ingre-
dients. Sulfur was later replaced by Sb penta- Kjeldahl, J. (1 849–1900). Danish analytical
sulfide. Its compn was: NB 16.0 to 21.0, chemist, inventor of the method for determining
Collodion Cotton 0.75 to 1.0, K chlorate 82.5 nitrogen in organic compounds, which is still
to 75.0, Sb2S5 and/or K nitrate 3.0 to 1.0%. used extensively (See below)
The function of the Sb pentasulfide was to Refs: 1) Hacl@’s (1944), 470 2) S. Veibel,
render the explosion more regular and more JChemEduc 25, 459 (1949)& CA 43, 776
complete (1949)
Kinetite is ve~ insensitive to heat, but too
sensitive to impact and friction. It was not
stable in storage, and sometimes expld spon- Kjeldahl Method. A method of detg the N in
taneously with no apparent cause an organic compd by digesting the substance
Refs: 1) Daniel (1902), 392 2) Colver with coned sulfuric acid in the presence of
(1918), 142 3) Marshall, Diet (1920), 54 catalysts such as selenium, Devarda’s alloy,
4) Nao6m, NG (1928), 353 5) Giua, Trat- etc. This treatment transforms the N into
tato VI (1) (1959), 394 Amm sulfate. By adding an excess of caustic
and distg the liberated ammonia into a measured
quantity of standard sulfuric acid (which is
Kinite (Brit). A Dynamite consisting of NG later titrated), it is possible to determine the
25–27, Ba nitrate 30–36, wood flour 30–36, amount of N in the substance
Na carbonate 0.5– 1.0 &Amm oxalate 0.5–10% In using Devarda’s alloy (Cu/Al/Zn-50/45/5)
Ret Giua (1958), 338 for N content analysis, it is advisable not to
 K 14

heat the flask until the evolution of hydrogen of 1.22, 13 & 63g/liter, respectively. The %
and other gaseshas ceased. This minimizes the knallgas reacted at final press and temp was
risk of initiating a hydrogen-air expln. As an a function of initial concn and rose abruptly
added precaution, the entire app should be at the threshold composition. The partial
placed behind a safety shield (Ref 6) molrd density of knallgas, which is proportional
Refs: 1) J. Kjeldahl, ZAnalChem 22, 366 to the potential heat release per unit, increased
(1883) 2) W.C. Cope & G.B. Taylor, US with temp (Ref 1)
BurMines Tech Paper 160, 10–13 (1917) Calculated detonation properties of knallgas
3) Scott & Furman (1939), 632–35 & 2492 and heavy knallgas were compared from 1 to
4) R.B. Brandstreet, ChemRevs 27, 331 (1940) 15 atm using an 18ft, 1“ diameter detonation
5) Hackh’s (1944), 471 6) W.G. Cameron, tube. The detonation velocity was determined
Chem&Ind 1948, 158 &CA 42, 3964 (1948) by using ionization probes to measure the time
for a wave to traverse 8.984ft. Pressures were
measured with an oscillogram instrumented
Klaffke’s Explosive. A blasting powder com- transducer. Knallgas mixts were prepared by
posed of K nitrate 73.9, C 13.4 & cellulose 12.7% premixing H ~ or D2 and 02 and storing under-
Ref: A. K.laffke, FrP 396496 (1908) &CA ground for 3–5 days. Theoretical calculations
4, 2733 (1910) were based on Chapman-Jouguet detonation
theory with assumption of equilibrium. Stable -
detonation velocities in heavy knallgas at 25°
Klepsydra. See Clepsydra under Chronographs agreed with those predicted by Chapman-
in Vol 3, p C308-L Jouguet detonation theory from 1 to 15 atm
(Ref 2)
Refs: 1) J.A. Luker et al, JChemEngData 6,
KMA Block. A Ger substitute expl. See under 253 (1961) &CA 55, 21590 (1961)
Ersatzsprengstoffe in Vol 5, p El 22, Table E 15 2) L.B. Alder et al, JChemEngData 6, 256
(1961) &CA 55,21590 (1961)

KMP (Powder). See under Plastomenite

Knallquecksilber (Ger). See under Mercuric
Fulminate or Mercury Fulminate in Vol 6,
Knallgalert. A Russ pre-WWI expl used for pp F217-L to F223-L
rock blasting contained NG 88.6, pyroxylin
6.7 & DNT 4.7%
Rejl Anon, SS 12,409 (1917) Knallsilber (Ger). See under Silver Fulminate
/ in VO1 6, pp F223-R to F224-R

Knallgas (Ger). An exptl mixt of Hz and 02,

or air. The effect of initial mixt density on Knallzundschnur (Ger & Swiss). Detonating
the initiation of detonation in knallgas and the Fuse or Primacord. See under Detonating
detonation properties of “heavy” knallgas Cords or Detonating Fuses in Vol 3, pp
(2D2+02) have been studied D103-R to D107-L
Initial mixt composition ranges of knallgas
and w vapor in a detonation tube were varied
by controlling temps at 100, 200 & 300°, for Knecht Compound. Knecht (Refs 1 & 2)
knrdlgas densities of 0.64–1 .8, 8.5–16 & 46– treated cellulose with 65% nitric acid (d 1.14
62g/liter, respectively. Ignition was by hot g/cc) and obtained an addition product. After
wire. The threshold composition decreased removing the acid retained mechanically he
as initial mixt density increased. Threshold established that the addition compd contained.
compositions were 62, 44 & %36% knallgas nitric acid corresponding to 7.7% N. This is
at 100, 200 & 300°, or initial mixt densities approximately equivalent to one N02 group for
 K 15

every anhydroglucose unit. Drowning the ad- Wilson, Ardeer (1936), according to F.D.
dition product in w caused nitric acid to split Miles, “Cellulose Nitrate”, Oliver & Boyd,
off, and Knecht thought that it was an excep- London (1955), 56 8) G. Champatier & R.
tionally labile nitrate. I-Gusserrnan (Ref 3) Marton, BullFr 10 [5], 102 (1943) 9) Ur-
found it to be a rather unstable addition pro- ba6ski 2 (1965), 321–23, 353
duct. Champetier & Marton (Ref 8) examined
‘ the ultra-violet reflection spectrum, and found
that it contains a band at 270–305rrw which Knetmaschine (Ger for Kneading Machine).
is not present in the spectrum of NC. They An apparatus for mixing solid ingredients in
considered that this supports the view that the the presence of liquids. Several types were
Knecht compound is an individual substance used in Ger for mixing proplnts & expls, such
differing from NC as the Columnar type (Saulenknetmaschine)
Cellulose regenerated from the addition (Ref 2, pp 105–06; Ref 3, p 237); Werner-
compound may demonstrate a certain degree Pfleiderer Misch-und Knetmashine (Ref 1, p
of nitration (0.5–2.2% N). The properties of 75; Ref 3, p 227; Ref 4, pp 585–87), and
the compound are similar to those of hydro- others. In France, Chaudel-Page kneaders are
cellulose, eg, glittering fibers, increased h ygro- in general use (Ref 4, pp 588–9)
scopicity and higher reactivity, Refs: 1) Barnett (1919), 75 2) Naoiim,
X-ray investigations by Hess & Katz (Ref 4) Exph (1927), 105–06 3) Stettbacher
suggest that the addition product is probably (1933), 227,237 4) Urbafiski 3(1967),
compatible with the formula C6H1 005 .HN03. 585–89
The X-ray diagram of the compound is a char-
acteristic one differing from that of cellulose.
They concluded that it was produced by the Kochsalzsprengstoffe (Kitchen Salt Explosives).
action of 86% nitric acid Ger substitute expl mixts containing a large
According to the expts of Andress (Ref 5) amount of Na chloride, used during WWII.
the composition of the Knecht compound after See under Ersatzsprengstoffe (Substitute Ex-
being kept under reduced press for some time plosives) in Vol 5, pp E121-L to E122-R
should be denoted by the formula 2C6H ~005 .HNC)3.
He demonstrated that the compound produces
a characteristic X-ray fiber diagram Kofler Micro Hot State Apparatus. Electri-
I@er, Wilson (Ref 7) established that its cally heated apparatus which might be con-
composition after drying under a high vacuum is sidered a modification and improvement of
2C15HI0C)5.HN03. H20. The product of ab- the Fisher-Johns apparatus. It permits micro-
sorption of nitric acid vapors by cellulose is, scopic studies of fusion, sublimation, crystal-
according to Wilson, not a Knecht compound, lization and explosion phenomena
since it did not give the characteristic X-ray Refs: 1) L. Kofler, Mikrochemie 15, 242
diagram though its chemical composition is (1934) 2) N.D. Cheronis & J.P. Entrikin,
approx that of the Knecht compound Semimicro Qualitative Organic Analysis, T.Y.
Trogus (Ref 6) collected data concerning the Crowell Co, NY (1947), p 36 3) A. Weiss-
concn of nitric acid to produce the Knecht berger, Physical Methods of Organic Chemistry,
compound, and concluded that it is formed 2nd edit, Part 1, Interscience Publishers Inc,
when a mixt of ~most equivalent quantities NY (1949), pp 78–9, 883–85 4) Arthur H.
of the hydrates HN03.H20 and HNOS.3HZ() Thomas, Laboratory Apparatus & Reagents,
act on cellulose Philadelphia (1950), pp 877–80, Catalog No
Refs: 1) E. Knecht, JSocDyers and Colorists 6886-A; (1974), pp 876–77, Catalog Nos
12, 89 (1896) 2) E. Knecht, Ber 37, 549 6608–H 10 thru 6608-H40
(1904) 3) C. Hriussermann, AngChem 23,
176 (1910) 4) K. Hess & J.R. Katz, ZPhys-
Chem 122, 126 (1926) 5) K.R. Andress, Kohlen-Albit (Ger). One of the Kohlenspreng-
ZPhysChem 136, 279 (1928) 6) C. Trogus, stoffe (coal mining explosives). Its compn was
Cellulosechem 15, 105 (1934) 7) G.L. similar to Gesteins-Koronit. It was used as a
 K 16

permissible expl in coal mines for a short time, Kohler Powder. K chlorate 70, sulfur 20.0 &
but because of its large flame on expln was charcoal 10%. Very, sensitive and dangerous
replaced by AN expls mixt, similar to Berthelot’s Powder (See Vol
Refs: 1) Naofim, NC (1928), p 428 2, p BI06-L
2) Clift & Fedoroff 2 (1943), p K1 Rej Pi%ez Ara (1945), p 206

Kohlensprengstoffe (Coal Explosives). A group Kolax. A Ger expl of the Carbonite type
of Ger expls permitted for use in coal mines: contg NG 25, K nitrate 26, Ba nitrate 5,
Kohlen-Carbonit. NG 25, K nitrate 34, Ba woodmeal 34 & starch 10%O.Super- Kolax
nitrate 1, flour 38.5, spent tan meal 1 & soda was a modification of the above used in Eng-
ash 0.5%. Qe 506kcal/kg, Temp of Expl land: NG 28.5, Collodion Cotton 1.0, K
1561°, Vel of Deton 3160m/see, d 1.16g/cc, nitrate 16.5, Ba nitrate 5.0, Amm oxalate
Trauzl test value 235cc, Charge limit 900g, 9.5, woodmeal 30.5 & starch 9.0%. Both are
equivalent to 501 g of Brit standard Gelignite no longer on the permitted list
Refs: 1) Marshall 1 (1917), 376 2) Marshall Refs: 1) Marshall 1 (1917), 375 2) Marshall,
2 (1917), 492 3) Barnett (1919), 140 Diet (1920), 54 3) Clift & Fedoroff 2 (1943),
4) Naotim, NG (1928), 401 p K1 4) PATR 2510 (1958), p Ger 102-L
Kohlen-Koronit III. NG 4, K chlorate 68,
Na chloride 14, paraffin 8, MNN 5 & wood
meal 1%. OB -2.6%; Trauzl test value, 195CC Kolfit (Ger). An expl mixt patented by H.
Refs: 1) Naofim, Expl (1927), 147 Kolf in 1890 for use as a smokeless proplnt,
2) PATR 2510 (1958), Ger 101-R but also suitable as a blasting expl. It was
Kohlen-Salit. NG (gelatinized with NC) 12.5, prepd by nitration of residues from flour mills,
vegetable meal’ 2.5, aromatic nitrocompounds starch and sugar plants, distilleries, breweries,
7.0, AN 41.0 & alkali chlorides 37.0%. OB etc. Oil cakes, moss, and pine needles were
-2.6%, Trauzl test value 260cc also nitrated. The resulting nitrated substances
Refs: 1) Nao6m, NG (1928), 411 2) Fedor- were treated under 5 atm press with sulfides
off & Clift 4 (1946), 49 3) PATR 2510 or polysulfides, and then mixed with saltpeter “
(1958), Ger 101-R previously saturated with Nitrobenzene
Kohlen-Silesia 4A. K chlorate 80, resin 16 & Refs: 1) Daniel (1902), 394 2) Fedoroff
Nitroresin 4%. Silesia No 4 contd K chlorate & Clift 4 (1946), 50 3) PATR2510 (1958),
80 & resin 20% p Ger 102-L
Refs: 1) Barnett (1919), 111 2) Fedoroff
& Clift 4 (1946), 50
Kohlen-Westfalit I. NG 4.0, AN 83.0, K Kolf’s Blasting Powder. Ger mining expl pa-
nitrate 7.0, Ba nitrate 2.0, meal 2.0’& TNT tented in 1892. A mixt of equal parts of NC,
2.0%. OB +16.4%, Trauzl test value 230cc Nitrolignin & Nitrostarch 50, Nitrosugar 38,
Refs: 1) Naofim, NG (1928), 435 2) PATR NG 8, saltpeter 2 & aniline 2%
2510 (1958), p Ger 102-L Refs: 1) Daniel (1902), 394 2) Fedoroff
Kohlen-Westfalit IV. NG 3.’2, AN 73.0, K & Clift 4 (1946), p 50
nitrate 2.8, alkali chloride 15.0, meal 1.0 &
DNT 5.0%. OB +8.8%, Trauzl test value 200cc
Refs: 1) Naotim, NG (1928), 435 2) PATR Kolf’s Powder. A proplnt (greenish-brown
2510 (1958), p Ger 102-L leaflets) used at the end of the 19th century
Kohlen-Westfalit V. NG 4.0, AN 83.0, K in England. It consisted of equrd parts of NC,
nitrate 8.0, Ba nitrate 2.0, potato meal 1.5 Nitrostarch & Nitrolignin, gelatinized by a
& Montan wax 1.5%. OB +13.5% & Trauzl volatile solvent, and mixed with about 0.570
test value 230cc sulfur and 2’%0K nitrate
Refs: 1) Naofim, NG (1928), 435 2) PATR Refi Daniel (1902), p 394
2510 (1958), p Ger 102-L
 K 17

Kollodiumwolle. Ger & Swiss for Collodion Refs: 1) Stettbacher (1933), pp 174, 333
Cotton 2) Stettbacher (1948), pp 60, 97 3) Stett-
bacher (1952), pp 82–3, 99 & 126
Kolner Dynamit Fabrik. A method, patented
in 1885, of impregnating Dynamite cartridges
with such materials as Al oleate in order to Koronit. One of the Ger expls of the chlora-
make them more flexible tite class, developed during WWI in order to
Refi Daniel (1902), 395 conserve NG. It contains K nitrate and/or
Na nitrate 70–80, Nitroderivatives of toluene
and/or diphenylamine and/or naphthalene
Koln-Rottweiler Sicherheits-Sprengpulver. 12–20, vegetable meal 1–5, solid hydrocar-
One of the older Ger safety expls consisting bons and/or oils and fats 3–5 & NG (not
of: Amm Nitrate 93.0, vegetable oil 4.9, gelatinized) 2–6%
sulfur 1.2 & Ba nitrate 0.9%;;; Refs: 1) Marshall 3 (1932), p 112 2) Davis
Rejl Daniel (1902), p 395 (1943), 361

Koronit or Favorit is, according to Marshall

Kolowratnik’s Explosives. Chlorate eXplS (Ref 1), a Ger chlorate blasting expl. Its
contg PA 40, K chlorate 10–20, Na nitrate nonpermissible modification, Gesteins-Koronit
25–35, Na carbonate 5 & wood flour l(l%o Tl, (See Vol 6, p G73-L) contains Na chlorate
Refs: 1) R. Kolowratnik, BritP 26884 (1912) 72, DNT & TNT 20, NG 3-4, vegetable meal
& CA8, 1672 (1914) 2) Colver (191 8), 1–2 & paraffin 3–4% (Ref 2). Bebie (Ref 3)
325 and Warren et al (Ref 4) list this expl under
the name Coronit (See Vol 3, p C543-R).
The permissible modification, Kohlen-Koronit
Konig Explosives. J.B. IG6nig patented in 1890 (qv), contains according to Ref 1, not more
a method of prepn of expls by nitration of high than 68 parts of K or Na chlorate, not more
bp hydrocarbons derived from the distn of coal, than 12 parts of aromatic hydrocarbons or
bituminous shales or residues of petroleum re- nitrocompds (but no trinitrocompds), not
fineries, paraffins, and ozokerite more than 4 “parts Blasting Gelatin, not more
Refl Daniel (1902), 395 than 4 parts of powdered coal, with the re-
mainder consisting of Na chloride, paraffin,
etc
Konovaloff Reaction. A color test for primary These expls were eventually replaced by
or secondary nitro-compds. Samples are Perkoronits, which are similar to Koronits
treated with Na hydroxide soln, the salt form: except that they contain perchlorates rather
ed is extrd with w, and ether is added to this than chlorates
extr. Upon dropwise ,addition of ferric chlor- Refs: 1) Marshall, Diet (1920), 55 2) Naofim,
ide, a red to reddish-brown color develops in NG (1928), p 428 3) Bebie (1943), p 52
the ether 4) F.A. Warren et al, “Chlorates and Perchlor-
Refi E.F. Degering, “An Outline of Organic ates, Their Manufacture and Uses”, NAVORD
Chemistry”, 4th Ed, Barnes & Noble, NY Report 7147, Vol 1 (1960, p 205 (Contract
(1945), 355 NOrd 18471)

Kontinuierliche Verfahren. Continuous” methods, Koronit V. A Ger permissible Dynamite contg

such as those of Schmid, Meissner & Biazzi, NG 4, K chlorate 65, Na chloride 14, naph-
for the prepn and purification of expls and pro- thalene 10, MNN 5 & woodmeal 2% (Ref 1).
plnts, have been used extensively in Ger. According to Marshall (Ref 2), the name
Some of these methods will be described under Koronit was given in 1931 to CMoratit 1
Nitration in Vol 8 of Encycl (See Vol 2, p C209-L), which contains K and/or
 K 18

Na chlorate 70–80, Nitroderivatives of toluene the expls. For this reason, the Trauzl test
and/or naphthalene and/or diphenylamine 12– has been the subject of numerous investiga-
20, vegetable meal 1–5, solid hydrocarbons tions, principally by Kast, Selle, Neubner
and/or oils and fats 3–5 & NC (not gelatinized) (Refs 1,2 & 3), and at the US BurMines
2–6% (Ref 5)
Refs: 1) Naoi’im, Expls (1927), 147 In the course of these investigations, Neubner
2) Marshall 3 (1932), 112 3) PATR 2510 (Ref 3) found that better results are obtained
(1958), p Ger 102-R if, instead of firing a standard 10g charge, the
weights are varied until expansions between
250 and 325cc are obtained. The weight
Kostevich, Michael M. (1877–1957). A former (w) corresponding to a 300cc expansion is
Colonel of the Imperial Russian Guard Artillery calculated by interpolation. By dividing 300
and head of the Russian chemical warfare sec- by w and multiplying by 10, a value is obtained
tion during WWI. After the revolution he which is more representative than the old
worked in Engl, Fr and Belg. He built and Trauzl value. This new value is called the
directed a chemical laboratory for the Czech Kraftzahl or KZ of the expl. The following
Skoda works. From 1930-1936 he taught table compares these values with older Trauzl
chemistry at the Technical Institute in Paris. test values determined by various investigators
From 1937 he was chief of the research de- (Kast, Stettbacher, Zschokke, Will& Brunswig):
partment in the explosives plant at Villa
Trauzl Block Expansion (cc)
Maria, Argentina. Author of numerous publi- Explosive Old Value -u value “
cations on” ordnance and expls including books
entitled, “Trinitrobenzol and Trinitrotoluol” Nitromannite 650 675
and “Methods for Removing Explosives from’ Blasting Gelatin 520–61 O 554–575
Artillery Shells by Burning” NG 515–563 540–545
Refi A.A. Schrimpff, SS 32319 (1937) Nitropentaerythrite 460 500
Gelatin Dynamite (60%) 410 465–472
Tetranitroanisol 390 440
Kraft Dynamite. Patented by C.G. Bjorkmam Guhr Dynamite 350 419
at the end of the 19th century. It contained NC (13% N) 325-420. 400–426
NG 55.36, K chlorate 16.96, ‘K nitrate 15.18 Tetryl 340–350 405
& pulverized cork 12.50% TNB 330 386
Refl Daniel (1902), 396 Hexanitrodiphenylsulfide 325 380
Hexanitrodiphenylamine 320 376
Picric Acid 300–365 376-385
Kraft Paper. A strong, relatively inexpensive TNT 285–300 350–353
paper made primarily from pine by digestion Trinitrocresol 275 336
with a mxit of caustic soda,”Na carbonate, Dinitrobenzene 250 311
Na sulfate &’Na sulfide (Ref 3). It is used Nr-@e-baseProplnt 150 226
extensively in Dynamite cartridges (Ref 2) (13% NC)
and ‘in pyrotechnic flare and signal cases(Ref 1) Double-base Proplnt 150 226
Refs: 1) S:M. Kaye et al, “New Flare Case (40% NG)
Materials”, PATR 3215 (1 96$) 2) Blasters’ Lead Azide 115 165
Hdb (1969), 30–33 3) CondChemDict Mercuric Fulminate 110–150 226
(1971), 499-L Black Powder 30–112 95
Refs: 1) H. Kast, SS 15, 171 (1920)
2) H. Kast &H. SeHe, Gliickauf, 1927; 900
Kraftzahl (KZ or Strength Number). “It has 3) R. Neubner, SS 15, 3, 53–4, 82, 126,
been recognized for some time that erdarge- 162, 194 (1928) 4) Marshall 3 (i932),
ments in the lead block cavity, obtained in 143 5) N.A. Tolch & G. St.J. Perrott,
the Trauzl test (See Vol 1, pp XXV-XXVI), “The Trauzl Block Strength Test of Dyna-
are not exactly proportional to the power of mites”, US BurMines RI 3039 (1930)
6) Stettbacher (1948), 113
 K19

Kratites. Expls “containing Amm .Perchlorate, 25–5%. It could also contain up to 20% of
NC and NC in various proportions, based on added Amm oxalate, chlorate or sulfate.
requirements for strength, brisance, sensitivity, Other nitrated amines, such as those of toluene,
etc xylene or naphthalene, could be used in lieu
Rej3: 1) Daniel (1902), 396 .2) P~rez Ara of aniline
(1945), 219 Refl Daniel (1902), 397

Kreulen’s Aluminum Block. See Aluminum Kubin & Sierch. Patented in England in 1884
Block (of Kreulen) in Vol 1, p A145-L a safety expl consisting of a regular Dynamite
to which was added 20–50% of Amm chloride
or sulfate. This expl can be considered as an
K-Salz (Ger). See under Cyclonite in Vol early Wetterdynamite
3, p C611-L Rejl Daniel (1902), 398

KSG Powder. An older Brit 33-grain sporting Kumuliatwnyi Zariad (Shaped Charge). Mixts
smokeless powder which is no longer used containing Geksogen (RDX) or TEN (PETN)
Rejl Marshall 1 (1917), 327 with TNT or other expls or phlegmatizers
were used in Russ ~aped charges
Refi Gorst (1957), 95, 98 & 100
KS Powder. An older Brit 42-grain sporting
smokeless powder which is no longer used
Refi Marshall 1 (1917), 326 Kup Powder. A mixt containing Ba nitrate
80, sulfur 20%, plus charcoal
Refi Daniel (1902), 398
K3-Stoff (Ger). A ~highly dispersed silica,
prepd by a special process, used during WWII
in some “Tetan” expls Kurzschlusszunder. Ger short-circuit primers
Ref G. R6mer, “Reports on Explosives or igniters, such as the Schaffler, Reinecke
(Germany)”, PBL Rept No 85160 (1946), p 3 systems as well as the Eindrahtzunder (single
wire igniters) are described in the Ref
Refi Beyling-Drekopf (1936), pp 216–22
Ksilil (Russ, Xylite~ in Fr, Ksylit in Polish,
TNX). ‘A term given to commercial Trinitro-
xylene (TNX) which consists chiefly of the Kynarkite. An early permitted expl containing
t rinitro derivatives jof meta-, with some ortho- NG 25, woodmeal 35, Ba nitrate 3, K nitrate
and para-xylenes. It is a greyish-yellow sub- 28, Amm oxalate 5 & w 3.7%. BalPend value
stance prepd by the nitration of commercial for 40Z sample, 2.21” swing compared to 3.27”
xylene by mixed nitric-sulfuric acid. It is for Brit 60% Gelignite. Charge limit in gallery
insol in w. Ksilil i! slightly more. sensitive to test 2002
initiation, and about as sensitive to impact and Refs: 1) Barnett (1919), 135 2) Marshall,
bullet test as TNT; It was used in composite Diet (1920), 55–6
expls as a partial s~bstitute for TNT
Refi: 1) PATR 21,45 (1955), p Rus 1O-L
2) Gorst (1957), 100 3) Urbaiiski 1 (1964), Kynite. A Brit safety expl invented by A.T.
396 Cocking of Kynoch, Ltd: NG 25–27, Ba &
K nitrates 30–36, woodmeal & starch 40–43

Kubin Explosives.
I
IA
safety expl, patented in
& Na carbonate (added) 0.5%. To this could
be added 0.5 to 10% Amm oxalate
1893, containing AN 75–95 and Nitroaniline Refs: 1) Daniel (1902), 398 2) Marshall,
Diet (1920), 56
 K 20

Kynite, Condensed: Brit safety expl manufd greatly during the South African War of 1901,
by Kynoch, Ltd and packaged in a non water- when holders of its preferred stock received
proof parchment paper wrapper: NC 24–26, dividends equal to 7 times the price of the
starch’ 32.5 -35.0, woodmeal 2.5–3.5, Ba stock. At that time, the company manufd
nitrate 3 1.5–34.5 & Ca carbonate O to 0.5% Dynamite, Gelignite, NC, Kynite, Cordite &
Refs: 1) Daniel (1902), 398 2) Thorpe 2 Smokeless Pdr, as well as various munitions
(1917), 438 3) Marshall, Diet (1920), 56 Refi Daniel (1902), 309

Kynoch Gelignite. Gelignite manufd by {, Kynoch Smokeless Powder. One of the older
Kynoch, Ltd in England. It contained NC ‘ Brit 30-grain sporting powders. It contains
54:63, Collodion Cotton 3–5, K nitrate 26– NC 52.1, DNT 19.5, K nitrate 1.4, Ba nitrate
34 & woodmeal 6–9% 22.2, woodmeal 2.7, ash 0.9 & volatiles 1.2%.
Refi Daniel (1902), 340 Qc 807crd/g; gas vol 726 l/kg at STP
Refs: 1) Marshall 1 (1917), 327 2) Barnett
(1919), 86 3) Thorpe 4 (1949), 530
Kynoch Limited. A Brit expls company with
plants at Kynochtown (Essex) and Ferrybank
Arklow (Ireland). This company prospered KZ. See Kraftzahl in kis Vol
 -..
....... .. ..
 L1

L-Alloy. A Rus fusible expl consisting of 95% (alpha, beta, etc), or any other that is so shielded
TNT and 5% Trinitroxylene, mp 74°. It has an that me gamma radiation at the surface of the
expl power similar to that of TNT, aJthough it package does not exceed 10 milliroentgens per
differs from the latter in detong more readily 24 hours at any time during transport
due to the fact that during the cooling process For more detailed information, consult the
very fine TNT trysts are formed ICC Regulations (Ref 1) or Ref 2
Refs: 1) Ya.I. Leitman (according to A.G. Refs: 1) Agent T.C. Georges Tariff No 19,
Gorst), “Potokha i Vzryvchatyiye Veshchestva”, published by Interstate Commerce Commission
Oborongiz, Moskva (1949) 2) IJrbaiiski 3 Regulations for Transportation of Explosives
(1967), 248-49 and other Dangerous Articles by Land and
Water in Rail Freight Service and by Motor
Vehicle (Highway) and Water, including Spe-
Labels for Shipping Explosives and Other Dan- cifications. for Shipping Containers; issued 5
gerous Materials. US Interstate Commerce
The Aug 1966; available from T.C. George, 63
Commission Regulations specify that the fol- Vesey Street, New York, NY 10007 2) sax
lowing labels be provided when expls or other (1968), 308-62
dangerous materials are shipped or transported:
Flammable liquids: diamond-shaped label,
bright red in color, with each side measuring Labile Nitrocellulose (Knecht Compound).
4“. Printing must be in black letters inside of Knecht found that when cotton is immersed
a black line border, measuring 3.5” on each side in 60% nitric acid, it forms a “labile” nitrate
Fkrmmable solids and oxidizing materials: from which the nitric acid can be removed by
same shape, size and lettering as above, but washing with w. Using an acid with a d of
the color shall be bright yeHow 1.415, he obtained a cellulose with 35.8%
Corrosive liquids, alkalies or acids: same shape, absorbed acid, corresponding to C6HI 005 .HN03
size and lettering as above, but the label shall Refs: 1) E. Knecht, Ber 37, 549 (1904)
be white in color 2) Marshall 1 (1917), 151
Compressed gas: same shape, size and lettering NOTE: See Cellulose Nitrates in Vol 2 of
as above, but the color of the label, shall be Encycl, pp C 100-Lff
red for flammable gasesand bright green for
nonflammable gases
Poison (gas, liquid or solid) and tear gases: Lactic Acid Nitrate (Nitrolactic Acid),
same size and shape of label as above, but with CH3CH(ON02)COOH; mw 135.09, N 10.37%;
a white label with letters in red light yellowish oil mist with w, ale, eth & benz;
Explosives, propellant powders and special insol in ligroin. May be prepd from lactic acid
fireworks: rectangular white labels with red using Zn acetate in a mixt of fuming nitric
letters reading Explosives A or Explosives B and coned sulfuric acids. Decomps at RT, too
Radioactive materials (Groups I or II): diamond- unstable for use
shaped label, white in color, with each side Refs: 1) Beil 3, 279 2) A.H. Blatt & F.C.
measuring 4”. Printing is in red letters inside Whitmore, “A Literature Survey of Explosives”,
a red-line border. Group I materials are those OSRD 1085, 56 (1942)
which emit any gamma radiation, either alone
or with electrically charged particles or cor-
puscles (alpha, beta, etc). Group II materials LACTOSE AND DERIVATIVES
are those which emit neutrons and either or
both of the types of radiation characteristics Lactose (Milk Sugar), C~2H2201 ~.H20; mw
of Group I materials 360.31, monoclinic spheroidal trysts (from w),
Radioactive rnaterrizls (Group HI): same as Wp 201 –202° (becomes anhydr at 1200), bp
above except that the lettering and border line (dec), d 1.53g/cc at 20°. Present in the milk
are in blue. Group III materials are those which of mammals, and is produced cornniercially
emit electrically charged corpuscular rays only from whey, a by-product of the cheese industry.
 L2

It is hydrolyzed by dil mineral acids to glucose deton (4225 m/see as detd in 1.25” x 8“ car-
and galactose. Termansen (Ref 2) found that a tridges). Its sensitivity to impact is comparable
homogeneous mixt of lactose with 12.5% PETN to PETN, and it is fairly insensitive to friction
is not expl, however, lactose contg 12.5% Hexa- and insensitive to static electricity. The thermal
nitromannitol has expl props. Lactose yields stability of Nitrolactose is satisfactory; 65.5° KI
expls on nitration (See below) test – 28 minutes; loss on heating for 8 days
Refs: 1) Beil 31, 407 2) J.B. Termansen, at 50° – 0.7%; at 75° for 24 hours – 170; 54
ArchPharmChem 59, 713-41 (1952) &CA 47, hours – 23%; at 100° for 10 hours – 20% loss
319 (1953) 3) Merck (1968), 605 (Ref 7)
4) CondChemDict (1971), 502-L

Lactose Hexanitrate, Cl2H1605(ON02)6; a Lafaye Explosives. Lafaye patented in Fr in

white amorphous material with mp about, 70°, 1888, a method of prepg NC from pure wood
was isolated from the alc mother liquors k the cellulose, the resulting product being cheaper
crystn of the octanitrate (Ref 6). It is a less than NC obtained from cotton
powerful expl than the octa-compd Ref Daniel (1902), 400
Sj6berg, in 1888, patented expls contg mixts
of nitrolactose, nitromolasses and Na nitrate, as
well as admixts of the above with Amm nitrate, Laflin and Rand Powder Co. One of the fust
mphthalene and paraffin. These expls were expl manufg companies in the USA. Its fiist
unduly heat sensitive (Ref 2). Crater patented BlkPdr plant was erected near Orange, NJ in
the use of nitrolactose with materials such as 1808 (Ref 1). Another plant was built at
MF and K chlorate, or LA or DDNP in blasting Orange Mills, near Newburgh, NY, and a plant
cap charges (Ref 4), as well as its utilization at Pompton Lakes, NJ, manufd proplnt pdr
together with oxidizers such as Amm nitrate in for small arms. It consisted of Guncotton
blasting expls (Ref 5) 67.25, NG 30 and metallic salts 2.75%, glea-
Refs: 1) Beil 31, 418 la) W. Will & F. tinized with acetone. A dense shotgun pdr of
Lenze, Ber 31, 82 (1898) 2) Daniel (1902), similar compn was also made (Ref 2). The
558–59 3) A. Pictet &H. Vogel, CR 185, Pompton Lakes, NJ plant was purchased by
332 (1927) 4) W. deC. Crater, USP 1759565 dupont and expls including initiators, such as
(1930) &CA 24,3649 (1930) 5) W. deC. MF, LA, blasting caps, etc were manufd there
Crater, USP 1945344 (1934) &CA 28, 2538 Refs: 1) Daniel (1902), 400 2) Marshall,
(1934) 6) Davis (1943), 242 7) Blatt Diet (1920), 56 3) VanGelder & Schlatter
OSRD 2014 (1944) (1927), 98

Lactose Octanitrate (Nitrolactose),

C~*H~~O~(ONOz)*; mw 702.31, N 15.96%, Lake’s Explosives. Mining expls patented in
OB to C02 –9.1%, white monoclinic needles Engl in 1894. Typical formulations included:
(from methanal), mp 145–46° (dec), bp (ig- 1) Na nitrate 76, nitronaphthalene 8 & nitro-
nites at 246-480), d 1.684g/cc; insol in w, sol phenol 16%
in acet, methanol and AcOH; d sol in cold ale, 2) Na nitrate 58, nitromphthalene 8 & nitro-
sol in hot; reduces Fehling’s soln on warming phenol 34% .
May be prepd by stirring lactose with mixed 3) Na nitrate 74, nitrophenol 10, sulfur 8,
nitric-sulfuric acids until the mass forms a charcoal 4 & rosin 4%
solid agglomerate [1p lactose in 15p acid, con- Ref Daniel (1902), 401
sisting of 1 vol nitric (d 1.5) and 2 vols coned
sulfuric]. The mixt is transferred to ice w
and pulverized under w. The product may be Lambotte Explosives. Complicated mixts of
purified by crystn from alc (Ref 1) nitroglucose, sawdust, Pb oxide, Ba sulfate, etc
Nitrolactose is comparable in brisance (sand Refl Daniel (1902), 401
crush test) to Tetryl, but has a lower vel of
 L3

Laminac 4116. A binder and adhesive most between warm rollers. In the resulting “lami-
often specified for use in pyrotechnic flares nated” product, the outer layers burned rela-
and signals. It is a proprietary product manufd tively slowly with a temp of about 1500°,
by the American Cyanamid Co, and belongs to while the inner slab burned rapidly with a
the class of thermosetting alkyd-styrene resins temp of about 3000°. Similar proplnts were
more commonly called unsaturated polyesters prepd during WWH
(with added styrene). Since the liq resin is re- Ref Davis (1943), 318
latively low in viscosity, it can be added to
solid powds without any volatile solvent. For
activation, 1–2Y0 of methyl ethyl ketone per- Lamm Explosives. Lamm patented, in 1888 in
oxide (tradename Lupersol DDM) is mixed Fr, the use of waxes, such as carnauba, as
with the resin. This “catalyst”, actually a coating agents for hydroscopic ingredients of
curing agent that reacts”chemically, converts . expls. He also proposed several expl mixts
the resin first into the gel state, then in strongly contg DNB in combination with K or Amm
exothermic reaction into a hard solid. The re- nitrates
action is accelerated by the promoting agent Refi Daniel (1902), 401
Co naphthenate (tradename Nuodex). Laminac
is usually admixed as 4–9% of the formula wt
Refs: 1) D. Anderson & E. Freeman, “The LaMotte’s Explosive. DNN 7p and TNT 5p
Kinetics of Thermal Degradation of the Syn- were fused together and mixed with 88p of
thetic Styrenated Polyester, Laminac 4116”, Amm nitrate. After the mixt cooled, 2p of
JApplPolymerSci .1,192 (1959) 2) D. pyrites were added
Anderson & E. Freeman, “Characterization of Rejl E. LaMotte, USP 911019 (1909) & CA
Saturated Polyesters by Differential Thermal 3, 1088 (1909); BritP 7921 (1908) & CA 3,
Analysis”, AnalChem 31, 1697 (1959) 2382 (1909)
3) V. Hogan & S. Gordon, “Pre-ignition and
Ignition Reactions of the Propagatively Reacting
System Magnesium-Sodium Nitrate-Laminac’!, Lance Missile (XMGM-52A). US surface-to-
Combstn&Flame 3 No 1, 3–12 (1959) surface missile weighing approx 2814 Ibs with a
4) EngrDesHdbk, “Milita~ Pyrotechnics Series, 30 mile range. It is launched from a con-
Part Three – Properties of Materials Used in verted M113 armored personnel carrier chassis,
Pyrotechnic Compositions”, AMCP 706-187 and is intended as a divisional support weapon.
(Ott 1963), 157-58 5) G. Weingarten, As such it will replace the Honest John and
“Polymerized Laminac Resin 4116 – Heats of Sergeant rockets. It is powered by a storable
Formation and Combustion, and Carbon, Hy- liq fuel rocket motor and guided by a simple
drogen, Oxygen Content”, PATR 3032 (1963) inertial system. It has a small nuclear warhead,
but other types are also available. An extended
range Lance is under development with a
Laminated Powders. Progressive burning pro- 50–60 mile range. The Sea Lance XMGM-52B
plnts originated by the Fr during WWI and used is a marine conversion for firing from a gyro-
in large caliber guns. One of these powds was scopically stabilized launcher
prepd as follows: A quantity of Ballistite, Refs: 1) E. Luttwak, “A” Dictionary of Modem
prepd by mixing 50p of NC with 50p of NC War”, Harper & Row (1971), 120 2) F.O.
(12% N), was rolled between heated rollers DuPre, Ordn 57, 271-L (Jan-Feb 1973)
until a sheet of desired thickness was obtained. 3) Anon, Ordn 57, 501-R (May-June 1973)
tiother portion, consisting of 50p of DNT
and 50p of NC (12% N), was rolled to form a
sheet thinner than the previous one. A strip Land. One of the raised ridges in the bore of
of the first mixt was sandwiched between two a rifled gun barrel.
strips of the second mixt, and the ensemble Note: The caliber of small-arms ammo, except
combined into a laminated product by pressing for shotgun ammo, is expressed as the diameter
 L4

of the bore of the weapon in inches. Thus, Lanthanum Triazide. See in Vol 1 of Encycl,
calliber .30 ammo is intended for a weapon p A554-R
having a bore of 0.30 inch diameter across the
lands and, although the outside diameter of the
bullet is a few thousandths of an inch greater Laser, Application to Explosives and Weapons
than the bore diameter, it is customary to speak Technology. A device used for the amplification
of this ammo as caliber .30. The same is applied or generation of coherent light waves, the term
to the bore of the gun Lzserbeing an acronym for light amplification
Refs: 1) Ohart (1946), 64 & 98 2) Ord- by stimulated emission of radiation. Unlike
TechTerm (1962), 172-R the waves emitted by an ordinary light source,
such as an electric lamp, the laser produces a
light beam that does not diffuse. Moreover, a
Landauer Explosives. Fr expls, patented in laser organizes the energy waves emitted by a
1891, in which chlorates and perchlorates are stimulated atom so that they travel in the same
desensitized by coating them with fatty ma- direction, at the same frequency, and perfectly
terials, tar or nitrated hydrocarbons. Follow- in step with the stimulating radiation. This
ing are some expl mixts proposed by Landauer: property is known as coherence. A laser thus
1) K chlorate 48.8, tar 24.4, DNN 24.4 & produces a very narrow band of frequencies
sulfur 2.4%; 2) K chlorate 20, tar 20, NC 40 similar to that of a radio oscillator, but in the
& coconut oil 20%o;3) K chlorate, 22.2, tar infrared and visible-light portions of the spec-
55.6 & NG 22.2%; 4) K perchlorate 3, tar 1, trum (Ref 15)
DDN 10, NC6, NG 75 & sawdust 5%; 5) K The highly parallel, intense beam of coherent
perchlorate 2.0, tar 18.4, DNN 4.0, K nitrate radiation emtited by the laser has found a
42.9 & Amm nitrate 32.7% multitude of important applications in the
Refi Daniel (1902), 402–403 military area. These range from anti-missile
applications, communications, surveillance,
range finding (ground and airborne), tracking
Land Mines. See Mines (Military) in Vol 8 (ground, sea, air), weather reconnaissance,
of Encycl metal working, nondestructive measurement,
defensive and offensive weaponry, to field
surgery (Refs 1, 16, 27 & 29)
Landsdorf Dynamite. Dynamite contg NG 75, Picatinny Arsenal adapted the laser for remote,
kieselguhr 20 & Amm urate 5% wireless initiation of thermal batteries and other
Refs: 1) Daniel (1902), 403 2) Fedoroff devices contg expls, proplnts and pyrotechnics
& Clift 4, 51 (1946) in expts to demonstrate the feasibility of using
a thin beam of infrared radiation in lieu of a
method requiring wires. The wires, which can
Landsdorf Powder. BlkPdr type compn contg act as an antenna to the detriment of the de-
K nitrate 73, Amm urate 9, charcord 9 & vice contg ~em, were removed and replaced
sulfur 9 by a thin transparent window to provide an
Ref: Daniel (1902), 403 optical path between the laser beam and the
reactive material to be initiated. Reportedly
offering a savings in the cost of thermal bat-
Landskrona Powder. Swiss proplnt, invented teries and squibs, the method also contributes
by E. Schenker before 1890 and manufd in to increased safety in environments which could
Landskrona, Sweden. It was made by gela- cause undesired ignition. The laser beam, pro-
tinizing pure NC with amyl acetate, and was grammed to deliver a series of pulses as required,
used by the Swiss and Danish armed forces can be directed thru the air on a line-of-sight
Re~ L. Gody, “Traite des Mati?res Explosives”, path or thru a maze of fiber optics in any di-
Namur (1902), 641 rection dictated by the geometry of the equip-
 L5

ment used. Upon striking the expl material, observer, either on the ground or in an aircraft,
the pulse excites electronic and vibrational trains a laser beam on a target. A laser-seeker
energy levels, causing it to ignite (Ref 3) in the nose of the artillery shell, which is fired
A laser-initiated pyrotechnic system (Zr- in the general vicinity of the target, picks up
Amm perchlorate) for spacecraft application the laser spot on the target. On the basis of
has been shown to be superior to conventional information received from the laser-seeker, a
electroexpl initiation (Ref 22). Primary high guidance system sends out course directions to
expls such as LA and LSt can be initiated di. fins that deploy after the shell leaves the gun
rectly. Q-switched-mode lasers can directly barrel. The fins then change the course of
deton PETN, RDX, and Tetryl in a properly de- the shell so it will hit the target
signed device and can be useful where micro- On the basis of test firings, accuracies on
second simultaneity is important (Ref 6) the order of 1–3 ft at any range can be ob-
A “hardened” laser optic system that resists tained with this shell, compared with a probable
X-rays was developed by Space Ordnance error of 45–60 ft with conventional 155mm
Systems, Inc, to assist missiles in reaching ammo. The shell can be used in the 155mm
their target. The system can withstand very howitzer with no modifications to the artillery
hi~ temps and the tremendous bursts of X- piece
rays from high altitude thermonuclear explosions Another area of laser use applied to expl
which may be used to destroy incoming ballistic materials involves its employment to excite
missile warheads. The X-rays would be re- Raman spectra for studies of crystal structure,
leased by defensive missiles fired in the general lattice dynamics, phase transitions and vibra-
vicinity of incoming weapons. Called LE ED, tional mode frequencies. Compds studied in-
an acronym for laser energized explosive device, clude T1N3 (Refs 10, 17 & 23), NaN3 (Ref 18),
the system was developed to end the danger of KN3 and RbN3 (Ref 4), NH4N3 (Ref 7), BaN3
premature expln or failure of proplnts or pyro- (Refs 5,8& 24), LA (Ref 9), HMX (Ref 25),
technics in the presence of radiofrequency, RDX (Ref 11) and Amm perchlorate (Ref 26)
electrostatic energy, X-rays, or dense electron In the course of an investigation to provide
fields. If, while still in their high-energy state, bright light sources of min volume and weight,
the X-rays released from a nuclear expl impact a search was conducted for new sources of
upon a warhead, they are quickly stopped and chemically generated light. Chemical systems
their electromagnetic energy is converted into were investigated in a flash photolysis laser
heat energy. The resulting surge of energy apparatus in order to discover new output
might shatter the outer casing of the warhead wave lengths and new molecules which produce
and create a shock wave that could damage the lasing (Ref 12)
interior mechanisms. LEED, constructed of The principle of using the products and energy
low ‘Z” materials, utilizes a laser energy pulse from an expl detonation to produce a popula-
tran:;mitted along nonmetallic, fiber optic con- tion inversion suitable for lasing has been studied.
ductors instead of conventional connecting me- The design of a 175mm disposable laser deto-
tallic electrical cables, bridgewires, and spark nation cartridge (LDC) was explored, and it
gaps such as those used in interior warhead was predicted that the energy stored in 30
mechanisms (Ref 2) grams of expl can be converted into a 60
The US Army (Ref 29) successfully tested kilojoule laser pulse with a one millisec pulse
a laser-guided artillery shell that could revolu- duration. A program is outlined to construct
tionize the role of artillery on the battlefield. a prototype LDC and to measure its perfor-
With the new shell, whose course can be mance (Ref 19)
changed in flight to bring it down on a target Lasers have also been employed to study
with high accuracy, artillery would have, for fast chemical reactions, those taking place in
the first time, a capability of attacking moving the time domain of a few billionths of a second.
targets, such as tanks Capellos et al at PicArsn, have employed Q-
The guided projectile homes in on a target switched Ruby and neodynium lasers, which
in the following manner. A forward artillery provide an intense pulse of monochromatic

I
 L6

light of 347 and 265nm, respectively, with (1973) 22) L.C. Yang et al, National De-
time durations of the order of 12 nanoseconds. fense 58, 344–47 (1974) 23) C. Christoe
The ultra-violet light induces electromagnetic & Z. Iqbal, Solid State Comm 15, 859 (1974)
excitation in molecules absorbing the laser 24) Z. Iqbal, JChemPhys 61, 1230 (1974)
energy, and by subsequently applying the 25) Z. Iqbal et al, JChemPhys 60,221 (1974)
principle of absorption spectroscopy, kinetic 26) H. Prask et al, ProcArmySciConf (1974)
and spectroscopic information relating to the 27) Anon, National Defense, Vol LIX, No 327
electronically excited states of various energetic (Nov-Dec 1974), 195,243 & 257 28) C.
molecules have been derived. The systems Capellos & G. Porter, JCS 70, FaradayTransII,
studied to-date include s-TNB, s-TNT, triphenyl- 1159–64 (1974) 29) J.W. Finney, “Artillery
amine, and mono- as well as di-nitronaphthalenes Shell Guided by Laser”, The New York Times
(Ref 13, 14,20,21 & 28) (Jan 29, 1975), 1 & 17
Written by S. M. KAYE

Refs: 1) D. Fishlock, Ed, “A Guide to the Laser”, Latent Heats of Fusion, Vaporization. See
MacDonald, London (1967), 68–84 (The Laser under Heat, Latent in this Vol of Encycl, p
on the Battlefield) 2) Anon, Ordn 52, 298 H58-R
(Nov-Dec 1967) 3) Expls&Pyrots 3, No 10
(1970), 2 4) Z. Iqbal, JChemPhys 53, 3763
(1970) 5) Z. Iqbal, C.W. Brown & S.S. Launchers. See Vol 2 of Encycl, p C28-R
Mitra, JChemPhys 52,4867 (1970) 6) L.C. (Rocket Launcher) and Vol 6 (1974), p G139-R
Yang & V.J. Menichelli, ApplPhysLet 19, (Grenade Launcher) & G185 (Guided Missile
473–75 (1971) 7) Z. Iqbal & M.L. Malhotra, Launcher)
SpectrochimActa 27A, 441 (1971) ..8) Z.
Iqbrd & M.L. Malhotra, JChemPhys 55, 528
(1971) 9) Z. Iqbal, W. Garret, C.W. Brown Launoy Powder. A mixt of Na nitrate, sawdust,
& S.S. Mitra, JChemPhys 55,4528 (1971) nitrated bran and sulfur
10) Z. Iqbal & M.L. Malhotra, JChemPhys Refi Daniel (1902), 423
57, 2637 (1 972) 11) Z. Iqbal et al, PATR
4401 (1972) 12) M.Y. DeWolf Lanzerotti,
“Chemical Laser’ Research”, PATR 4354 (1972) Lava Fire Bomb. USA incendiary bomb de-
13) C. Capellos & K. Suryanarayanan, “Micro- veloped during WWII, designated as M74. It
second Flash Photolysis of 1,3,5-Trinitrobenzene weighs 10 lbs and consists of a hexagonal pipe
Solutions and Product Formation with 254nm 19“ long, inside of which is a plastic cup fdled
Steady State Illumination”, PATR 4342 (1972) with “synthetic lava” consisting of GOOP (Mg
14) K. Suryanarayanan & C. Capellos, “Flash pdr coated with asphalt particles), white P and
Photolysis of 2,4,6-Trinitrotoluene Solutions”, other ingredients. When clusters of these bombs
PATR 4407 (1972) 15) Encycl Britannica are impacted on targets, their burning contents
13, 733–34 (1973) 16) L. Goldman, flow much like volcanic lava .
“Applications of the Laser”, CRC Press, Cleve- Rej Anon, ArmyOrdn 29, 208 (1945)
land, Ohio (1973), 121 –26 (Lasers in the Mili-
tary) 17) Z. Iqbal, “Advances in Raman
Spectroscopy”, Heyden, London, Chapt 23 Lavoisier, A. L. (1 743–1 794). Fr Chemist,
(1973) 18) Z. Iqbrd, JChemPhys 59, 1769 regarded as the father of modern chemistry by
(1973) 19) J. Hershkowitz & M.Y. DeWolf virtue of his study of combstn and the role of
Lanzerotti, “Preliminary Design Study For An oxygen. He formulated the theory of the con-
Explosive Product Laser”, PATR 4465 (1973) servation of matter, and laid the basis for che-
20) C. Capellos, “Nanosecond Flash Photolysis mical nomenclature. From 1775 to 1791 he
of Triphenylamine Solutions”, PATR 4439, was in charge of expl manufg in Fr (“Regisseur
(1973) 21) C. Capellos & K. Suryanarayanan, des Poudres”). He was unjustly accused and
“A Ruby Laser Nanosecond Flash Photolysis executed during the Fr revolution
System, 1,4-Dinitronaphthrdene”, PATR 4445 Ref Hackh’s (1944), 481-R; (1969), 381-R
 L7

LAW. Acronym for light assault weapon. The Lead Aceto-Bromate. See in Vol 1 of Encycl,
USA M72 66mm anti-tank rocket-launcher p A29–1
weighs 4.5 lbs with one unguided rocket, and
has a range of 500–600 yds. The disposable
launcher-rocket package is 25” long and ex- Lead Aceto-Chlorate. See in Vol 1 of Encycl,
tends to 34” for firing p A29-L
Rejl E. Luttwak, “A Dictionary of Modern
War”, Harper & Row (1971), 40–41 & 120
Lead Aceto-Perchlorate. See in Vol 1 of Encycl,
p A29-L
Lead (Plumbuml Pb. at wt 207.19. bluikh-
white: silvery, g~ay m~talj mp 327.4°, bp 1740°,
d 11.34 at 20°/40, d at mp 10.65. Highly lus- Lead Aceto-Sodium Perchlorate. See in Vol
trous when freshly cut, tarnishes upon exposure 1 of Encycl, p A29-L
to air; very soft and malleable, easily melted,
cast, rolled and extruded. Occurs chiefly as
sulfide in galem (86.8% Pb), also as carbonate Lead Acetylide. See in Vol 1 of Encycl, p
in cerussite (77.570 Pb) and as sulfate in angle- A76-R
site (68.3% Pb). May be prepd by roasting and
reducing Pb ores. Sol in hot coned nitric acid,
in boiling coned HC1 or sulfuric acid, in acet ac. Lead-Antimony (For Use in Ammunition).
Attacked by pure w, weak organic acids in the Material used by the USA Armed Forces for
presence of O. Resistant to tap w, HF, brine the manuf of bullet cores, base ftiers and point
& solvents (Ref 2) fflers. Three grades are covered in specification
Its general uses as a metal are innumerable MI L-L-13283B (MR) (19 Aug 1970) with the
(Ref 2). In the manuf of expls it is used, in following compn requirements:
either pure or alloy form, in many types of Grade 1 Grade 2 Grade 3
equipment such as nitrators, drying pans, Lead + antimony, 99.2 99.2 99.2
bearing metal, pipes, tanks, etc. In ammo, %, min
it is used as the core of bullets,j shrapnel balls Antimony, % 1.0–2.5 9.0–10.5 9.0–9.1
and shot, and for the prepn of oxides and srdts Copper, %, max 0.10 0.10 0.10
used in expl and pyrotechnic mixts
One of the most recent uses for Pb is the The material shall be” clean and of uniform
addition, in the form of foil or coil of wire, to compn, and shall be free from segregations, dross,
proplnt pdr as a decoppering agent for the bore oxides, blow holes, hard spots, foreign material
of the gun. The Pb is placed between the pro- and other injurious defects. The material shall
plnt charge and the projectile be furnished in commercial cylindrical ingots
Pb is highly toxic by inhalation of dust or of spectiled dimensions
fumes. Tolerances 0.2mg/cc in air. A cumula- Refs: 1) Gmelin, Syst Nr 47, Teil.3 (1970),
tive poison, FDA regulations require zero Pb 905ff 2) Spec, “Lead-Antimony” (For Use
content in foods (Refs 3 & 4) in Ammunition), MlL-L.13283(MR) (1 9 Aug
Refs: 1) Gmelin, Syst Nr 47, Teil C, Lfg 1 1970)
(1969), lffi Teil Al (1973), 6ff 2) E.J.
Mullarkey, IEC 49, 1607 (1957) 3) Merck
(1968), 611-R 4) Sax (1968), 863 5) Cond- Lead Azide. See in Encycl, Vol 1, A545–A587
ChemDict (1971), 507-R Addnl Refs: 1) B. Reitzner, “Influence of
Silver Coatings on Ignition Behavior of Col-
loidal Lead Azide”, PATR FR L-TR2 (1960),
Lead Acetates. See in Vol 1 of Encycl, pp PB148915 2) B. Reitzner, “Influence of
A28–29 Water on Thermal Decomposition of Alpha
 L8

Lead Azide”, PATR FR L-TR5 (1960), PB- Lead Bromate (Monohydrate). Pb(Br03)2 .H20;
148916 3) J.I. Bryant & M.D. Kemp, mw 481.06, colorless trysts, mp (decomp at
AnalChem 32, 758–60 (1960) (Polarographic 1800), d 5.53g/cc; S1sol in cold w, moderately
analysis) 4) B. Reitzner, J.V.R. Kaufman & in hot w. Poisonous~ Pure Pb bromate is not
E.F. Bartell, JPhysChem 66,421 –26 (1962) dangerous, but when prepd by the action of Pb
[Decompn of alpha LA] 5) H.W. Voight acetate on an alkali bromate, the unstable
Jr & F.H. Schmitt, PATM 1673 (1965) (Low- diaceto-diplumbo-bromate is always present.
impulse LA fdm to be used in applications This complex explodes violently on heating,
calling for light-initiated plane wave explosives) striking or rubbing
6) Spec, “Lead Azide (Special Purpose, For Refs: 1) Gmelin, Syst Nr 47, Teil C2 (1 969),
Use in Ammunition)”, Ml L-L-14758 (1 O May 374ff la) E. Giizel & E. Marcus, ZAng-
1968) 7) Anon, “Lead Azide RD-1333”, Chem 38, 929 (1925) 2) I. Victor, ZAng-
US Spec Ml L- L-46225C (26 Aug 1968) Chem 40, 841 (1927) &CA 21, 3324 (1927)
8) P.G. Fox, J.M. Jenkins & G.W.C. Taylor, 3) Anon, Chem&Ind 46, 690 (1927) & CA
“Spontaneous Explosions in Lead Azide Solu- 21, 3170 (1927) 4) Merck (1968), 61 2-R
tions”, Explosivst 17, No 8, 181–84 (Aug 1969) 5) Sax (1968), 864-L 6) CondChemDict
9) G. Cohn, Ed, Expls&Pyrots 3 (3) (1970) (1971), 508-R
(Scanning electron microscopic examination of
pure, dextrinated and RD 1333 LA) 10) L.
Avrami & N. Palmer, “Impact Sensitivity of Lead Carbonate. See in Encycl 2 (1962), C59-L
Lead Azide in Various Liquids with Different
Degrees of Confinement”, PATR 3965 (1969)
11) M.F. Zimmer & L.D. Lyston, “Dynamic Lead Carbonate, Basic. See in Encycl 2 (1962),
Pressure Measurements on Small Amounts of C59-L
Detonating Lead Azide”, Explosivst 18, No 1,
12–15 (Jan 1970) 12) R.W. Hutchinson,
S. Kleinberg & F.P. Stein, “Effect of Particle- Lead Chlorate (Normal). See in Encycl 2 (1962),
Size Distribution on the Thermal Decomposition C188-R
of c+Lead Azide”, JPhysChem 77, No 7, 870–
875 (1973) 13) Director, Explosives Re-
search and Development Establishment, Waltham Lead Chlorate (Basic). See in Encycl 2(1962),
Abbey, Essex, England [Abstract reported by C 189-L
G. Cohn, Ed, Expls&Pyrots 7 (4) (1974); New
Lead Azide compns RD 1343 & RD 1352]
Lead Chlorite. See in Encycl 3 (1966), C245-R

Lead Azidodithiocarbonate. See in Vol 1 of

Encycl, p A637-L Lead Chromate. See in Encycl 3 (1966), C280-L

Lead Bichromate. See Lead Bichromate in Lead Dichromate. See in Encycl 3 (1966),
Vol 3 of Encycl, C284-R C284-R

Lead Block Compression Test. See under Lead 2,4-Dinitroresorcinate (LDNR). See in
Compression (or Crusher) Tests for Determina- Encycl 5 (1972), D1274-R
tion of Brisance in Vol 3 of Encycl, C492-L
to C493-L
Lead 4,6-Dinitroresorcinate, Basic. See in
Encycl 5 (1972), D1275-R
Lead Block Expansion Test. See under Trauzl
Test in Vol 1 of Encycl, XXV–XXVI
 L9

Lead Hydroxide-2,4,6-Trinitroresorcinate. See rubbed with sulfur or red phosphorus, the mass
in Encycl 5 (1972), D 1277-L ignites. It is used with amorph P as an igni-
tion surface for matches, and in pyrotechnic
applications (Ref 5). Anderson, in 1908, pro-
Lead Imide. See in Encycl 1 (1960), Al 69-L posed its use as an additive to expls to increase
their power; for example 1) PA 40 & Pb02
60%; 2) PA 20, TNT 10, Guncotton 15, NG
Lead Mononitroresorcinate. See in Encycl 5 10 & Pb02 45%. Colver (Ref 1a) had consi-
(1972), D1271-L derable doubt as to the safety of mixts of this
type. McNutt (Ref 2) proposed using Pb02
in primer mixts, for example, Pb02 25, Pb
Lead Nitrate. See under Nitrates in VO1 8 of dinitrophenolazide 15, Ba nitrate 30, Sb tri-
Encycl sulfide 18, Ca silicide 6 & TNR 6%
The USA military specification (Ref 6)
details the following requirements for Type I
Lead Nitroaminoguanidine. See ti VO1 1 of (low alkalinity), Type II (high alkalinity),
Encycl, p A2 12-R Class 1 (subsieve) and class 2 (100 mesh,
nominal) Pb02
Composition
LEAD OXIDES
Lead Oxide, Yellow, (Lead Monoxide,
or Litharge
Type I Type 11
Lead Protoxide or Plumbous Oxide). PbO, mw Lead dioxide, rein, % 95.0 95.0
223.21, yellow to yellowish-red, heavy, odorless Water-soluble salts, max, % 0.05 0.05
pdr or minute, tryst scales; mp 888°, bp (vol Acidity None None
at red heat); d 9.53g/cc; insol in w, ale; sol in Alkalinity as Na2 C03, max, % 0.01 0.10
acet ac, dil nitric acid, in warm solns of fixed Ammonium salts None None
alkali hydroxides. It may be prepd in the lab by
heating Pb nitrate, carbonate or hydroxide; Particle Size Distribution
commercially, it is made by heating Pb to a
Percent Maximum Class 1 Class 2
temp considerably above its mp and continually
skimming off the litharge produced. It is used Retained on a No 100(149 micron) sieve – 0.1
in some primer compns Retained on a No 140(105 micron) sieve – 10.0
Litharge is toxic as a dust. Wear dust mask, Retained on a No 200 (74 micron) sieve 0.0 –
and wash thoroughly before eating or smoking. Retained on a No 325 (44 micron) sieve 5.0 –
Keep away from feed or food products Larger than 20 microns 20.0 –
Refs: 1) Gmelin, Syst Nr 47, Teil C, Lfg 1 Smaller than 5 microns 15.0 –
(1969), 5 lff la) Mellor (1946), 705
2) EngDesHdbk, “Properties of Materials Used Refs: 1) Gmelin, Syst Nr 47, Teil C, Lfg 1
in Pyrotechnic Compositions”, AMCP 706-187 (1969), 147ff la) Colver (1918), 324
(Ott 1963), 161-65 3) Merck (1968), 2) J.D. McNutt, USP 1906394 (1933), USP
613-R 4) Sax (1968), 865–6 5) Cond- 1930653 (1933), USP 2009556 (1935)
ChemDict (1971), 51O-R 3) EngDesHdbk, “Properties of Materials Used
In pyrotechnic Compositions”, AMCP 706-187
Lead Oxide, Brown or Lead Dioxide (Lead (Ott 1963), 169-70 4) Merck (1968),
Superoxide or Peroxide). Pb02, mw 239.21, 613-L 5) Ellern (1968), 51,60, 246, 280
dark brown tetragonal trysts, mp (dec to PbO 6) Anon, “Lead Dioxide, Technical”, Ml L-L-
and 02 at 290~, d 9.38g/cc. May be prepd 376B (Feb 1968) 7) Saks (1968), 865–66
from Pb acetate and Ca hypochlorite. Insol 8) CondChemDict (1971), 509-L
in w and alc; sol in acet ac and hot alk
It is an extremely strong oxidizing agent, Lead Oxide or Lead Tetroxide (Minium, Red
so care must be taken in mixing or storing Lead, Mineral Orange, Mineral Red, Ph.smbo,
with comb materials. When Pb02 is gently Puce, Orthoplumbate, Paris or Saturn Red).
 L 10

Pb304, mw 685.63, bright red scales or arnorph salt was found suitable. He also prepd and
pdr, mp (dec betw 500–300), d 8.32 to 9.16 studied the expl props of Pb Trinitro-N-methyl-
g/cc; insol in w and ale, sol in acet ac and hot nitrarnine Resorcinate & Phenolate, and Pb
HC1. May be prepd by carefully heating un- Trinitrobenzoate for possible use as deton
fused litharge at 470–80° for several hours in agents. AU were unsatisfactory
a current of air. The hot pdr acquires a deeper Ref J.D. Hopper, “Study of Lead Salts of
tint, becoming violet and then black. On Nitrocompounds as Substitutes for Mercury
cooling, the color changes to red. Used as an Fulminate”, PATR 480 (1934)
oxidizer in pyrotechnics and as an ingredient
in some expls, eg, in the Austrian expl “Lederite”
to the extent of 20% Lead-Shot Metal. An alloy of Pb and As.
The USA military specification (Ref 3) The As content may range from 0.3 to 0.8%
contains the following chemical requirements: and may be added either in the form of white
As or arsenical dross. The As imparts a greater
fluidity to the metal and increases its tendency
% by Weight
to assume a spherical shape in passing thru the
Minimum Maximum
air when dropped from the top of a Pb shot
Assay as Pb304 98.0 – tower hito cold w. About 0.025% Na sulfide
Insoluble matter in nitric acid – 0.10 is added to the w in order to prevent oxida-
Water-soluble substances — 0.05 tion of the shot
Carbon compounds (as C) – 0.010 Rej CondChemDict (1950), 393-R; not found
Manganese (Mn) — 0.0005 in later editions
Lead oxide is highly toxic as a dust. Use
with adequate ventilation, and keep away from
food and food products Lead-Sodium Thiosulfate. (Lead-sodium ~
Refs: 1) Gmelin, Syst Nr .47, Teil C, Lfg 1 Hyposulfite, Sodium-lead Trithiosulfate).
(1969), 122ff la) EngDesHdbk, “Properties Na@b(h ,03)3, mw 635.59, white, small,
of Materials Used In Pyrotechnic Compositions”, heavy trysts, mp (dec at 30-400); sparingly
AMCP 70&187 (Ott 1963), 166–68 2) sol in w; readily sol in Na acetate or Na thio-
Ellern (1968), 197 3) Anon, “Lead Oxide, sr.dfate solns. May be prepd (Ref 1) by mixing
Red, Analyzed Reagent”, Ml L-L-51336 (Nov solns of Na thiosulfate and Pb acetate, fol-
1969) 4) Sax (1968), 865–66 5) Cond- lowed by alc addition. On concg the soln,
ChemDict (1971), 51 O-R the liq separates into two layers. The bottom
layer is removed and treated with more ale,
whereupon the mixt solidifies to a white, amorph,
Lead Perchlorate. See under Perchlorates gelatinous mass of variable compn. On diln,
the arnorph mass turns tryst, which on drying,
corresponds to the above formula. It is used
Lead Picrate. See under Picrates in the prepn of matches. Poisonous\
Refs: 1) Mellor 10 (1934), 551 2) Merck
(1968), 614-L 3) Ellern (1968), 76 & 78
Lead Plate Test for Detonators. See undel 4) Sax (1968), 865–66 5) CondChemDict
Plate Tests for Explosives (1971), 511-R

Lead Salts of Nitrocompounds. Hopper (Ref), Lead Stearate. See under Stearates
at PicArsn, prepd and characterized Pb dinitro-
resorcinate, Pb dinitrophenolate, and Pb di-
nitrophthalate as possible substitutes for MF Lead Styphnate. (Lead 2,4,6- Trinitroresorcinate).
in priming compns. Only the dinitroresorcinate See Encycl 5, D1277-Lff
 L11

Lead Styphnate, Basic. (Lead Hydroxide Lead Trinitroresorcinates. See under Trirsitro-
Styphnate, Hydroxide-2,4,6 -Trinitro-
Lead derivatives of Dihydroxybenzene in Vol 5
resorcinate). See Encyc15, D1277-L of Encycl, pp DI 277-Lff

Lead Sulfocyante. See Lead Thiocyanate Leaking Gun. Brit for recoilless gun. See
Encycl 2, (1962), C28-R
Refi J. Corner, “Theory of the Interior Bal-
Lead Tetraethyl (Tetraethyl lead, Lead Tetra- listics of Guns”, Wiley, NY (1950), 243
ethide, Tetraethyl Plumbane). Pb(C2H5 )4,
mw 323.45, colorless liq, fr p –1 36°, bp
about 200°, also stated as 227.7° with decompn, Lecithin. A mixt of the diglycerides of stearic,
d 1.653g/cc at 20°; insol in w; S1sol in ale, palmitic and oleic to the choline
acids, linked
sol in benz and eth. May be prepd by the ester of phosphoric acid. Yellowish-white,
action of Pb chloride on Zn ethyl or on a waxy mass, obtained either from eggyolk or
Grignard reag. Used extensively as an anti- soybeans. Insol in w; sol in ale, chlf and eth.
knock addition to gasoline, and has been pro- Lecithin was used in Composition C (RDX
posed by Fr investigators as a flash reducer 88.3, nonexpl oily plasticizer 11.1 & lecithin
in proplnts (Ref 2) 0.6%) to help prevent the formation of large
ReJ3: 1) Beil 4,639, (591)& [1018] trysts of RDX which would increase the sensi-
2) A. Demougin, MP 25, 139 (1932–33) tivity of the compn (Refs 1 & 4)
3) Merck (1968), 1025-L 4) Sax (1968), Lecithin used by the USA armed forces is
870-L 5) CondChemDict (1971), 856–57 covered by a military specification (Ref 3)
contg the following requirements: (1) moisture,
1.O%O max, (2) benz insol matter, O.l% max,
Lead Thiocyanate (Lead Sulfocyanate, Lead (3) acid no, 24 max, (4) acetone insoluble
Rhodamide). Pb(SCNh, mw 323.38, white, matter, 68’ZOrein, and (5) Lecithin, 19.0% min
odorless pdr, mp (dec 190–95~, d 3.82g/cc; Refs: 1) O.E. Sheffield, “Handbook of Foreign
sol in about 200p cold, 50p boiling w; sol in Explosives”, FSTC 381-5042 (Ott 1965), 67–8
alkali hydroxide and thiocyanate solns. May 2) Merck (1968), 615-L 3) Anon, “Lecithin
be prepd by the action of a sol Pb srdt (ace- (For Use in Explosives)”, Ml L-L-3061 B (June
tate or nitrate) on K thiocyanate (Ref 1). It 1969) 4) Anon, “Properties of Explosives
has found extensive use in stab priming and of Military Interest”, EngDesHdbk AMCP
ignition mixts. Examples are: 1) priming mixt: 706-177 (Jan 1971), 53–4 5) CondChem-
Pb(SCN)2 25, Sb2S3 17, LA 5 & KC103 53%; Dict (1971), 513-R
2) igniting mixt: Pb(SCN)2 45 & KC103 55%
(Ref 2)
The requirements of the USA armed forces’ Lecorche-Jovinet Sensitivity Test. Test for the
are covered by a military specification (Ref 3) stability of proplnts contg NC. Any nitrous
which contains the following criteria: (1) form – acid present is absorbed by diethyldiphenyl-
discrete crystals, (2) color – white or yellow, urea to form ethylphenylnitrosamine, which
(3) granulation ,–100% shall pass thru US can be detected by testing with c+naphthyl-
standard sieve No 140 (105 microns), and 75% amine-HCl
thru sieve No 325 (44 microns), (4) Pb as Refi H. L6corch6 & P.L. Jovinet, CR 187,
Pb(SCN)2, 99.3% rein, (5) thiocyanate as 1147–8 (1928) &CA 23, 3345 (1928)
Pb(SCN)2, 99.3% rein, (6) chloride, as PbC12,
0.20% max, (7) Na, as thiocyanate, 0.20%
max, (8) moisture, 0.20% max, and (9) insoluble LEDC. See Low Energy Detonating Cord
matter, 0.2070 max
Refs: 1) Beil 3, 157, (68) & [116]
2) Ellern (1968), 54 & 353 3) Anon, Lederite. An older Austrian mining expl contg
“Lead Thiocyanate (Sulphocyanate)”, M I L- K nitrate 45, red lead (Pb3 04) 20, leather
L-65A (12 Feb 1968) scrap 18, sulfur 15 & PA 2%
Refi Daniel (1902), 404
 L12

LEE D. Acronym for Laser Energized Explo- cotton 23.3, lycopodium 4.7 & urea 1.9%.
sive Device. See under Laser For use in cannon, these powds were mixed
with about 3.5% cottonseed ofi as a water-
proofing agent
Lennard-Jones, Devonshire Equation of State. Refs: 1) Daniel (1902), 405 2) VanGelder
Derived forgases at high d,in terms of inter- & Schlatter (1927), 859
atomic forces, using statistical mechanics. The
atom in a dense gas was considered similar to
that in a liq or tryst, subject to multiple col- Leonit (Leonite). Ger permissible Dynamite
lisions at all times (Ref 1). This method was contg NG 4, K perchlorate 35, AN 10, Na
later extended to liqs (Ref 2) and solids (Refs nitrate 3, crude TNT 11, woodmeal 7 & alkali
3 & 4), and was used by Murgai and others chloride 3070
for the calcn of the expl properties of TNT and Refs: 1) M. Giua, “Dizionario di Chimica”,
PETN (Refs 5 & 6) Torino (1951), 166 2) B.T. Fedofoff et al,
Refs: 1) J.E. Lennard-Jones & A.F. Devonshire, “Dictionary of Explosives, Ammunition and
PrRoySoc A163, 53–70 (1937) &CA 32, 1533 Weapons” (German Section), PATR 2510
(1938) 2) Ibid A165, 1–11 (1938) & CA (1958), 107-R
32, 6118 (1938) 3) Ibid A169, 317–38
(1939) &CA 33,4098 (1939) 4) Ibid
A170, 464–84 (1939) & CA 33, 9071 (1939) Lesmok Powder. One of the older American
5) MY. Murgai, JChernPhys 21, 1403–4 (1953) sporting powds manufd by DuPont’
&CA 47, 11738 (1953) 6) Ibid, Proc- Ref Marshall 1 (1917), 330
IndianAcadSci 39A, 176–84 (1954) & CA 48,
1322 (1954)
Note: See Encycl 4, pp D287-L to D288-L Le Sueur’s Explosive. Prepd by mixing 12.5p
of molten paraffin wax with 11p sulfur and
54p Na nitrate. After cooling, the mixt is
Le Marechal Powders. Prepd by mixing finely granulated thru a screen and blended with
pulverized K, Na or Amm chlorate (about 22.5p of pulverized K chlorate
84%) with molten stearic or palmitic acid Ref: E.A. Le Sueur, USP 923435 (1909) &
(about 16%). After cooling, the mass was CA 3, 2227 (1909)
pulverized and mixed with a small quantity
of finely powdered charcoal, which served to
increase the flammability of the product. The Leuschel Explosives. Ger expls prepd by im-
resulting expl was loaded into cartridges by pregnating moss with glucose, starch, sugar or
extrusion glycerin solns, drying the mixt and nitrating
Refi Daniel (1902), 404 the resulting product
Ret Daniel (1902), 405

Lenite. A mixt of PA and collodion cotton

Ref.’ Daniel (1902), 404 Levoglucosan Trinitrate. See under Fructosan
Trinitrates, Vol 6 of Encycl, F208-L

Leonard’s Smokeless Powders. Several varieties

of proplnt manufd at the end of the 19th Levulose Trinitrate. See under Fructose, VO1
century by the Leonard Smokeless Powder Co 6 of Encycl, F208-L
of Manchester, NJ, using as one of the ingre- Addtd Refi: 1) Beil 1, (460) 2) H.A. Lewis,
dients, urea dissolved in acct. Typical compns USP 1947530 (1934) &CA 28, 2538 (1934)
contd: 1) NG 31.6, Guncotton 52.6, lyco- 3) ibid, CanP 340567 (1934) & CA 28, 4234
podium 10.5 & urea 5.3%; 2) NG 70.1, Gun- (1934)
 L 13

Lewin Explosives. Patented in Fr in 1887, tented, between 1889 and 1894, several expls
consisting of nitrated residues of cane sugar named “Nico Powder” and Acme Powder
“ plants, either alone or mixed with NC, NC, (Encycl 1 (1960), A93-R)
Na nitrate, rye flour, paraffin, tar, etc. They Ref.’ Daniel (1902), 5 & 406
were also known as “Sandhoulites”
Ref Daniel (1902), 406
Lichenin (Moss Starch). C6HI ~05; mw 162.14,
mp 10°. White gelatinous mass, resembling
starch in props. S1 sol in cold w; sol in boiling
Lewisite (L). Dichloro (2-chloro-vinyl) arsine. w giving a colloidal soln and sol in HC1. On
C1CH:CHASC12;mw 207.35, dk-grn oily liq, nitration it yields an expl, Lichenin Penta-
fr p –18°, bp 190°, liq d 1.89 at 20°, vap d nitrate (qv)
7.2 (compared to air), decompn temp (above Refs: 1) Beil, not found 2) Karrer (1947),
1000). Vap press 0.087mm Hg at 0°, 0.394mm 357 3) Dor6e (1947), 435 4) Merck
at 20°, 32.50mm at 1000. Volatility 967mg/m3 (1968), 618-R 5) CondChemDict (197 1);
at 0°, 2300mg/m3 at 20°, 8890mg/m3 at 30°. 515–6
Odor, usually geranium-like, very little odor
when pure. Flash p, none; rapidly hydrolyzed
in liq or vap state to HC1 and chlorovinyl- Lichenin Pentanitrate. Cl 2H1 SOS(ONOZ)S;
arsenious oxide. The later is a nonvol blister- mw 549.28, white solid, N 12.75% (theory),
forming solid not readily washed away. L is 12.40% (found). May be prepd by method de-
stable in steel or glass containers scribed by Reilly (Ref 2) as follows: At RT
In use, a moderately delayed-action casualty with stirring, gradually add 1p of freely powd
gas. A “blister gas”, toxic lung irritant and sys- lichenin to 50p of a mixt consisting of 3p by
temic poison. It produces immediate and strong wt of H2S04 (d 1.84) and lp of HN03 (d
stinging sensation of the skin 1.50). Stop the agitation, allow the nitrate to
Refs: 1) Anon, OrdTechTerm (June 1962), settle,. and decant the supernatant liq. Pour
68-R 2) Anon, “Military Chemistry and the ppt and remaining spent acid into ice w.
Chemical Agents”, TM 3-215 (Dee 1963), Filter and purify the pentanitrate, first by
26–27 boiling in S1acidic w, then in S1alkaline w,
Note: See Encycl 2 (1962), C 168-R and finally with neutral distd w. Dry at a low
temp
Lichenin Pentanitrate is insol in w, eth and
Lezinsky’s Explosive. A mixt of whole wheat benz; readily sol in acet, et acet and amyl
flour 27p with resin 53p is treated with 20p acet; sol in eth-alc mixts. It is an expl compd,
nitric acid and, without washing, combined with decompg at high temps, giving off oxides of
100 to 300p of K chlorate nit rogen
Ref G. Lezinsky, USP 909915 (1909) & CA Refs: 1) Beil, not found 2) Reilly (1938),
3, 1088 (1909) 42

L.F. Dynamites. Abbr for Low-Freezing Dyna- Liebert. Patented in 1889 in Fr, a method of
mites. See Vol 5 of Encycl, D1 584-L & nitrating glycerin with mixed nitric-sulfuric
D1588-R to D1593-L acids in the presence of Fe sulfate or AN
Refi Daniel (1902), 407

L.G. Powder. Brit abbr for Large Grain BlkPdr

formerly used in cannons Liebert Dynamites. Low-freezing dynamites
Ref Daniel (1902), 406 prepd from NG mixed with 3-5% iso-amylic
d
alc nitrate. It was claimed that these were
more powerful than those prepd from NG alone
Liardet Explosives. Liardet of Australia pa- Refi Daniel (1902), 407
 L 14

Life of Guns. See under Erosion of Gun Barrels to be stable for long periods of time in dif-
in Encycl 5 (1972), El 12-R to E120-R fused light. Samples standing in the labora-
tory, protected from direct surdight, showed
no signs of discoloration after 6 months. In
Ligdyn. A South African Dynamite contg NC direct sunlight, however, DADNPh darkened
40, Na nitrate 45, woodmeal 13 & wheat rapidly eventually acquiring a dark brown color.
flour 2% (Ref 2). An expln of 4210 lbs of To detn the effect of exposure on its expl
Ligdyn in 1913 was reported caused by friction strength, DADNPh samples subjected to from
in a packirrg machine (Ref 1) O to 20 hours of sunlight were fired in a
Refs: 1) A.B. Denne, JSCI 32,627 (1913) Sand-Test bomb. The results showed that
&CA7, 3229 (1913) 2) Marshall 1, 362 DADNPh undergoes no loss of strength on
(1917) one hour exposure, with no makred decrease
even after 3 to 5 hours, despite a marked
darkening in color (Ref 3)
Light, Effect on Explosives. Many expls un- Eggert (Ref 8) and McAuslan (Ref 7) re-
dergo slight changes in compn when subjected ported on the initiation of explosions by light.
to direct light, especially sunlight or ultraviolet Evidence was presented for photochemical
radiation. Mitra & Shrinivasan (Ref 5) studied and/or photothermic effects in various nitrides,
the effect of sunlight on thin layers of TNT azides, acetylides and perchlorates
and Tetryl. In the case of TNT, they noted a Refs: 1) C. Krauz & O. Turek, SS 20, 49
lowering of its mp, a reduction in sensitivity, (1925) &CA 19,2747 (1925) 2) W.M.
and a color change from light buff to yellow- Munzinger, ChemZtg 56, 851–52 (1932);
orange to dark brown with continued exposure. abstracted in Chim&Ind 29, 783D (1933)
Tetryl exhibited a mp decrease with no change 3) L.V. Clark, IEC 25, 667 (1933) 4) Kast-
in sensitivity. Nitrous fumes were evolved and Metz (1944), 247 5) B.N. Mitra & N.
exposed surfaces became brown, but much Shrinivasan, JSciIndRes 6B, No 2, 31 –5
more slowly than for TNT. Krauz and Turek (1947)& CA 41, 5723 (1947) 6) T. Ur-
(Ref 1) noted a TNT mp decrease from 81.4° bafiski, RocznikiChem 21, 120–23 (1947)
to 73.5° after 4 months direct sunlight exposure, &CA 42,4856 (1948) 7) J.H.L. McAuslan,
and extracted Trinitrobenzoic acid and Tri- ProcRoySoc A246, 248 (1958) 8) J. Eggert,
nitrophenol as breakdown products JPhysChem 63, 11–15 (1959) & CA 53,
Urbarlski (Ref 6) followed the photochem 12680 (1959)
decompn of NC, NC (1 1.9% N) and Hexogen
on exposure to UV radiation by the liberation
of iodine from K iodide soln, and derived rate Light Emission (Luminosity Effects) from
equations. NC continued to decomp even after Detonations and Explosions. “Detonation
See
the UV source was removed, becoming in- (and Explosion), Luminosity (Luminescence)
creasingly acidic, and was judged less stable Produced on” in Encycl 4, (1969), D425-L
than NC. The NC rate of decompn remained to D434-L, and “Detonation (and Explosion);
constant with time. NC evolved oxides of N2, Spectra and Spectrographic Measurements in”,
became acidic, and was finally judged useless D548-R to D549-L
as an expl material. Hexogen, although chang-
ing color from white to yellow, produced no
volatile products capable of oxidizing K iodide Light, Production of. See under Pyrotechnics
Munzinger (Ref 2) exposed pure NC to
sunlight and noted only sli@t yellowing after
several months. However, NC contg gelatini- Lightning Protection. It is policy in the USA
zes such as castor oil or tricresyl phosphate to install lightning protection on bldgs and
was affected in a matter of days, yellowing structures used for manufg, processing, handling
and becoming less sol in et acet or acet or storing expls, ammo, expl ingredients, and
Diazodinitrophenol (DADNI%) was found other hazardous materials, particularly where
 L15

operations cannot be shut down during electri- was heated on a w bath until the lignin was
cal storms and personnel evacuated completely dissolved, whereupon the nitration
Approved lightning protection systems are product was pptd by dilg the soln with w
the integrally mounted system, the separately Fischer and Schrader (Ref 4) nitrated lignin
mounted shielding system (mast type), and the by treating it with 31.5% nitric acid at RT,
separately mounted shielding system (overhead completing the operation with moderate heating.
ground wire). Details of all of these systems Only 4.3% N was found in the prod, to which
are described in the Ref the formula C39Hz ~ ~ ~N3 (OCH3 k was as-
The purpose of these installations is to pro- signed on the basis of analysis. At the same
vide a metrd path of low resistance for the dis- time, Konig (Ref 5) nitrated lignin at low temp
charge of electrical currents from the air to to obtain a prod contg 3% N
the ground without damage to the structure Powell and Whittaker (Ref 6) nitrated lignin
or contents. These systems also serve to pre- with mixed nitric-sulfuric acids at –5°C, and
vent the charging of structural metal components isolated the nitration prod by pptn with ice
as a result of induction when lightning strikes and w. It was a red powd with the empirical
nearby compn C4ZH3901 @Oz)s
Refi Anon, “Safety, Safety Manual”, AMCR Kiirschner et al (Refs 7, 8 & 11) prepd
385-100 (April 1970), Chapt 8, 8-1 to 8-36 nitrolignin by direct nitration of wood pulp.
A soln of nitric acid (d 1.40) in alc was used
at the temp of boiling ale. Under these condi-
Lignin. A polymer found in wood (25–30%). tions cellulose remained unchanged. Lignin,
The structure of tlie lignin monomer is still on the other hand, was nitrated and dissolved
not completely known. Its similarity to in the rdc soln. Nitrolignin was then separated
coniferyl alcohol, noted more than 75 years from the soln with w, in the form of an amor
ago (Ref 1), is confirmed by the fact that it yellow powd. The yield of nitrolignin was
can be oxidized to vanillin and hydrogenated 15–1 7% of the wt of wood pulp. According
to compds of the cyclohexylpropyl type. to the type of wood used to prepare the lignin,
Lignin is removed from wood by both the the N content of the fully nitrated prod varied
sulfate and soda paper pulp processes, and from 3.0 to 4.5%. On the basis of his own
limited runts have been recovered from these expts, Ktirschner suggestedthe following func-
sources and other wood waste. It has been tioned compn for nitrolignin:
used as a component of Dynamites, and has Cl SHI aOz(COOH)(OH)~(OCHa)@Oz)
been nitrated In order to separate lignin from carbohy-
Refs: 1) P. Klason, SvenskKemTid 9, 133 drates, stronger reagents were used in the expts
(1897) 2) F.F. Nerd & W.J. Shubert, SciAm of Friese et al ( Refs 9 & 12) for the nitration
199, No 4, 104-13 (1958) 3) F.E. Brauns of wood pulp, namely normal mixed acids. In
& D.A. Brauns, “The Chemistry of Lignin”, this way nitrolignin with a higher N content
Academic Press, NY (1960) 4) I.A. Pearl, was obtained. When nitric-sulfuric acids
“The Chemistry of Lignin”, Marcel Dekker, (1:2 ratio) were used, a prod contg 8.45% N
NY (1967) 5) CondChemDict (1971), was obtained with a yield of 55%
516-R Although nitrolignin was used in early proplnts,
mining expls and sporting powds (Refs 1 & 2),
Urbafiski (Ref 14) states that it is unsuitable
Lignin Nitrate (Nitrolignin). A general term for manufg nitro compds likely to be of prac-
employed to designate nitrated products contg tical value as expls
lignin, such as wood, straws, jute, esparto grass,
flax and hemp fibers (Ref 1)
The earliest expts devoted to the nitration Lignin Dynamites. Mixts prepd by impreg-
of lignin, previously isolated from woodpulp nating sawdust with NC were known by this
by means of HC1, were reported by Hdgglund name. They sometimes contd metallic nitrates
(Ref 3). Lignin mixed with fuming nitric acid Refi Daniel (1902), 408
 L 16

Refs: 1) Daniel (1902), 559, 706–08 Limiting (or Critical) Charge Density-Diameter
2) E. Durnford, “Manufacture of Nitrolignin of Explosive Charges. See Detonation Velocity-
and Sporting Powder”, Whittaker & Co, Charge Diameter and Density Relationship in
London (1912) 3) E. H2igglund, Arkiv- Encycl 4 (1969), D641-L to D656-L
ChemiMinerGeol 7, 20 (1918) 4) F. Fischer
&H. Schrader, BrennstoffChem 2, 217 (1921)
5) F. IG6nig, Cellulosechem 2, 93, 105, 117 Limparicht Explosives. According to Daniel
(1921) 6) W.G. Powell & H. Whittaker, (Ref 2), the following compds were patented
JCS 125, 357,364 (1924) 7) K. Ktfrschner, in 1888 as expls, but do not appear to have
ChemZtg 48, 461 (1924); BrennstoffChem 6, found any practical application:
117, 177, 188 (1925); JPraktChem [2], 118, 1) Barium m-Triazobenzene Sulfonate,
238 (1928); Cellulosechem 12, 281 (1931); (N3C6H4S03)2Ba; needles which expl at
ZellstoffFaser 32, 17, 81, 87 (1935), Ibid 33, 130° (Ref 1) 2) Potassium m-Triazobenzene
1,49, 121 (1936) 8) K. Ktirschner & F. Sulfonate, N3C6 I-$ S03 K; very unstable, expl
Schindler, ZellstoffFaser 33, 121 (1936) at about 130° 3) Barium Triazobenzene
9) H. Friese &H. Fiirst, Ber 70, 1463 (1937) Disulfonate, N3C6H3(S03)2Ba 4) Ba-
&CA 31, 6869 (1937) 10) R.S. Hilpert, rium Triazobrombenzene Sulfonate,
W. Kriiger &G. Hechler, Ber 72B, 1075–82 (N3C6H3BrS03 ~ Ba 5) Sulfodiazoben-
(1939) &CA 33,5813 (1939) 11) K. zoic Acid, HOS02(N2 )C6H3COOH; very sen-
Kiirschner & K. Wittenberger, Cellulosechem sitive to shock and heat 6) Sulfodiazobrom-
18, 21 (1940) 12) H. Friese & W. Liudecke, benzoic Acid, HOOCC6H2 Br(S03H)N2; more
Ber 74, 308 (1941) &CA 39,4547 (1941) sensitive to shock than previous compd
13) K. Freudenberg, W. Lautsch & G. Piazolo, 7) Hydrazinobenzenedisulfonic Acid,
Celhdosechem 21, 95–6 (1943) &CA 38, H2NNHC6H3(S03H)2
5081 (1944) 14) Urbar%ki 2,435 (1965) Refs: 1) Beil 11, 80 2) Daniel (1902), 408

Lignite (Brown Coal). A brownish-black coal Limpet Charge. HE grenade or mine which
in which the alteration of vegetable matter has uses a magnet for adherence to the metrd
proceeded further than in peat, but not as far sides of tanks or ships
as in sub-bituminous coal. There is no sharp Rejl S. Fordham, “High Explosives and Pro-
distinction between these three materials, but pellants”, Pergamon Press, NY, 166 (1966)
in generrd, lignite is denser, darker in color,
and contains more C than peat. Lignite con-
sists of w 9– 12, vol comb matter 31 –38, Lindeman Explosive. BritP of 1899 for an expl
f~ed C 27-43, and ash 5–20% (Ref 3) consisting of NG, K chlorate and MNB or DNB
Lignite in powd form has been used as a Ref Daniel (1902), 408
component of blasting expls, for example,
Explosive of Kolowratnik (19 12) contains
PA 45, Na nitrate 40, sawdust 9 & lignite 6% Lindner Explosive. FrP of 1895 for an expl
(Ref 1). Marcusson (Ref 2) nitrated lignite contg AN 93.2, naphthalene 5.5 and K chlorate
with fuming nitric (d 1.52) and mixed nitric- 1.3%
sulfuric acids. The prod was sol in acet, and Refi Daniel (1902), 409
consisted of various nit rocornpds
Refs: 1) Colver (1918), 325 2) J. Mar-
cusson, ZAngChem 34, 521–2 (1921) & CA Linear Shaped Explosive Charges. Picatinny
16, 1496 (1922) 3) CondChemDict (1950), Arsenal developed a linear shaped demolition
398; (1971), 516-R charge (Ref 1) capable of felling trees up to
40” in diam. The charge is 7“ long, 2.4”
high and 4.7” wide, and contains 1.5 lbs of
Limiting Charge. See Charge Limit or Limit Comp B. It is more efficient than other
Charge in Encycl 2 (1962), Cl 51-R to C 153-L shaped charges, such as conical shaped and
 L 17

platter charges, because of its exceptional side- various points in an expl charge. Those of the
cutting ability. The claim is made that this manifold type are made by loading expls into
charge uses 50-705Z0less expl than more con- channels machined, molded, or cast into metal
ventional bulk and ring tree-cutting expl de- or other inert components and by constructing
vices arrays of detong cord. These arrays are limited
Moses (Ref 3) describes linear expls consisting to relatively large systems by the spacing needed
of tube-like containers ffled with burning or to prevent initiation or damage due to radial
detong expls of the following types: blast effects of adjacent cords (See Fig)
1) Safety jiize used for mining and quarrying
consists of BkPdr in cotton and polyethylene
cov,ers, wax dipped; 2) Detonating cord used
for general blasting and demolition consists of
PETN or RDX in a waterproof textile sheath;
AVEPATH
3) Mild deton fuze is smaller than type (2);
it is used to transfer detons, and has a metal ,---. -, ----------------- <-;-;;.---.;; ... .. . . . ... .. . . . ,
sheath; 4) Confined deton fuze is similar to
type (3) except that the metal sheath is wrapped .------ .--- =-. ------- f:-------- -------- ----- -------
in fiberglas and polyethylene to contain the
fragments; 5) Flexible linear shaped charge is Line Wave Generator of the Manifold Type
a detong cord with a V-shaped cross-section
used to cut metal The advent of mild detonating cord (MDC)
Linear shaped charges as well as expl cords has opened new possibilities in manifold type
have been developed for use in commercial wave shaping devices
cutting operations. One special application is Another line wave generator of the manifold
a cast iron pipe cutter called “Jetcutter”. It type consists of perforated sheet expl (See Fig)
makes a straight and clean cut in cast iron pipe
from 6 to 12“ in diameter by means of a re-
usable f~ture and an expendable shaped charge
insert. A forced entry tool, dubbed “Jet-Axe”
cuts thru 5“ of roofing material and thru fire
doors and similar structures. Rapid egress
systems are being developed for aircraft and
other passenger carrying vehicles (Ref 3)
Line Wave Generator of Sheet Explosive
Refs: 1) S.J. Lowell & R.T. Schimmel, “XM 184
Linear Shaped Demolition Charge for Felling
Large Trees”, PATR 3408 (1966) 2) J.E. A dupont version (Ref 1) is in the form of,~er-
Drake, Asst Product Mgr, Explosive Technology, forated equilateral triangles measuring 10.9
Box KK, Fairfield, Calif 94533; Abstracted in on a side and are prepd from “Detasheet”
Expls&Pyrots 2 (2) (1969) 3) S.A. Moses, flexible expl. The sheet expl is perforated in
Ordn 56, 355–57 (1972) such a manner that a deton initiated at any
one of the apexes will proceed as a straight-
line deton zone to the opposite edge
Lined Cavities of Explosives (Lined Cavity In addition to such generators, warped
Effect). See under Detonation, Munroe- surfaces may be used to produce line waves
Neumann Effect (or Shaped Charge Effect) of any desired curvature. The circular front
And Lined-Cavity Effect In, Encycl 4 (1969), generated by the point initiated deton of a
D444-R to D450-R plane charge may also be modified by warping
the plane and by transmitting to other expl
surfaces: An example, illustrated below, is the
Line Wave Generator. Devices for controlling generation of a straight-line wave by means of
the sequence of arrival of detonation waves at warped sheet expl
 L18

—fLaT C,I?CLAC,RSEGMENT
Of SHEET EUPLOSIVE may be prepd by treating K Iinoleate with
PO,N1 OF
lN171~T!ON trichlorhydrin at 160° in a stream of H2.
V sol in eth, benz and chlf; less sol in ale,
methanol, Iigroin & CS2
The nitrated compd was proposed by Reid
and Earle (Ref 2) as a constituent of expl
mixts, eg, 1P nitrolinolein and 9p NC
Linolein Nitrate (Nitrolinolein). A prod obtd
by nitration of Iinolein (See above) and used
HOLLOW CONE or
DET0N4110W ARRIvES $HEE1 E~PLOSIVE in some expl mixts
SIUULT4NE0USLY al bLL
POINIS ON 1!41S LINE If Refs: 1) Beil 2,461 & (214) 2) FrP
i+e-=c
251985 (1895) 3) Daniel (1902), 670
4) CondChemDict (1971), 519-L
Line Wave Generator
of Warped Sheet of Explosive
Linseed Oil (Boiled Oil, Bung Oil or Bung
Refs: l) New Explosives Specialties Brochure Hole Oil). The oil obtained by hot pressing
on Line-Wave Generators, dtiont Co, Explo- the seeds of the flax plant. Consists of gly-
sives Products Div, Wilmington, Del 19898; cerides of linolenic, linoleic, oleic, stearic,
Abstract in Expls & Pyrots 5 (12) (1972) palmitic and myristic acids. Yellowish liq,
2) Anon, Engrg Design Hdbk, “Explosive peculiar odor, bland taste
Trains”, AMCP 706-179 (Jan 1974), 3-12 to “Boiled linseed oil” is a misnomer, since
3-13 the oil does not boil. Small amts of driers
(oxides of Mn, Pb or Co, or their naphthe-
nates, resinates or linoleates) are added to hot
Linen Fiber (Flax, Byssus). The bast fiber of linseed oil to accelerate drying. The “boiled
the flax plant, an annual herb about 2 ft high. oil” becomes thicker and darker. It is com-
It is grown in Europe and Egypt for the fiber bustible, with a flash p of 403°F and an
and in the USA, USSR & Argentina for the autoignition temp of 650”F (Ref 4)
seeds (linseed oil). The nitrated unbleached For many years, boiled linseed oil has been
prod was proposed by Trench (Ref 1, p 773) used to coat Mg powd to protect it from cor-
for use in expl compns rosion when used in pyrotechnics. Mg powd
Nitrated Linen Fiber (Nitroflax, in Fr Nitrolen). and oil are mixed together- and allowed to stand
Product resembling cotton NC and prepd by in a warm place in shallow trays for about
nitrating unbleached flax. When nitrated under 48 hours, before the other chemicals are added.
identical conditions, flax gives a more viscous Lately there has been a tendency to replace
prod than cotton. In order to lower the linseed oil with polyesters, or to use no coating
viscosity of nitroflax, the temp of nitration at all, but there can be no doubt that linseed
is raised. Nitroflax has been used in some oil renders good protection. Stores made
celluloids (Ref 1, p 120), and was proposed with Mg coated with linseed oil are good for
(Ref 1, p 773) as a basic ingredient in commer- several years, which is not the case with un-
cird expls, other components being collodion coated Mg (Refs 2 & 5). Linseed oil has also
cotton, glycerin, ozokerite, resin, etc been used for coating K chlorate used in expls
Refs: 1) Daniel (1902), 120 (under Celluloid) (Ref 1)
& 773 (under Trench) 2) Hackh’s (1944), The requirements of the USA armed forces
345-R for boiled linseed oil are covered by Federal
Spec TT-L-I 90C (Ref 3) and are as follows:
(1) Set-to-touch (hours), 16 max; (2) Loss
Linolein (Glyceryl linoleate). A glyceride of on heating at 105’’*2° (% by wt), 0.3 max;
linoleic acid. It is one of the constituents of (3) Acid number, 7.5 max; (4) Saponification
linseed oil which induces drying. Yel oil; number, 189–195; (5) Unsaponifiable matter
 L 19

(% by wt), 1.50 max; (6) Iodine number (Wijs), better wpn of the linters and to have less short
170 rein; (7) Ash (% by wt), 0.50 max; (8) fibers adhering to the seed, deSegundo devised
Specific gravity, 0.928 to 0.938 at 25°/250; a special machine. He concluded that it is
(9) Appearance – the oil shall be clear and very difficult to completely remove all the fuzz
transparent at 65° (149QF) when examined by without employing chemical methods
transmitted light Note: See also Cotton Linters in Vol 3 of
Refs: 1) Colver (1918), 278 2) Anon, Encycl, p C547-L
EngDesHndbk, “Properties of Materials Used Refs: 1) Marshall 1 (1917), 163; 2 (1917),
in .~rotechnic Compositions”, AMCP 706-187 697; 3 (1932), 30 2) E.C. deSegundo,
(Ott 1963), 173–4 3) Federal Specifica- JSCI 37, 118T–123T (1918) 3) CondChem-
tion TT-L-19~ “Linseed Oil, Boiled, (For Use Dict (1971), 520-L
In Organic Coatings)” (Dee 17, 1964)
4) CondChemDict (1971), 519-R 5) R.
Lancaster et al, “Fireworks, Principles and Liquefaction Test. A test used to det the exu-
Practice”, Chemical Publishing Co, NY, 42–43 dation of Dynamites. In Engl, the test was
(1972) conducted as follows: A cylinder of approx
equal length and diameter was cut from a
cartridge of Gelatin Dynamite to be tested.
Linters. Fleecy short fibers (1/8” to 1/4” in With paper removed, the base of the cylinder
length), consisting chiefly of cellulose, which was placed on a sheet of pasteboard and held
adhere to cotton-seed after it has been passed fast by a pin driven vertically thru its center.
once thru a cotton-gin. These are usually re- After conditioning at 29–32° (85–90°F) for
moved from the seed by a second and third 144 hrs, the height of the cylinder was measured.
ginning to yield first and second cut Iinters. If it did not shrink more than 25% of its ori-
The first cut fibers are the longer and are used ginal height, the Dynamite passed the test.
mainly for padding, upholstery, mattresses, Another condition of acceptability was that the
etc. Second cut linters are suitable for the upper cut surface retain its flatness and sharp-
prepn of various NC’s after special treatment ness of its edges
consisting of boiling in caustic soda, followed In Germany, the test was conducted by
by bleaching heating an entire cartridge for 5 days at 30°
Purified linters are used extensively in the (86”F). The requirement was that no NG
USA for the prepn of NC, but longer fibers should exude and, after cooling, that the car-
are preferred in Engl. During WWI, Engl tridge dimensions remain unchanged
also used material called “slivers” (Ref 1, 3, Refs: 1) Marshall 1 (1917), 163 2) Naoiim,
p 30), which was staple cotton in the form of NC (1928), 314
unspun strips – an intermediate stage in the
manuf of yam. Although more expensive than
cotton waste, it yielded purer and more stable LIQUID. AIR AND
Cordite LIQUID OXYGEN EXPLOSIVES
In Fr, three kinds of cotton material were Liquid Air and Liquid Oxygen Explosives
used in NC manuf (1) Waste No 1, which originally consisted of porous combustible
consisted of bleached waste from spinning and materiaJs impregnated with liquid air. Soon
weaving mills using long-staple cotton of Egypt- after liq oxygen became commercially avail-
ian and American origin; (2) Waste No 2, con- able it began to replace liq air in these explo-
sisting of unbleached spinning-mill waste and sives. Consequently this article is devoted al-
(3) Linters, similar to American linters, which most entirely to Liquid Oxygen Explosives
must be free of cotton waste. According to commonly called LOX. It should be noted
deSegundo (Ref 2), some short fiber cotton that LOX are not to be confused with Fuel-
called “fuzz” still remains on the seed after Air Explosives (See FAE in Vol 6, p F3).
removing the long fibers and linters by ginning For LOX the oxidizer is liq and the fuels are
and delinting machines. In order to effect either solids or liquids, while in FAE the oxi-
 L 20

dizer is atmospheric oxygen and the fuels are and their fume characteristics make them un-
usually gaseous or liquid droplets at the time suitable in many underground mines even if
of explosion. General references on liq air and they are non-gassy. The following tabulation
liq oxygen expls are Refs 2, 3, 5, 7, 8, 14, 16, (from Ref 18) shows that LOX consumption
19&52 in the 1950’s amounted to some two to three
In what follows we will examine: percent of the total expls used
1) The history of LOX
Table 1
2) Typical LOX compositions
SALES (Millions of Pounds) OF INDUSTRIAL EXPLOSIVES*
3) Uses
Black Other than
4) Detonation and sensitivity characteristics
Year Blasting Permissible Permissible LOX
5) Recent Patents
Powder
1) lhto~. LOX, or more precisely Liquid
Average
Air Explosives, were invented by Linde in 1895,
1935-1939 65.4 45.7 253.6 Not available
who called these expls Oxyliquits (Ref 1).
1949 20.1 91.6 505.6 13.9
They were made by impregnating porous com-
bustible solids with liquid air shortly before 1950 20.7 109.4 576.0 13.8
1951 14.0 108.3 611.2 20.3
firing the charge. Usually the combustibles,
in some type of combustible cartridge, were 1952 10.6 95.5 636.7 21.9
soaked in liq air just before loading into the 1953 9.5 89.9 669.0 22.5
bore hole. Liq air expls were used extensively 1954 10.3 75.9 615.8 17.7
in 1899 in the driving of the Simplon tunnel 1955 6.6 93.7 687.2 19.3
between Italy and Switzerland 1956 5.6 97.7 (8 14.4) Not available
Liq nitrogen has a much lower heat of vapori- *Data ~ndly supplied by Robert W. Van Dolah,
zation than liq oxygen, and thus evaporates Chief, Division of Explosives Technology,
more readily. Becuase of this, liq air (a mixt Bureau of Mines, Pittsburgh, Pa
of nitrogen and oxygen) becomes progressively
Since then the use of LOX has declined
richer in oxygen as it is warmed or even in greatly, as ANFO and Slurry Explosives began
storage. This makes it almost impossible to to replace them. An indication of the decline
control the oxygen content of a liq air expl in the use.of LOX is given in the patent litera-
charge, even if it is fired promptly after pre- ture. For example, a 1936 review (Ref 8)
paration. Variable oxygen content can result lists 64 German patents on LOX. Undoubtedly
in poor performance, or even non-performance, by 1936 there were also many patents issued
and in uncontrolled explosive fumes. Thus, in the USA, UK and France. In the period of
the natural tendency to replace liq air with 1936–1 960 a considerable number of patents
liq oxygen in these expls began as soon as liq on LOX is listed in CA. Some of these are
oxygen became commercially available. This abstracted in Section 5 below. Since 1960,
occurred some years prior to WWI however, the number of LOX patents has de-
During WWI the Germans used LOX (and clined drastically. Almost none is listed in
also liq air explosives) extensively in coal, the most recent Quintennial Index of CA
iron and potassium mines, in tunneling and in 2) Typical LOX Compositions
demolition work. In 1922 LOX were used in Both Liq Air and Liq Oxygen expls contain
Mexican silver mining and a few years later . porous combustible material as fuel. These
they were introduced into the copper mines fuels are generally contained in paper or cloth
of Peru and Chile cartridges. Occasionally liq fuels such as pe-
In the USA, LOX have been used primady troleum are mixed with the porous solids; eg,
in the strip mining of coal. For example, in some of Linde’s early compositions (Ref 1)
1950, 99.5% of all the LOX used was in coal contained kieselguhr mixed with petroleum.
mining (Ref 18). Most of this must have been Carbonized cork was also used in early Liq
for moving overburden, since LOX are non- Air Expls, although charcoal was the original
permissible (not allowed by law in gassy mines), absorbent. More recently, as liq air was replaced
 L 21

Table 2
LOX Compositions and Properties

Initial Composition (a) Initial Relative Detonation Rate

(parts) Sp Gr, g/cc Strength (b) (m/see)
38/225 LampBlack/LO 0.23 (C) 0.95 4200
57/230 LampBlack/LO 0.33 (c) 1.14 5000
65/225 Gas Black/LO 0.33 (c) 1.16 5000
49/12/21 5 Gas Black/FeSi/LO “ — 0.94 —
36/28/193 Woodpulp/Kieselguhr/LO 1.07 0.92 4180
49/12/216 Woodpulp/Lampblack/LO 0.76 0.80 3350
58/7.3/167 Woodpulp/Kerosene/LO 0.93 0.95 4660
64/26/182 Woodpulp/Kerosene/LO 1.09 0.80 4080
33/49/21 8 Fuel Oil/MgCO~LO — 0.99 4000
47/210 Carbene /LO (d) 0.24 (C) 1.13 5200
6430 (e)
(a) Before any appreciable evaporation of liq oxygen (LO)
(b) Relative to 40% Dynamite on a volume basis
(c) “Unsoaked” fuel; “soaked” sp gr not given
(d) Carbene is polymerized acetylene
(e) in an iron tube; presumably all other detonation rates are for unconfined cartridges

by liq oxygen, lampblack became the absorbent LOX have been almost entirely replaced by
most commonly used in LOX (Ref 12). The ANFO or Slurry Explosives
fuel content of LOX compositions should be ‘ In actual practice LOX were always prepared
capable of absorbing 5 to 6 times their weight near the explosion site. Usually a paper cartridge
of liq oxygen containing the absorbent fuel was “soaked” in
Many other fuels such as soot, turf, corkmeal, Iiq oxygen. The soaked cartridges were quickly
powdered anthracite, woodmeal, carbene (poly- placed in the borehole and fired promptly. Ex-
merized acetylene), calcium hydride, and spongy tensive tests (Ref 3) showed that firing had to
aluminum have been tried. Physical and chemical occur within 5 to 15 minutes after soaking,
properties of many LOX fuels are given by otherwise enough liq oxygen evapd to affect
Howell et al (Ref 3) and O’Neil & Van Fleet LOX performance or even cause misfires. The
(Ref 5a) LOX charges were generally fired with blasting
Several of the potentially useful LOX com- caps. Under favorable conditions, LOX charges
positions with some of their physicrd amd de- can be initiated by flame, but this type of initia-
tonation characteristics are listed in Table 2 tion is uncertain, and the performance of LOX
(taken from Ref 6). Some recent LOX compo- thus initiated tends to decrease. As discussed
sitions are given ‘in Section 5 in Section 4, the sensitivity of LOX to flame
3) Uses, In section 1, we showed that most can be a safety hazard
of the LOX in the USA are used in the strip In some operations, a cartridge packed with
mining of coal. In Europe LOX were also ex- absorbent fuel was inserted in the borehole and
tensively used in open pit mining, tunneling and filled with liq oxygen thru a tube reaching to the
construction. Indeed, in the first half of this bottom of the cartridge. A vent for evapg oxy-
century, LOX were used in most expls applica- gen had to be provided
tions, although not extensively, where fumes Yet another method was to make cartridges
were not a problem. O’Neil & Van Fleet (Ref with two compartments, one for absorbent and
5a) consider LOX economical arid safe (See the other for liq oxygen. After insertion in the
Sect 4 on LOX safety). La .Magna (Ref 9) borehole, the partition was ruptured (either by
prefers LOX to Dynamites. IsI the last decade pressure from the oxygen or by mechanical
 L 22

means from outside) to mix the liq oxygen what is known of LOX detonation character-
with absorbent. To increase the allowable time istics
between liq oxygen impregnation and firing Perrott (Ref 4) examined the effect of packing
(from 10 minutes to 16–22 minutes), Wakabayshi density on the relative strength of six liq oxygen-
(Ref 21) suggests precooking the borehole by lamp black compns, and measured their detona-
pouring small amounts of Iiq oxygen into it tion rates, D. Relative strengths on a weight
4) Detonation and Sensitivi~ Characteristics basis increased as packing density increased
a) Detonation Characteristics. LOX are except that the relative strength at the highest
commercial explosives and as such are used pri- packing density tested (0.46g/cc “unsoaked”)
marily in breaking and moving rock and over- was low. On a volume basis the compn at the
burden. From a practical point of view, it is lowest packing density (0.19g/cc “unsoaked”)
important to have a measure of the effectiveness had the highest relative strength. Detonation
of LOX blast in fracturing and moving the rate increased from 4500 to 6000m/see, although
“burden”. No single universally accepted mea- it is not clear whether this increase, as expected,
sure of blast effectiveness exists today, and cer- occurred as packing density was increased.
tainly none existed in the 1920–1 940 period Perrott also found that substituting Al for some
when most of the exptl studies of LOX were of the absorbent did not increase D but made
carried out. Practical experience suggests that the compn easier to detonate
the effectiveness of an explosive for fracturing In a subsequent study (Ref 5) Perrott found
“burden” is related to its brisance. Brisance is that 1% inch diameter cartridges of LOX, con-
a measure of the shattering power of an explo- taining lamp black, gave optimum blast results
sive and is closely related to the detonation at an “unsoaked” packing density of 0.30g/cc.
press (commonly called PC, or Chapman- This takes into account not only the strength of
Jouguet pressure) of the explosive (See Brisance the LOX but also their effective “life”, ie, the
in Vol 2, p B265–300). The effectiveness of maximum allowable time between “soaking”
an explosive for moving “burden” is related to and firing. For example, 5 minutes after
its strength or power (See Vol 4, p D730-L). soaking, LOX cartridges were found to have a
It is customa~ to rate explosive strength on a relative strength (on a volume basis) 11 SYO
relative basis, ie, as a percentage of the strength that of a standard Dynamite, but after 25
of some standard explosive – usually TNT or minutes their strength was only 65?40of the
some standard Dynamite. This rating is based Dynamite. Perrott suggests using as large a
on comparison tests, the most common of which cartridge diameter as practicable to reduce
is the Ballistic Mortar Test (See Vol 2, p B6-R) oxygen evapn. He also made further measure-
Unlike the relation between brisance and PCJ, ments of detonation rate and found that ‘it
expl strength is not readily related to some de- is controlled by the finest particle size com-
tonation characteristic of the explosive. At- ponent of the absorbent. Clark & La Motta
tempts to relate strength to detonation energy (Ref 7) also found that D increases as absorbent
are not wholly successful. Relative strength, particle size decreases. For gas-black LOX, D
based on ballistic mortar tests, correlates rather varied from 4000 to 6200m/see, while for
well with computed nRT, where n & T are the lamp black LOX D varied from 4200 to 5000
computed moles of gas and detonation temp of m/see. Perrott states that LOX will burn with-
the explosive, and R is the gas constant. Al- out detonation when unconfined but will de-
though n & T can differ appreciably with the tonate erratically when ignited under confine-
equation of state used in the computation, it ment ~
appears that ratios of nRT (at least for similar Okada (Ref 15) states that the oxygen to
explosives) do not suffer from this drawback carbon ratio for LOX of maximum brisance is
In the early expls literature (and much of 2.6. This is essentially the theoretical ratio to
the LOX work is in the “early” literature) convert all the carbon to C02. This writer be-
there is a great deal of confusion between lieves that Okada really meant maximum strength
brisance and strength rather than maximum brisance, as the latter
Now; with the above caveat, we can examine depends not only on compn but also on pack-
 L 23

ing density no comparisons with experimental results.

Okada’s conclusions are supported by Streng In this writer’s opinion, Cook’s vahes (Table
& Kirshenbaum (Ref 20) who found that a 12.20 of Ref 18a) of TCJ are too high and his
stoichiometric mixture (33 mole% CH4) of liq PCJ are too low; the products probably contain
methane and liq oxygen had a higher brisance more free carbon than shown. However, there
(in this case they really measured brisance) is little doubt that most LOX detonations are
and a higher detonation rate than other mixts “hot”, ie, they will readily ignite firedamp
containing from 6 to 80 mole tZo CH4. They (Refs 2,3, 12& 14). Also the computed de-
also determined the expl limits and detonation tonation velocities (estimated from Cook’s
rates of these mixts and examined the sensiti- PC,) show a much greater variation with compn
vity of the stoichiometric mixt to impact, and density than the experimental data of
shock waves, and flame & sparks. Their results Table 3
are summarized below: b) Sensitivi@ Characteristics. Early
~ Table 3 investigators (Refs 5a & 9) tended to over-
Mole % CH4
estimate the safety of LOX because they were
Liquid Density Detonation Rate non-explosive before mixing, and because they
6 1.05 Failed became non-explosive, even after a misfire, as
20 0.98 3325 the oxygen evapd. An interesting comment,
33 0.88 5110, 5130 by Wakabayashi (Ref 21), significant in these
40 0.83 5110 days of terrorist bombings, is that LOX are
50 0.76 4620, 4610 burglar-proof. Nevertheless, modem consensus
67 0.65 Detonated is that LOX are more dangerous to handle
80 0.50 Failed than conventional Dynamites (Refs 7, 12, 14,
17 & 21)
Although the above are not practical LOX
One of the most serious faults of liq oxygen
compositions, these results are of considerable
explosives is the ease with which they inflame
interest. They show that the detonation limits
and the rapidity with which they burn, amount-
of LOX compns are quite wide, and that D ing practically, in the majority of cases, to their
(at least for liquid methane-liquid oxygen mix- exploding from fue. Denues (Refs 10 & 11)
tures) is not strongly affected by considerable has found that treatment of the granular car-
changes in compn or even density
bonaceous absorbent with an aqueous solution
Cook (Ref 22) studied a chemically similar of phosphoric acid results ~. an explosive which
mixt consisting of 78/22 LOX/kerosene (stoich- is nonflammable by cigarettes, matches, and
iometric to C02 & H2 O), but the kerosene, ie, other igniting agents. Mono- and diammonium
the fuel, in his case was frozen, so that he dealt phosphate, ammonium chloride, and phosphoric
with a slurry rather than a solution. His results acid were found to be suitable for fireproofing
are as follows: the canvas wrappers. Liq oxygen expls made up
Density D pCJ from the fireproofed absorbent are still capable
1.04g/cc 224~/sec 10.4kbar of being detonated by a blasting cap. Their
Note that D for the slurry is much lower than strength, velocity of detonation, ahd length
for the liq CH4–liq oxygen solns even though of life after impregnation are slightly, but not
the apparent slurry density is higher than those significantly, less than those of expls made
in Table 3. Possibly this is due to incomplete from ordinary non-fireproofed absorbents
reaction, even though Cook emphasizes that he containing the same amount of moisture
used mechanical stirring. Cook’s D is also very Streng & Kirshenbaum (Ref 20) found that
low compared to the D’s in Table 2, for prac- a stoichiometric mixture of liq methane and
tical LOX compns containing solid absorbent liq oxygen will explode from the flame of a
fuels safety fuse
Cook (Ref 18a) presents theoretical calcu- Some LOX compns are liable to self ignite
lations of the detonation parameters of several (Ref 12). Cook (Ref 18a) makes the interest-
carbon black–liq oxygen compns. He gives ing suggestion that many LOX compns do not
 L 24

self-ignite only because they are so cold Streng & Kirshenbaum (Ref 20) exploded
Clark & La Motta (Ref 7) showed that LOX stoichiometric liq methane-liq oxygen by the
made with gas black or lamp black are more discharge of a 0.1 microfarad condenser,
sensitive to impact than the standard Bureau charged to 1500V, across 1–3mm air gaps
of Mines 4W0 straight Dynamite. Impact 5) List of Recent Patents on LOX
sensitivity increased when small amounts of Review of liq air blasting explosives since
iron oxides, aluminum dust or ferro-silicon 1920: a tabulation of 64 German patents
were added to the LOX. Impact sensitivity with brief abstracts. J. Mayer, SS 31, 405–07
also increased as absorbent particle size was (1936) &CA 31, 1211 (1937)
reduced. As the oxygen evapd, impact sensi- Liq oxygen is used with an intimate mixture
tivity, as expected, decreased of a main mass of a solid combustible material
In tests of materials saturated with liq oxygen such as lamp black together with starch in a
and subjected to 7 1–75 lb drop weight” tests, proportion materially to reduce the sensitivity
the following were found acceptable (one de- of the explosive (eg, 1()-SWO of 300 mesh
tonation/40 impacts or none/20): fluorocarbon starch). H. Sauvage, USP 2076279 (1937)
oils & greases,graphite, hrdogenated biphenyl & &CA 32, 3697 (1937)
molybdenum disulfide lubricants, polyethylene Granular carbonaceous material such as
& pure poly fluorocarbons. The following ex- “Bugbird carbon” is impregnated with a solu-
plode: synthetic elastomers & Thiokols, cellu- tion of a fire-proofing material such as Amm
lose-based papers, silicone-based oils & greases, phosphate or Ca chloride and the treated ma-
thermoplastics (except pure Teflon), thermo- terial is used as a carrier for liq oxygen. G.B.
setting plastics, petroleum-based oils and greases Holderer, USP 2119050 (1938) & CA 32,
(Ref 17) 5630 (1938)
LOX are sensitive to sympathetic detona- A carbonaceous absorbent is used together
tion, ie, detonation initiated by a nearby charge with at least‘MYo of phosphoric acid and at
separated from the LOX by an air gap (Refs least %2% water, based on the weight of the
7 & 20) dry carbonaceous material, serving to avoid
The pseudo-LOX of liq methane-liq oxygen undue flammability. A.R.T. Denues, USP
are exploded by bullet impact (Ref 20) 2297538 (1943) &CA 37, 1606 (1943)
LOX compositions are sensitive to friction The prepn of a liq oxygen explosive, es-
(Refs 12 & 14) and to static discharge. Assonov pecially useful in mining operations, is de-
(Ref 13) attributes the premature explosions scribed. It is safe to handle and is character-
of Iiq oxygen on absorbents (fuels) to small ized by high brisance and power. Activated
dust particles. As the charge is dropped into or adsorbent C (1 50–250 mesh), free of hydro-
the borehole, the small particles become de- phobic and of low-temperature volatile ma-
tached from the adsorbent. These particles terials or impurities having low ignition points,
are carried upward by the oxygen vapors and is treated with phosphoric acid or a salt of
become electrostatically charged by friction. phosphoric acid in a wei~t ratio of 2.5 to
18% of C, and sufficient water to form a slurry.
Potentirds of the order of 15000–20000
The slurry is dried with agitation at 250–
volts were measured on thew particles. A dis-
450°F, and the resulting product is then placed
charge of such potentials suffices to initiate
in fireproofed canvas bags and dipped in liq
the LOX. Dust can be minimized by moisten-
oxygen. The amount of oxygen taken up by
ing the adsorbent with 20–2S% of water or by
each part of the treated C is ‘V.8 parts. This
providing specird capsules for the expl. Good
product can be ignited but not detonated by
results were obtained by using briquet ted
fibrous vegetable matter, peat, straw, wood burning paper, and is not affected by rifle
pulp and the like as absorbents. Such briquets fire of 0.30 caliber soft nose bullets. It can be
did not produce dust when dropped from a detonated with a Primacord detonator. L.P.
height of 25m. The brisance of the LOX made Barlow, USP 2723188 (1955) &CA 50, 4510
of such briquets was ordy %3-470 less than (1956)
that of ordinary LOX H. Sauvage, BritP 791930 (1958) & CA 52,
 ,L25

17716 (1958) claims preparation of combustible orifice. Its vel of deton was 14050ft/wc
material (starch) for LOX in the form of com- J.P. Perdrizet, FrP 1132039 (1957) & CA
pressed pellets using a press of at least 15kg/cm2 53, 18487 (1959) claims highly brisant, small-
The disruptive power of these expls compares diameter, low-cost, shock-resistant LOX car-
very well with permanent expls tridges are made with fuels obtained from pulp
F.L. Shea, Jr., USP 2872305 (1959) & CA residue from the extraction of starch from
53, 7597 (1959) claims preparation of LOX potatoes, and sugar from beets
by grinding a suitable bituminous material to F.W. Brown, USP 2879149 (1959) &CA
a preferred particle size of 65–95%’ thru 200 53, 11840 (1959) claims prepn of a low-cost
mesh, and flaah-calcining at >1150°F, prefer- expl having high brisance and gas-forming abi-
ably 1350–1 650°F, with an oxidizing gas lity but much lower fire and detonation sen-
containing sufficient oxygen to oxidize all but sitivity than conventionrd liq oxygen-carbon
about 10% of the volatile matter in the feed, black expls by mixing 10–80% (preferably 20%)
which volatile matter should be w 15–20% of lampblack or carbon black with 90–20% AN
the feed. The product thus obtained is then and then saturating with liq oxygen. Such an
immersed in liq oxygen to form the expl expl has a rate of deton of 6000m/sec. Re-
H. Sauvage, FrP 1112288 (1956) &CA 53, sistance to fire is substantially increased by
8630 (1959) claims preparation of LOX for incorporation of up to %10%0water based on
open-air shooting by the same processes as the solids
usual, but adjusting the sacking of the carbon Andrew Hyslop, Jr, USP 2886424 (1959)
black in such a way that CO is formed in the & CA 53, 15570 (1959) describes processes
explosion. The brisance of these expls is for making mixts of liq oxygen and finely
claimed to be about 50%0higher than that divided fibrous or spherical hydrocarbons (I)
of PA for use as expls. These mixts are less hazard-
J.P. Perdrizet, FrP 1114985 (1956) & CA ous than similar prior-art mixts. The mixing
53, 15570 (1959) describes LOX which are, chamber is cylindrical, open at the top, with a
insensitive to shock and have a prolonged life. funnel-shaped bottom. Thru two nozzles,
They contain as a fuel a dry starch paste ob- jets of atomized oxygen are made to intersect
tained from potatoes or manioc, which is free near the middle of the chamber. A downward
of fatty matter and has a grain size between directed spray of atomized liq (I) is congealed
12 and 64 mesh/cm. In cartridges containing as spheres or strands on mixing with the oxygen.
this type of ffing and used in the vertical The mixt of oxygen and congealed (I) is col-
position, the very finely pulverized starch is lected in a container below the congelation
divided into several compartments by horizontal chamber. Hydraulic, diesel, lubricating oils,
and vertical divisions of impregnated paper or kerosene and gasoline may be used. The
tissue, impermeable to Iiq oxygen, to diminish particles of (I) are preferably <0.01 inch in
the height of the liq oxygen and thereby its diameter. Liq nitrogen may be used to make
flowing out. The fflling is compressed in a the divided (1) for later mixing with liq oxygen.
higher or lower degree to give cakes of variable Water but not carbon tetrachloride, may be
density, preferably having an apparent density atomized into the chamber with 4 parts oil to
of 0.45–O.65g/cc produce less-sensitive expls
S.W. Martin, USP 2812246 (1957) & CA C. McKinley, USP 2939778 (1960) & CA
52, 3346 (1958) claims prepn of impact- 54, 17888 (1960) claims prepn of a liq expl
resistant LOX from an adsorbent carbon ob- which is relatively safe to prepare, store and use
tained by flash-oxidation-crdcination of a finely under controlled conditions, by dissolving in
divided swelling bituminous coal (with a vola- liq oxygen a fuel, preferably methane or its
tile content of >1 2%) in a stream of oxygen- admixture with small amounts of heavier,
contg gas at 800° or more. An expl prepd normally gaseous hydrocarbons; natural gas is
from this carbon was insensitive to impacts an excellent fuel. Stoichiometric proportions
of > 1200ft-lb. It failed to detonate when are used for maximum disruptive effect
burned in semi-confinement with a 0.25 inch Written by J. ROTH
 L 26

Refs: 1) G. Linde, Ber 32,925 (1899) LIQUID EXPLOSIVES

2) G.S. Rice, USBureauMinesTechpaper 243 A liquid explosive, as the term implies, is
(1920) 3) S.P. Howell et al, USBurMines an expl substance that is Iiq at ambient temp.
TechPaper 294 (1923) 4) G.St.J. Perrott, Liquid Explosives (LE) can be pure compounds
Eng&MinJ 117, 610 (1924) & CA la 1909 or mixts of miscible compounds, including
(1924) 5) G.St.J. Perrott, TransAmInst- aqueous solutions. Expls containing a mixt
MiningMetEng @reprint) (1925) &CA 19, of liq and solid phases, eg, the so-called
3020 (1925) 5a) F.W. O’Neil & H. Van Slurry Explosives, as well as Liquid Oxygen
Fleet, TransAmInstMiningMetEng 1562A Explosives (LOX), are described in separate
(1926) &CA 20, 1524 (1926) 6) Marshall articles
3 (1932), 157 7) L.V. Clark & A. La Motta, In the present article we will review the his-
USBurMines RI 3169 (1932) &CA 26, 3669 tory, uses and characteristics of LE under the
(1932) 8) J. Mayer, SS 31,405 (1936) following headings:
&CA 31, 1211 (1937) 9) L. La Magna, 1) History
Industria (Milan) 53, 315 (1939) &CA 36, 2) Typical LE
6347 (1942) 10) A.R.T. Denues, AmInst- 3) Specialized Uses of LE
MiningMetEng, TechPubl 1199 (1940) &CA 4) Detonation Phinomena in LE
34, 5661 (1940) 11) A.R.T. Denues, US- 5) Initiation Phenomena in LE
BurMinesBull 429 (1940)&CA 34, 8281 6) Brief Abstracts of Recent Publications
(1940) 12) Davis (1943), 355–57 on “LE which were not specifically drawn upon
13) V.A. Assonov, Kislorod 1944 No 3, 28 in the, discussion of the items above. Greater
&CA 40, 3605 (1946) 14) W.E. Tournay detail on specific LE will be found in Encycl
et al, USBurMines Bull No 472 (1949) & CA articles on the individual explosive, eg, under
44,4679 (1950) 15) J. Okada, JSocHigh- Ethylene Glycol Dinitrate (EGDN) (Vol 6,
PressCasInd 18, 97 (1954) &CA 49, 16436 pp E259ff), Glycerol Trinitrate (NG) (Vol 6,
(1955) 16) L.N. Marchenko, “Oksilikvity pp G98f0, etc
no Otkrytykh Gornykh Rabotakh” (Oxyli-
quits in Open-pit Mining), Ugletekhizdat, 1 ) History. The first LE of practical im-
Moskva (1955) 17) A.J. Zachringer, Mis- portance was NG. It was discovered by an
siles&Rockets 4, 14 (1958) & CA 52, 21109 Italian chemist, Ascanio Sobrero, in 1846.
(1958) 18) Cook (1958), 5 18a) Ibid, The “taming” of NG by Alfred Nobel is de-
314–15 19) A.D. Yakhontov et al, “Oksldik- scribed in the article on Dynamite in Vol 5,
vity, Ikh Proizvodstvo i Primeneniye” (Oxy- p DI 586-R. Even today NG and its close
liquits, their Manufacture and Uses), GosNauk- chemical relative EGDN are the best known
TekhIzdat, Moskva (1958) 20) A.G. Streng sensitizers for conventional Dynamites. In
& A.D. Kirshenbaum, JChemEngData 4, 127 recent years, however, Slurry Explosives, whose
(1959) &CA 54,897 (1960) 21) T. Waka- Iiq phase is primarily aqueous Ammonium Ni-
bayashi, KoatsuGasu 4 (2), 87 (1967)&CA trate (AN), and which contain no NG or EGDN,
69,68687 (1968) 22) M.A. Cook, “The have been steadily replacing Dynamites (Ref 32)
Science of Industrial Explosives”, Graphic Late in the nineteenth century, Herman
Service & Supply, IRECO Chemicals, Salt Sprengel patented a series of simple oxidation-
Lake City, Utah (1974), 170–77 reduction mixts for use in commercial blasting.
These so-called Sprengel explosives typically
consisted of coned nitric acid, or liquid N02,
mixed with liq fhels such as nitrobenzene,
Liquid DNT. See Drip OilinEncycl5(1972),
carbon disultide, petroleum, etc. They were
D1 546-L to DI 547-L
intended to be mixed immediately before use.
Because of handling difficulties Sprengel expls
never became very popular (Refs 4 & 6)
Mixts of liquid N02 with liquid fiels are
rdso known as Panclastites. They hre very sen-
 L 27

sitive to shock and must be handled most LX-01, also called NTN, an all-purpose
carefully after mixing (Ref 4). In the 1950’s AEC LE, consists of 51 .7/33 .2/15.1 NM/TNM/
liquid N204/kerosene mixts were briefly used l-Nitropropane (Ref 30, pp 18–25)
in strip mine blasting of overburden. Handling MEN-II, also called RX-01-AC, consists of
difficulties again led to the abandonment of 72.2/23 .4/4.4 NM/MeOH/Ethylenediamine
these expls (Ref 30, pp 3–4), A similar mixt was used
Use of LE in minefield clearance during in WWII for minefield clearance (Ref 5)
WWII is described in section 3 Monomethylamine Nitrate solutions contain-
In recent years Iiq Nitromethane, NM, al- ing 10 to 15% water are used as sensitizers in
though rarely used as a practical expl, has Slurry Explosives. Very recently a tank car
been studied from the point of view of initia- filled with such a soln blew up in a railway
tion and detonation theory probably more than yard in Wenatchee, Washington
any other expl, liq, solid or gas. Some of N2O4/fuel,usually in stoichiometric pro-
these studies are discussed in sections 4 & 5 portions, has been used in commercial blasting
and in Anilites (Ref 2 & Vol ‘1, p A443-R)
2) Typical Liquid Explosives. Probably PLX, a 95/5 mixt of NM and ethylenediamine,
the most important class of LE are the liq was used in clearing minefield (Ref 27)
nitrate esters. The most important members TNM/fuel mixtures, such as stoichiometric
of this family are NC (See Vol 6, p G98-R), mixts of TNM and hexane, benzene or nitro-
EGDN (See Vol 6, p E259-R) & DEGDN (See benzene, have been used in specirdized applica-
Vol 5, .p D1 232-L). The mono esters, MeONO ~ tions. They are extremely sensitive since se-
and EtON02 (See Vol ~ p E 143-R), are rdso veral accidents have been reported (Ref 3).
expl but are relatively unimportant in both This great sensitivity may be associated with
expl practice and theory their very small critical diameter (See Vol 4,
Another class of LE are the Nitromethanes. p D653-L). For example, the critical diameter
As already mentioned, NM is probably the of 87.5 /12.5 TNM/NBz is <0. lmm as compared
most thoroughly studied expl. Tetranitro- to M mm for NG (Ref 8a)
methane, TNM, is expl by itself, and forms
very powerful and very sensitive mixts with liq 3) Specialized Uses of Liquid Explosives.
fuels (See below)
Liq NG, EGDN, or their mixts are sensitizers
In recent years, many Fluoro derivatives
par excellence for Ammonium Nitrate, which
have been studied as potential high energy con-
stituents of proplnts. Many of these com- is the main expl ingredient of modern Dyna-
pounds are liquids and some are highly explo- mites. Why they are so effective is stilJ some-
sive. The Bis(2-Fluoro-2,2 -Dinitroethyl) Formal, what of a mystery. Possibly it is because both
FEFO has been studied by the military and the these liquids, and their mixts, are easy to ini-
AEC (Ref 30). Some theoretical studies of tiate, and because, once initiated, they will
Bis-Difluoramino Alkanes have been reported propagate in small (1 mm diameter) columns
(Refs 26 & 26e) Both NC and EGDN are gelled by Nitro-
LE mixts abound although few are used cellulose (NC) and form the matrix of water-
in practical applications. Some of these are resistant Gelatin Dynamites. The NG–NC gels
listed below:
are also the main constituents of double-base
Acenina is an equimolar mixture of
smokeless powders and of triple-base powders
HN03/H2 O/CH ~CN. It was used in a the-
oretical study by Davis et al (Ref 14) (which also contain Nitroguanidine). Nitro-
Anilites are mixts of liq N 204 and benzene. glycerin is also a constituent of many modem
They are not used at present (See Vol 1, p high-energy composite propellants
A443-R) The use of a coned aqueous soln of Mono-
Dithekite is 63/24/14 HN03/Nitrobenzene/’ methylamine Nitrate as a sensitizer for Slurry
H20. Cook used it in his investigation of Explosives was mentioned in the preceding
“detonation plasma” (Refs 6, pp 190–94 & section
Ref 7)
 L 28

The above constitute the main uses of LE, 4J Detonatwn Phenomena in Liquid Ex-
amounting to millions of pounds yearly. How- plosives. Detonation parameters of LE are
ever, none of these uses is for the LE by itself, similar to those of solid expls of comparable
ie, solely as a liq. Neat NG has been used in density and energy content. This is shown in
“shooting” oil wells during the secondary re- Table 1 which is to be comapred with Table
covery of oil. When oil production from a pri- 3-5 of Ref 29
mary well began to lag, four secondary holes Nevertheless, LE detonations exhibit certain
were drilled around the primary well so that all phenomena not usually found in comparable
the holes, primary and secondary, were in the solid expls. Many of the unique characteristics
form of a “five spot”. The secondary holes of LE detonations are ascribable to their homo-
were then loaded with neat NG and shot. geneity, whereas most solid expls are hetero-
Water was then pumped into the secondary geneous. These effects, peculiar to LE, will
holes which forced oil into the primary hole now be described in some detail
by displacement. It was claimed that neat A) Similarities in Detonation in Liquid and
NG produced better rock fracturing and fis- Gaseous Explosives
suring than Dynamites, and thus facilitated Above we have stressed that detonation
oil displacement by the water that penetrated parameters of LE and solid explosives are com-
into the cracked strata (Ref 1) parable. Nevertheless, LE often exhibit detona-
LE may be used for cutting breaks in a tion phenomena that resemble gaseous detona-
forest fire. This is done by stretching plastic tions more than detomtions of solid expls.
tubing along the path where the break is de- A simplistic view, but one that has some merit,
sired, falling it with LE and detonating it. A rationalizes the “dual” nature of LE as follows:
path free of underbrush and foliage is thus the resemblance to solid expls is due to the si-
cleared with very little danger of ignition of milar densities of most LE and solid explosives;
flammables along the path (Refs 21 & 23) the similarities with gaseous expls are due to
Minefield clearance by LE was studied during the homogeneity of LE and gaseous expls
WWH. A system developed in these studies (solid expls except for perfect single crystals
consisted of a number of rubber hoses, placed are heterogeneous)
in parallel on a suspected minefield. They An excellent review (with 27 references) of
were then loaded with a liquid mixture of NM the similarities of LE and gaseous expls is given
and ethylenediamine and detonated. A varia- by Dremin & Rozanov (Ref 17a). They point
tion of this scheme was to gel the above mixt out the following main similarities:
(Santocel ARD proved to be a usable gelling a) Detonation velocity changes insignifi-
agent), spread the gel over the suspected mine- cantly with charge diameter until a critical dia-
field and detonate it (Refs 5, 5a, 5b & 5c) meter is reached below which propagation of
Conversely, a recent development is claimed detonation ceasesabruptly
to have produced a “liquid” land mine. Liquid b) The critical diameter depends strongly
Astrolite, a proprietary expl compn of the on the energy content of the expl. Thus dilu-
Explosive Corp of America, Issaqua, Washing- tion of the expl with inert additives lowers
ton (See Sect 6), is spread over” the ground the critical diameter sharply
c) The detonation is attenuated upon pass-
where it remains “active” for up to 4 days.
age from a narrow container into a large volume,
This “landmine” is not detectable by standard
eg, in passing from a cylinder into an expanding
mine detectors. It is fired by a standard cone
blasting cap (Refs 24& 25) Dremin & Rozanov suggest that these simi-
An itneresting use of LE (usually NM) is larities can be rationalized on the basis of a
in the Explosive Gas Gun (See Vol 6, p E41 9-R) similar reaction mechanism for both LE and
 L 29

Table 1
Experimental Detonation Properties of Some Liquid Explosives (a)

Chapman-Jouguet
Detonation Chapman-Jouguet Heat of Temperature of
Velocity Pressure Detonation Detonation
LE Density ‘CJ AHdet (b) ~CJ
g/cc (m~ec) (kb) Kcal/g (K)
LX-01 (C) 1.24 6840 156 — —
(30, pp 18-25) (30, pp 18-25)
NC 1.60 7700 253 1.48 (d) 4000 (9)
(30, pp 18-45) (30, pp 18+5) 3500 (lo)

NM 1.16 6370 (14) 141 (lo) ‘ 1.23 3700 (9)

(30, pp 18-47) 3380 (13)
3380 (12)
55.5/44.5 1.31 6880 (12) 156 (12) — 3750 (12)
NM/TNM 4650 (g) (10)

TNM 1.64 6360 (12) 159 (12) — 2800 (12)

3100 (9)

TNT (liq) 1.45 (e) 6590 (e) (14) 182 (e) (14) l.ll (f) 3030 (12)
(30, pp 18-81)

(a) Bracketed numbers are Refs

(b) Highly confined samples in a calorimeter; H20 (liq)
(c) 51.7/33.2/1 5.1 NM/TNM/l-Nitropropane,
(d) Computed; should be reliable for this nearly oxygen-balanced explosive
(e) At 93°C
(f) For solid TNT with 0.02 kcal/g correction for heat of fusion
~) For a 50/50 NM/TNM mixture-

gaseous expls. We will examine this Wggestion experiment. Indeed, many authors use measured
in a later section D’s as a normalization parameter or adjustment
B] Experimental Detonation Temperatures factor for their equation of state. Agreement
The last column of Table 1 lists some ex- between computed and measured detonation
perimental detonation temperatures (TCJ) ob- pressure is a better test of the validity of an
tained by optical methods. Although there is equation of state, but this test is still far less
considerable disagreement between measurements sensitive than that provided, by agreement between
made by different investigators, these TCJ values computed and measured TCJ
are probably the best that are now available. Usually detonation temps are high enough
Detonation temperature is a very important to make reaction rates (extrapolated from data
parameter in detonation theory, inasmuch as obtained at much lower temps) at TCJ very fast –
it provides: 1) the best test for the validity of possibly so fast as to be no longer rate con-
an equation of state of the detonation products trolling (See Kinetics in this Vol). Thus, from
(See Vol 4. pp D268–298) and 2) insight into the point of view of chemical kinetics, temps
the chemical reaction rates in the detonation in the pre-detonation shock are of greater
process significance than TCJ (See Sect 5)
Most of the many equations of state (See fiere are conceptual difficulties in the
Vol 4, pp D268ff) proposed for detonation optional methods of measuring TCJ for LE.
products are capable of providing computed However, these difficulties are much less severe
detonation velocities, D, in good accord’with than for solid heterogeneous expls for which
 L 30

“Detonation Light” may have little relationship equations for a steady LVD then becomes a
to the detonation process (Ref 16). The main minimization problem where the LVD velocity
problems in TCJ measurements for LE arise is the minimum velocity consistent with the
from the fact that: 1) the detonation zone is constraints imposed by the coupled rate processes
“screened” by a highly absorbent shock zone D) Inhomogeneity of the Detonafi”on Wave
ahead of it; 2) the radiation received by fie Front in LE. The studies of Shchelkin (Ref 8),
detector comes primarily from the ‘foremost White (Ref 11) and others have demonstrated
front layers of the detonation zone and may that the detonation in most gaseous explosives
not necessarily correspond to T c, which is is unstable and the detonation wave front has
an equilibrium temp and 3) the radiation may a turbulent structure. The investigations of
not be blackbody or graybody. Nevertheless, Dremin and co-workers (Refs 13a, 17a, 17b,
these “detonation temperatures” for LE are 20 & 22), Mallory (Ref 19), Urtiew & Kusubov
the best we have at present. Incidentally, the (Ref 26b), Watson (Ref 26d), Persson (Ref 26c),
values listed in Table 1 appear to agree better Seely et al (Ref 26) & Cook and co-workers
with the BKW equation of state (Ref 12) than (Ref 32) have shown similar effects in the de-
with some other equations of state tonation wave fronts of LE. However, inhomo-
C) Low Velocity Detonation (LVD). LVD is geneities in the wave front were observed only
a phenomenon commonly encountered with LE. for rather “insensitive” expls, particularly in
LVD is a reaction wave phenomenon that expls diluted with inert additives. This is under-
propagates in LE at a constant velocity just , standable if, as suggested by Shchelkin (Ref 8),
slightly greater than the speed of sound in the the size of the inhomogeneities is determined
unreacted liquid. Thus a typical LVD pro- by the reaction time of the expl under classical
pagates at around 2000m/sec whereas a C-J (C-J) conditions. For “sensitive’? LE (eg, NG),
or High Velocity Detonation (HVD) in LE these reaction times are short and inhomogenei-
propagates at 6000 to 8000m/sec (See Table lties are too small to be resolved by instrumenta-
1). Both LVD and HVD can occur with the tion now available. The problem of wave front
same LE depending on confinement, charge instability in all LE is still unresolved. There
diameter and conditions of initiation. LVD may be certain LE that behave classically, ie,
can turn into HVD but not conversely. A their detomtion fronts are stable, uniform and
stable LVD requires that the speed of sound one dimensioned (Ref 18)
in the container wall exceeds the LVD velocity The detonation process, at least in “insensi-
The commonly accepted model for LVD is tive” LE, can bae visualized as follows (Ref
the so-called cavitation model. It is believed 17a): Microinhomogeneities in the LE (eg,
that precursor shocks, propagating thru the fluctuation in density or composition) result
charge container, produce cavitation zones in in non-uniform reaction rates in the shocked
the liq ahead of the LVD. The vapor bubbles LE. Because reaction rates are so strongly de-
(cavities) then act as sites for ignition and growth pendent on temp, these perturbations do not
of chemical reaction to support the LVD wave attenuate and eventually reach the shock front
(Ref 15) of the detonation wave and “bend” it, thus
Chaiken (Ref 28) has shown that the cavi- creating oblique shocks at its leading edge.
tation model is consistent with the classical Oblique or transverse shocks lead to the forma-
C-J picture of detonation, provided that addi- tion of triple shock configurations, and to an
tional constraints, due to the several rate pro- increase in the temp and pressure behind the
cessesthat take place in LVD, are imposed on oblique shocks over that obtainable behind
the classical treatment. In essence,he has smooth shocks. This, in turn, makes for more
shown that not all Hugoniot adiabatic states favorable conditions for the initiation of further
can be accessible from a given initial state, if reaction. At triple wave intersections, conditions
the precursor shock acts to couple rate pro- for reaction are particularly favorable. Thus
cessesahead of the reaction shock front with the wave front becomes a complex three-dimen-
rate processes behind this front. The solution sional cellular structure, quite different from
of the Rankine-Hugoniot (classical detonation) the classical one-dimensional uniform wave
front
 L 31

E) Failure Diameter 7heo~. Closely associated example of heterogeneous initiation. It is de-

with the inhomogeneity of the detonation front scribed in detail in the article on Impact,
in LE is the abrupt change from stable constant Initiation of Explosion By (pp 135-Rff). An-
velocity detonation to detonation failure as the other example of heterogeneous initiation is
diameter of the LE is decreased. Typically the shock initiation of LE containing purposely
the detonation velocity of many LE will change introduced inhomogeneities such as air bubbles,
very slowly as charge diameter is decreased, and Al or glass beads, etc. Detonations initiated by
at a further slight decrease in diameter to df, the such hydrodynamic hot spots are described in
failure diameter, detonation failure occurs the article on Hot Spots (pp H 170-Lff). The
abruptly, even though the detonation velocity uniform bulk heating of LE is an obvious ex-
has dropped ordy about 1% below that at in- ample of homogeneous initiation, but it is
ffite diameter. This phenomenon is inexpli- little different from the bulk heating of solid
cable in terms of the classical theories of the expls which has been described under Ignition
diameter effect on detomtion velocity (See (PP 111ftl Several related articles are in Vol
Vol 4, pp D641 +3). Dremin and co-workers 4 such as Decomposition, Thermal; Deflagration;
(Refs 13a, 17b &“ 22) have developed a theory Detonation, Thermal Theories & Thermochemistry
of failure diameter for LE which have non- and in Vol 2 under Burning and, Burning Char-
uniform detonation wave fronts. In its simplest acteristics. In what follows we will examine
terms this theory states that detomtion failure in detail the shock initiation of homogeneous
occurs when chemical reactions cease because (no bubbles etc) LE, since this is an initiation
oblique (transverse) wave interactions disappear. process unique to LE, although it can also occur
As discussed in the preceding section, most of in perfect single crystals
the chemical reaction for these LE occurs at The classicrd paper on the homogeneous
sites of trarxwerse wave interaction, but it is initiation of LE is that of Campbell et rd
entirely possible that some interaction sites will (Ref 1la). Their views have since received
not produce chemical reaction. Such no-reaction considerable international support (Refs 17,
regions propagate as dark waves. Obviously if 20, 26e & 31), but have been criticized by
the dark waves cover the entire cors$section Cook (Ref 32, pp 3-4). In this writer’s opinion
of the charge, transverse wave interactions there is considerable confusion and possibly a
cease, and, unless the LE is “sensitive” enough misreading of the original paper in Cook’s
to sustain detonation in a “smooth” shock, criticisms, and they will be omitted, although
failure occurs. However, if the dark waves some of Cook’s ideas on the initiation of LE
cover only part of the charge cros~section, will be presented later
detonation proceeds without change in velo-
city. The mathematical consequences of this FIO 8. Space-time
theory are given in Ref 17b and further ex- rcprcscntation of initia-
tion behavior of nitro-
panded by Enig & Petrone (Ref 26a). Although methnne.The initial shock
/ enters the nitromethrme
these quantitative treatments confirm the theory, De nt time O. U, = shock
they are not very useful for a priori computa- vcloc~ty, UP = particle

L
------ -- vcloc]ty, DO = r.letona-
tions of df because they involve parameters
tion velocity, steady
that are not usually available for new LE or ** 0,.:
s(nto, D* - detonation
LE mixtures velocity in compressed
!) I**: ni lromethane, t* = in-
That df for “insensitive” LE is associated t t, T-
duction time
with dark waves is shown by several experimented
studies (Refs 26, 26b & 26d) in addition to the The main ideas of Campbell et al (Ref 1 la)
Dremin refs cited above are best summarized by reference to the figure
above (Fig 8 of Ref 1 la). The entering shock
5} Initiation of Detonation in LE. The heats and compresses the LE. After an in-
initiation of detonation in LE occurs either duction time or delay of t*, thermal explosion
heterogeneously or homogeneously. Impact and detonation occur at the shock entry face
initiation of powdery solid expls is a prime where the LE has been hot longest. This de-
 L 32

tonation travels at a velocity D* >Do in the The induction time t* is of particular in-
shock-compressed LE until it catches up with terest, since it can be compared to the induc-
the original shock. At this point (d, t ~ in the tion time computed for an adiabatic thermal
figure) there is an overdrive in the detonation explosion (See Ref 6, pp 173–74 or Eq 6 of
of the virgin LE, but this decays fairly rapidly Article on Hot Spots, ‘p H 172-R) to provide
to a steady detonation~ropagating at a velo- a check on the correctness of the supposition
city Do. The overdrive occurs because the that the input shockgenerates a thermal ex-
particle velocity associated with D* is higher plosion (at the shock entry face). Unfortunately,
than that of a normal detonation. Note that an exact quantitative treatment of the induction
the “hyper-velocity” detonation D* travels a times of shock-generated’ thermal explosions
shorter distance than d because the initial suffers from: a) uncertainty of the shock-
shock has imparted a particle velocity Up to generated temperature in the LE and b) un-
the interface which has consequently moved certainty in the Arrhenius kinetic parameters
away from x = O over a distance Upt* (activation energy and pre-exponential factor)
In the original Campbell et al paper, NM, (See Kinetics in this Vol)
molten TNT, molten DINA & Dithekite were Campbell et al (Ref 11a) claim to have ‘ob-
the LE examined. Smear cameras, framing tained reasonable agreement between observed
cameras & ionization pin pairs were the diag- and computed induction times. They computed
nostic tools. Later studies, by Travis (Ref their shock-generated temps on the basis of
15a) using electrical transducers, Dremin (Ref constant specific heat, ie, no increase in Cv
17), using electromagnetic measurements of with an increase in temp. It is to be expected
particle velocity, and Persson & Sjolin (Ref that Cv for liquids increases with increasing
26c), using photomultipliers to record de- temp and this expectation has been confirmed
tonation luminosity, are in excellent accord for NM (Ref 31). Thus the Campbell et al
with the Campbell et al findings. Subsequent temperatures of about 11700K for the condi-
studies by Dremin (Ref 20) and Persson (Ref tions shown in Table 2 are too high. Based on
26c) showed that NC and EGDN also follow recent studies (Ref 31) these temps should be
this initiation mechanism. Berke et al (Ref about 1050°K. This means that a lower acti-
26e) also found that sever~ liq fluoramino vation energy then that used by Campbell et
alkanes behave analogoudy to NM, NC etc. al is necessary to get agreement between ob-
Most of the original and later studies were served and computed induction times for NM
made with NM as the principal LE. Conse- shock-heated to 1050”K. Although the above
quently all our subsequent discussion refers discussion suggests that quantitative agreement
to NM between experiment and theory is still to be
Table 2 gives average values of the NM param- achieved, the qualitative model for the shock
eters measured by Campbell et al (Ref 1la) initiation of LE appears to be on solid ground
Cook and his co-workers have championed
Table 2
a different model for the shock initiation of
Shock Velocity Us 4.5 LE (Refs 6, pp 173–94 & 32, pp 292–96).
(mm/ psec) In essence, this model states that initiation
Particle Velocity Up 1.7 occurs when a shocked region of LE becomes
(mm/ psec) “thermally superconductive” (as a result of
Input Pressure (kbar) 86 rising temp due to partial decompn of the
Detonation Velocity in 10.4 shocked LE) and a “heat pulse” flashes across
Compressed NM, D* the shocked LE and catches up with the ori-
(mm/psec) ginal shock front. As described in the article
Detonation” Velocity 6.26 on Heatpulse (p H59-L), alternate explanations
Steady State, Do are possible for some of the observations that
(mm/~sec) Cook considers to be the main experimental
Induction Time, t* %2 support for his “heat pulse”. Similarly, Dremin
(psec) et al (Ref 17) have suggested an alternate ex-
 L 33

planation for the phenomenally rapid “flash- NC was observed under these conditions but no
across” observed in some shock initiation ex- detonation. The possibility of light, produced
periments with LE by the shock compression of air pockets in
porous expls, contributing to the initiation and
61 Bn”ef Abstracts of Recent Publications propagation of detonation in porous expls is
on LE: discussed
a) Effect of Pressure on the Burning of Refi A.N. Dremin & S.D. Savrov, Doklady-
LE. An abrupt change in the burning of some AkadNauk 179 (3), 624 (1968) & CA 66,116108
LE occurs as pressure on the LE is increased. (1968)
Two alternate explanations for this effect e) Deflagration to Detonation Transition
are: 1) gas phase reactions are moved closer in LE. High-speed photography was used to
to the liq surface by increasing pressure, thus study the growth of explosion in various liq
transferring more heat to the LE and 2) increase expls. The liquids investigated included NC,
in the burning rate generates turbulence in the NM/HN03 mixts, H202 /Ethrmol mixts and
combustion front which then increases the heat DE,GDN. In one experimental arrangement, a
exchange bet ween combustion gases and the thin Mm of expl was confined between trans-
LE. Experiments with EGDN and EGDN gelled parent plates. Deflagration at the center of the
with a small amount of NC favor explanation (2) flrn was initiated by the rapid discharge of a
Refi K.K. Andreev et al, RussJPhysChem 35 condenser across a spark gap. The study rd-
(2), 204 (1961) lowed the growth of the burning and the
b) Iriitiation of LE by Gas Phase Deto- transfer to detonation to be photographed in
nation. Detonation of stoichiometric methane- detail
oxygen gas mixts was used to initiate liquid Ref: G.D. Coley & J.E. Field, ProcIntnCongr-
TNM-benzene mixtures. For 1.5/1 (by volume) HighSpeedPhotogr 1970, p 466 & CA 75,
TNM/benzene, initiation occurred only at initial 89718 (1971)
gas pressures above 2 atm. Initiation delay de- f) LE consisting of hydrazine, Hydrazine
creased with increasing initial gas pressure. For Nitrate, water (with & without added ammonia
4/1 (by volume) TNM/benzene (stoichiometric) or AN) & a thickening agent is claimed. This
the critical initial gas pressure was 0.66 atm. appears to be one of the “Astrolite” expls
The influence of initial pressure is explained Refi R.M. Bridge forth et al, USP 3523047 &
in terms of more efficient heat transfer from CA 74, 14701 (1971)
the gas detonation to the LE, but there are g) Calculated Shock Temperatures for
compensating effects and the surface temp of LE. A modification of Walsh-Christian model
the LE varies only mildly with initial pressure for metals was used in calculating shock temps
Ref V.E. Gordeev et al, FizGoreniya i Vzryva in NM, liq TNT and four liquid Bis(Difluoratino)
1 (2), 12 (1965) &CA 64, 1894 (1966) Alkanes. In this modification the heat capacity
c) A Generalized Shock Hugoniot for Organic increases with temp rather than staying constant
Liquids. The shock compressibility (1-h.rgoniot) as in the Walsh-Christian model
(See pp H179-Lff) of organic liquids, including Refi R, Shaw, JChemPhys 54,3657 (1971)
several LE, is expressed in the following general
form: Written by J. ROTH
u= 1.2C0 + 1.7~ Refs: 1) VanGelder & Schlatter (1927), 396
where U is shock velocity, Co is ambient sound 2) C.J. Bain, “Tests of Liquid Nitrogen Explo-
velocity in the liq and v is particle velocity sive”, PATR 985 (1939) 3) A., Stettbacher,
Refi I.M. Voskoboinikov et al, FizGoreniya i TechIndSweizChemZtg 24 (1941)&CA 36,
Vzryva 3 (4), 585 (1967)&CA 69, 37522’(1968) 4339 (1942) 4) Davis (1943), 353–55
d) Initiation of LE by High Intensity 5) L.H. Eriksen, “Properties of Liquid Explo-
Light. Stoichiometric mixts of TNM/benzene sives”, PATR 1524 (1945) 5a) L.H. Eriksen,
(See abstract b) were initiated by the radiation “Sensitized Nitromethane Liquid Explosives
of an argon flash bomb. Chemical decompn of for Mine Field Clearance”, PATR 1565 (1945)
 L 34

5b) L.H. Eriksen, “Sensitized Nitromethane of Explosive Behavior”, AMCP 706-180 (1972)
Liquid Explosives for Mine Field Clearance”, 30) B.M. Dobratz, “Properties of Chemical
PATR 1660 (1947) 5c) S. Axelrod, “Liquid Explosives and Explosive Stimulants”, UCR L-
Explosives”, PATR1681 (1948) 6) Cook 51319 Rev 1 (1974), Lawrence Livermore
(1958), 14, 173–74 & 190–94 7) M.A. Laboratory, Livermore, Calif 31) P.c.
Cook et al, 3rd ONR SympDeton (1960), 150 Lysne & D.R. Hardesty, JChemPhys 59, 6512
8) K.I. Shchelkin, ZhurEksptl i TeoretFiz 36, (1973) 32) M.A. Cook, “The Science of
2 & 600 (1959) &CA 53, 15724 (1959) Industrial Explosives”, Graphic Service &
8a) K.K. Andreev & A.F. Belyaev (1960), Supply Co (IRECO Chemicals, Salt Lake City,
197–98 9) I.M. Voskoboinikov & A. Ya. Utah) (1974), 16, 292-96, ?98 & 300–01
Apin, Doklady 130, No 4, 854 (1960)& CA
56, 619 (1962) 10) I.M. Voskoboinikov &
G.S. Sosnova, ZhurPrikladMeckh i TeckhFiz LIQUID PROPELLANTS
No 4, 133 (1961) &CA 56, 3712 (1962) Definitions & Overview. Liquid Propellants
11) D.R. White, PhysFluids 4,498 (1961) (LP) are liq substances that can be transformed
1 la) A.W. Campbell et al, PhysFluids 4, 498 into gases(usually hot) which act as driving
(1961) 12) C.L. Mader, Los Alamos Rept jets in a propulsion system. Propulsion systems
LA-2900 (1963), 14–17 13) J.T.A. Burton can be divided into rockets and jet en~”nes. The
& J.A. Hicks, Nature 202, 758 (1964) forward thrust of both rockets and jet engines
13a) A.N. Dremin & V.S. Trofmov, Zhur- is generated by the rearward ejection of a
PrikladMekh i TekhFiz, No 1, 126 (1964) & fluid jet thru nozzles mounted on the rocket
CA 61, 1698 (1964) 14) W.C. Davis et al, or jet engine (Ref 12, pp 439-41). In a rocket
PhysFluids 8, 2169 (1965) 15) R.W. Watson this fluid jet originates entirely from containers
et al, 4th ONR SympDeton”(196S), 117 (tanks) within the rocket. Jet engines, on the
15a) J.R. Travis, Ibid, 609 16) J.H. Black- other hand, ingest the surrounding medium (air
burn & L.B. Seely, TransFaradSoc 61, 537 or water) to produce their exhaust jet. Thus
(1965) 17) A.N. Dremin et rd, Combus- rockets can function in a vacuum (space)
Expl & ShockWaves 1, 1 (1965) 17a) A.N. whereas turbojets, ramjets etc, camot. Since
Dremin & O.K. Rozanov, Combus Expl & Jets are described in this Vol (See under Jet
ShockWaves 1 (2), 63 (1965) 17b) A.N. Fuels, pp J68-R f~ this article deals primarily
Dremin & V.S. Trofnov, 10th SympCombstn with rockets and liquid rocket propellants
(1964), 839 18) A.N. Drernin & S.D. Savrov, It is usually understood that a rocket motor
FizGoreniya i Vzryva 1, 36 (1966) 19) H.D. is that part of the propulsion system in which
Mallory, JApplPhys 37,4798 (1966) 20) A.N. the propellants are transformed into the ex-
Drernin et al, FizGoreniya i Vzryva 3, 11 (1967) haust jet, while a rocket engine is the entire
21) Anon, MachineDesign 40, No 28, 6 (1968) system, ie, the rocket motor, the proplnt con-
22) A.N. Dremin, 12th SympCombstn (1969), tainers, pumps, etc. In conventional solid proplnt
691 23) G. Cohn, Edit, Expls&.Pyrots 2, rockets, the motor and the engine happen to be
No 6, 1 (1969) 24) B. Johnson, Ordn 53, the same piece of apparatus, but this is not so
613 (1969) 25) G. Cohn, Edit, Expls&Pyrots in liq proplnt rockets
2, NOS 7 & 8 (1969) 26) L.B. Scaly et al, Liquid Propellants, sometimes called fiopergoh
5th ONR SympDeton (1970), 89 26a) J.W. if used for rocket propulsion (Ref 23), are di-
Enig & F.J. Petrone, Ibid, 99 26b) P.A. vided into two classes: monopropellants and
Urtiew & A.S. Kusubov, Ibid, 105 26c) P.A. bipropellants. A monoproplnt is a single sub-
Persson &T. Sjblin, Ibid, 153 26d) R.W. stance or a homogeneous compatible mixt that
Watson, Ibid, 169 26e) J.G. Berke et al, can be caused to react in the rocket motor
Ibid, 237 27) W.R. Tomlinson Jr & O.E. (combustion ch~ger) to generate the gases
Sheffield, EngDesHndbk, “Properties of Explo- that form the exhaust jet. A bipropellant con-
sives of Military Interest”, AMCP 706-177(1971) sists of two Iiq reactants – usually a fuel and
28) R.F. Chaiken, AstronauticaActa 17, 575 an oxidizer. The gas-forming process in a mono-
(1971) 29) Anon, EngDesHndbk, “Principles proplnt is initiated by heat and/or catalysts.”
 L 35

These agents can also initiate the gas formation 2) Representative LP Compositions
of biproplnts after the components are mixed. 3) Representative LP Applications
Certain bipropellants can, however, self-ignite 4) Performance Characteristics of LP
merely upon mixing. These are called Hyperbolic 5) Sensitivity and Hazards of LP
Propellants or Hypergols (See Hyperbolic Pro-
1) History. An excellent overview of the
pellants in this Vol, pp H254-L to H259-R)
history of liquid propellants, LP, and propulsion
Levy (quoted in Ref 23) also suggested the
systems using LP is given by Malina (Ref 12,
following additional designations: Ciztergols are
pp 10–23) and Truax (Ref 12, pp 23–26). In
LP that are decomposed by the action of cata-
what follows we draw heavily on this overview.
lysts; Monergols are homogeneous liquid bi-
The history of LP is conveniently divided into
propellants; Lithergoh are heterogenousbi-
three periods: Pre-WWII, WWII & Post-WWII
propellants, eg, solid C & liquid oxygen
Pre-WWII. The use of LP for space travel
LP are often classified into storable and
appears to have been first suggested by Ziol-
cryogenic liquids. The former, as implied,
kowsky in 1898, but not published until 1903
are stable liquids under ambient operating com
(Ref 1). He #so sugested the “pi@-back”
ditions. The latter require a liquefying plant as launch, ie, a rocket launched from another
they are gasesunder ambient conditions rocket, although this principle had been used
A universally accepted measure of the ef- much earlier in fireworks displays
fectiveness of LP is the specific impulse, usually The subject of LP remained quiescent early
designated by Isp. It is defined by: in the 20th century and thru WWI. In 1928,
1sp = c/g and Esnault-Pelterie (Ref 2) lectured on LP com-
c = Ve + (pe – p ~Ae/fi bustion problems. Between 1930 & 1933 the
where Verein fiir Raumschiffahrt (Society for Space
Ve = exhaust jet velocity Travel) experimented with LP engines using
pe = static pressure at the exhaust combinations of Iiq oxygen and gasoline or aq
pm = ambient pressure alcohol (Ref 12, pp 10–23). This society was
Ae = area of exhaust nozzle the precursor of the group that developed the
m = rate of exhaust mass flow V-2 rocket during WWH
The American Rocket Society began experi-
g = acceleration of gravity
menting with LP in 1932, using primarily liq
The units of ls~ are (lb-see)/lb or, as commonly oxygen-gasoline systems. Their work was later
used, sec (by c~ncelling the lbs in the numerator summarized by Wyld (Ref 6). In 1941 several
and denominator). For further details on the members of this society formed Reaction Motors,
measurement & computation of Ispwe Ref 12, Inc to produce the liq oxygen-alcohol engine for
pp 440-4 & 464-71 the Bell X-1 supersonic aircraft. In 1936
Subjects related to LP were previously de- Goddard summarized his studies of LP (Ref 3).
scribed in the following Encyclopedia article; His studies dealt more with combustion chamber
Burning & Combustion, Vol 2, pp B351 & B361, design and functioning than with specific LP.
with additional Refs in Vol 3, pp C425–8 & The Guggenheim Aeronautical Laboratory was
in Vol 4, pp D 173–75; Hydrazine, Its Salts started in the same year at the California In-
and Derivatives in this Vol, pp H 190-L to stitute of Technology for the purpose of study-
H206-R; Hydrogen Peroxide in this Vol, pp
ing design fundamentals of solid and liq pro-
H21 8-R to H222-L; Hyperbolic Propellants pulsion systems. A year later, Malina (Ref 4)
in this Vol, pp H254-L to H259-R; Ignition
published a paper on the chWacteristics of LP
in this Vol, pp 111 to 130-R; Jet Propulsion motors
in this Vol, pp J77 to J83; Liquid Explosives
These developments up to 1940 are well
in thisVol, pp L26 to L34
summarized by Mrdina (Ref 12, pp 10–23)
General references on the subject of LP are:
and we quote:
Refs 7, 9–15, 17, 18, 21, 23 & 27–29
“The literature published up to 1940 shows
In the present article we will review:
that the basic problems of designing successful
1) LP History
liquid propellant engines were correctly stated,
 L 36

at least in major outline. The properties of a Motoren Werke (BMW). By 1945 some 6000
number of propellants were fairly well known, fuel-nitric acid mixtures had been tested. Some
especially those combinations using liquid oxygen of these were hyperbolic
as the oxidizer. In connection with the rocket During WWII LP research in the USA was
motor, the thermodynamics of the combustion concentrated at the Jet Propulsion Laboratory
process and of the flow of the gaseous products of the California Institute of Technology,
thru the exhaust nozzle to produce thrust, Aerojet Engineering Corp, Reaction Motors,
were understood; and a beginning had been Inc, and the Navy Bureau of Aeronautics. These
made in solving the cooling problem, and the efforts are summarized in books by Zucrow (Ref
preliminary stages of development of suitable 7) and Sutton (Ref 9)
systems of propellant wrpply had also been One of the main LP developments of the Jet
reached. It may be noted that the greatest ad- Propulsion Lab efforts, later commercialized by
vance to be recorded in this article was the me- Aerojet, was the nitric acid-aniline JATO engine.
chanical design of the complete engine, although Monopropellant engines were also investigated
a number of basic discoveries were made, es- Liquid oxygen-alcohol proplnts were studied
pecially in the domain of propellants, and the at Reaction Motors, and resulted in the 1500
theory for guiding design was greatly expanded.” N4C engine, which powered the experimental
WWII. From 1932 onward, the study of LP X-1 supersonic airplane (Ref 5)
and LP engines proceeded under a cloak of The Bureau of Aeronautics investigated
secrecy in Germany. Much of this effort was nitric acid-aniline proplnts for JATO’S for large
concentrated at an Army establishment at flying boats such as the PBY-2 (Ref 8). They ‘
Peenemunde. This work culminated in the de- also developed a prototype engine for the
velopment of the V-2 rocket (originally called Gorgon, a radio-controlled winged missile. The
the A-4) in 1942. The LP of the V-2 consisted proplnt for Gorgon was a combination of mixed
of liq oxygen mixed with 75/25 ethanol/water. nitric-sulfuric acids and monoethylaniline
Mixing pumps were driven by an impulse turbine Post-WWII. After WWH most LP R&D
powered by steam from a hydrogen peroxide shifted from Germany to the USA and the USSR.
generator. This rocket motor delivered a Technical progress since 1945 in LP for rockets
55,000 lb thrust, at sea level, for 65 seconds to can be characterized by a host of minor im-
give an average specific impulse of 223 lb-see/lb. provements rather than major advances, and
The original V-2 traveled a distance of 120 miles some spectacular applications of LP in rockets
Similar LP systems were also developed and for military use and for space exploration, eg,
used at Peenemunde for jet-assisted takeoff in ICBM’S (Intercontinental Ballistic Missiles)
for aeroplanes (See JATO in this Vol, p,J67-L and in USA & USSR Moon, Mars & Venus
The Germans also developed LP systems “shots”. Thus the major developments since
based on hydrogen peroxide both by itself and WWII have been primarily in the application
mixed with fuels. The specific impulse of de- of existing, though improved, propulsion systems
composing 80% hydrogen peroxide (.’cold” to such highly publicized rockets as Sputnik,
engine) was a rather low 155 lb-see/lb. This Vanguard, Soyuz, Saturn, Vostok, Apollo,
was raised to 210 lb-see/lb by burning hydrogen Explorer, etc
peroxide with a fuel mixture of 30/57/13 hy- Efforts in LP per se have been largely re-
drazine hydrate/methanol/water. Mixtures of stricted to improving performance by increasing
hydrogen peroxide and hydrazine hydrate are the combustion pressure; and the developing
hyperbolic (Self-igniting – See Hyperbolic and testing of “exotic” mono and biproplnts,
Propellants (pp H254-L to H259-R) and such as the NF compounds and Fluorine-NHs
Hydrazine, Its Salts and Derivatives, pp H 190-L and Fluorine-H2 biproplnts (See Sect 2). So
to H206-R, in this Vol. These LP were used far there is no mention in the open literature
mostly in turbo pumps for Jet aircraft of the practicrd use of “exotic” proplnts (Ref
Work on LP engines using nitric acid as the 30, p 312)
oxidizer was carried out at the Bayerische 2) Representative LP Compositions. Com-
pared to the vast number of possible or even
 L 37

Table 1

Constituents Oxidant: Specific Specific

Combustible Gravity, Impulse,
Oxidant Combustible Ratio glee Sec Remarks

100% Nitric acid Turpentine 4.4 — 221

Fuming Nitric acid (FNA) Ethanol 2.5 — 219
FNA Aniline 3.0 — 221
FNA Ammonia 2.2 — 225
FNA JP-4 — — 225
99% Hydrogen peroxide Ethanol 4.0 — 230
99% Hydrogen peroxide JP-4 6.5 — 233
—
99% Hydrogen peroxide
Liquid oxygen (LOX)
Hydrazine
Ethanol
—
1.5 0.97
245
242
1 Fuels most
commonly used
LOX JP-4 2.2 1.02 248 f
LOX Turpentine 2.2 — 249
LOX Ammonia 1.3 — 250

Hydrogen peroxide Nitromethane — — 227

N204 Hydrazine — — 249
N204 Hydrogen 11.5 0.565 279
FNA Hydrogen 12.6 0.60 298
LOX Hydrogen 2.9 0.23 345
70% LOX
30% Ozone
100% Ozone
1 JP-4
JP-4
2.3
1.9
—
—
253
266
100%Ozone Ammonia 1.13 — 267 So-called
100%Ozone Hydrazine 0.63 — 277 “Zip-fuels”
(high energy fuels
Fluorine JP-4 2.6 — 265 in the USA)
Fluorine, Ammonia 2.6 — 288
Fluorine Diborane 5.0 — 291
Fuels most
(B2H6)
— commonly used
Fluorine Methanol 2.37 296
Fluorine Hydrazbe 1.98 — 298
Fluorine Hydrogen 4.5 — 352
Fluorine Hydrogen 9.4 0.46 371
100% Ozone Hydrogen 3.2 — 369
10WOOzone Hydrogen 2.65 0.23 373

practical biproplnt compositions, very few mono- number of usable oxidizers is fairly limited.
proplnts have been studied and even fewer are Storable oxidizers include: nitric acid (with
used. The following monoproplnts have been and without added N02 ), Hydrogen Peroxide,
investigated: perchloric acid, Tetranitromethane, N 204.&
Hydrogen Peroxide, Hydrazine, Nitro- CIF ~. Of these only nitric acid and Hydrogen
methane, sym-Dinitromethane and Methyl Peroxide are of practical use. Perchloric acid
Nitrate in ethanol (Refs 10 & 23).- Of these or Tetraidtromethane are too explosive when
only Hydrazine and Hydrogen Peroxide have mixed with fuels, and N204 or CIF ~ are not
been used and are being used in practical pro- really storable, as they boil at 22° and 12°
pulsion systems .,, respectively (Refs 10 & 23)
As stated above, many oxidizer-fuel combina- The most commonly used cryogenic oxidizer
tions are usable as biproplnts. However, the is liquid oxygen (LO). Other cryogenic oxidizers

.-
 L 38

include: N2 04, ozone, fluorine, chlorine- then the reaction products will consist of low
tritluoride (C1F3), nitrogen tetrafluoride (NF.4), molecular weight compounds at high temps,
bromine pentafluoride (BrF5 ), perchloryl thus assuring good performance;
fluoride (C103F), fluorine monoxide (F20), c) The proplnts should have large densities
and fluorine dioxide (F202) (Refs 10, 23 & 28) in order to minimize the dead weight of storage
Vast numbers of fuels may be combined with tanks;
the above oxidizers to form biproplnts. Many d) The oxidizers and reducing agents are
hyperbolic biproplnt systems are listed in this best handled as liquids. Hence it is desirable
Vol, pp H254-L to H259-R, under Hyperbolic to obtain proplnts which are normally liq in
Propellants. The foregoing tabulation (Table the operating temp range of service units (ie,
72, p 317 of Ref 23) lists several “common” from about –40 to +60”). For substances
biproplnts such as liquid oxygen and hydrogen special
Other, generally more “exotic” biproplnts cooling units must be provided;
are given in Table 10.2, p 165 of Ref 28 which e) Since it may be necessary to store the
is shown as Table 2 below: proplnts for long periods of time before use,

Table 2

Properties of Liquid Propellant Systems

Oxidant/ Is Endothermicity of fuel Tc Te Products at TE

Fuel Oxidant fuel ratio (see) (AHf’,2 ~SO,tg),kcdhole) (“K) ~K) ME (> 5% of total)

H2 O* 4“00 391 0 2980 1350 10.08 H20, H2

B2H~ o~ 2.00 344 7“5 3846 2592 20.32 H2, HB02, B203
C2H2 o~ 1.80 327 54”2 4172 2600 24.07 CO, H20, H2 , C02
N2H4 02 0.90 313 22.8 3410 1928 20.29 H20, N2, H2
Kerosene 02 2.60 3oi –5.9 3623 2228 25.29 H20, CO, C02, H2
H2 F2 9.00 410 o 4117 2018 13”64 HF, H2
B2H~ F2 5.20 371 7.5 4934 3130 22.52 HF, BF, H2 , H
C2H2 F2 1.50 306 54.2 4109 3294 29”96 HF, C(s)
NzH4 F2 2.30 363 22.8 4687 2702 21.33 HF, N2, H2
Kerosene F2 2.40 317 –5”9 3917 2748 25o26 HF, C(s)
Hz F2 9.00 410 o 4117 2018 13.64 HF, H2
H2 o~ 3“50 424 34.1 3123 1426 9“07 H2, H20
H2 F20 5“90 410 8 3589 1662 11.36 H2, HF, H20
Hz NF3 13”30 350 –29.7 3868 1682 16.43 HF, H2, N2
Hz C1F3 11.50 318 –39 3390 1356 16.78 HF, Hz, HC1
H2 F202 5“00 407 4.7 3362 1504 10”57 H2, HF, H20

Penner (Ref 10) has listed eleven attributes good proplnts should have high storage stabiLity,
that make an ideal liq biproplnt system. We ie, they must not decompose or change chemi-
quote some of them below: cally in any way during storage so that their
“a) Small negative or preferably positive use as a’proplnt is impaired;,
standard heats of formation of the reactants; f) For large-scale use it is, of course, im-
b) The reaction products should have low perative that proplnts which are readily avail-
molecular weights and large negative heats of able and preferably also of low cost are em-
formation. If conditions (1) and (2) are met, ployed. In practice this last requ~ement is
 L 39

essential since experience has shown that rare Thrusters are rockets for maneuvering and con-
and expensive chemicals which are needed in trolling the attitude of space vehicles. The usual
large quantities ussually become cheap and monopropellant for thrusters is catalytically de-
readily available in the course of time; composed H ydrazine. The usual catalysts are
g) The biproplnt mixt in a liq-fuel rocket iridium, rhodium or ruthenium and their mixts.
&ould be spontaneously combustible with For a review of Hydrazine thrusters see Refs
minimum time lag; and 33, 34 & 35. Russi (Ref 34) emphasizes that,
h) The reaction products should not be in spite of many studies and the general ac-
excessively corrosive or form solid deposits ceptance and apparent success of hydrazine
thereby leading either to increased or de- thrusters, new rocket motor design is still
creased ‘nozzle throat diameters” largely empirical. A biproplnt consisting of
31 Representative LP Applications. Before Hydrazine mixed with Hydrazine Nitrate has
proceeding with a description of the specific also been tried in thrusters but is no longer
uses of LP, it is instructive to compare them popular
with solid propellants. The choice between LP An informative compilation of the uses of
and a solid proplnt for a given application de LP is given in Table 3 from Ref 30a
pends on several “factors such as: specific im- The two interesting applications of LP are
pulse, safety, storability, rocket engine design in gas generation and in specialized ammunition
& special requirements The use of a monoproplnt gas generator offers
LP generally have the following advantages signii3cant advantages over conventional solid
over solid propellants: proplnts because of its capability for variable
a) Higher Specific Impulse; b) Rocket engines demand operation, high performance, solids-
with LP can be precisely crdibrated prior to free exhaust and constancy of flow over a wide
launching; and c) Rocket engines with LP can temp range. The monoproplnt gas generator
be throttled and even restarted after complete eliminates the need for’ falters and design com-
throttling promises such as oversize proplnt grains to ac-
LP generally have the following disadvantages count for the variation in burn rate over the
compared to solid propellants: temp range of –65 to +165°F (Ref 24)
a) More complex and less rugged rocket engines; Ammunition containing bulk-loaded mono-
b) Poorer stability; and c) Poorer reliability proplnts have the characteristics of low flame
The most spectacular, though hardly the temp, high energy, reduced smoke and flash,
most elagant, use of LP was hi the first stages and reduced fouling and longer barrel life.
of early ICBM and space exploration rockets. There is one disadvantage, however, that has
These used clusters of LP engines to achieve prevented exploitation of these good attri-
lift-off via “brute force”. For example, the butes. Liq monoproplnts do not burn stably
original Sputnik, Vostok, Atlas,, Titan, Vanguard, under the conditions existing in bulk-loaded
Thor, Apollo & Saturn used clusters of engines cartridges. High and erratic pressures occur,
powered with liquid oxygen/kerosene mixtures accompanied by high frequency, high ampli-
for the lift-off stage (Refs 30a & 32). More tude pressure excursions. It was shown that
specifically, Saturn I had a cluster of eight bulk loaded monoproplnts, eg, alkyl nitrate
liquid oxygen (LO)/kerosene H-1 rockets. mixtures, encapsulated to form small spheres,
Later Saturns and Titans used LP of higher produced proplnts of very repeatable and uniform
Isp, eg: Saturn-II and Saturn-IVB used LO/ initial surface area similar to conventional
liq Hydrogen; Post 1959 Titans used N204/ smokeless ball powder. Proper ignition and the
Hydrazine derivatives; Jupiter-C used LO/
resulting combustion involving the liquid drop-
Hydrazine derivatives; and the French Diamant
lets prevents agglomeration into a large unstable
I space booster used nitric acid/turpentine (Ref
bulk (Ref 25)
32)
More sophisticated uses of LP, which take
advantage of the LP engine’s capability of being
throttled and restarted, are in thrusters.
 L 40

Table 3

Current Liquid Bipropellant Applications

Engine System,
Common Thrust Level,
Propellant System, Designation Ibs. Application Area

L~ /RP-l (a) Thor 170,000 Space booster, IRBM

(Delta 1st stage)
H-1 200,000 Uprated Saturn I
Blue Streak 300,000 Space Booster
Titan I 300,000 ICBM
(lst stage)
80,000
(2nd stage)
Atlas 370,000–390,000 Space booster, ICBM
F-1 1,500,000 Saturn V, S-IC
Lo*/H* Centaur 15,000 Uprated Saturn I
S111(2 engines)
Saturn I, S11
D
(6 engines)
J-2 200,000 Saturn V, S11& S111
L02/NH3 , X-15 15,000–58,000 Experimental rocket plane
L02/C2H50H Redstone 75,000 SRBM
H20Z7JP:4 (l), JP-5 (a) *AR-2, 3 3300–6600 Auxiliary rocket engine
. for aircraft
Warrior 3500–10,200 Auxliary rocket engine
for aircraft
IRFNA (b)/UDh4H (C) AJ1O-118 7500 Space booster (Delta
2nd stage)
Lance Surface-to-surface missile
Agena 16,000 Space booster (2nd stage)
IRFNA (b)/MAF-l (d) Bullpup Air-to-surface missile
IRFNA (b)/~F-3 (e) TD- 174 Air-to-air missile
IRFNA (b)@AF-4 (f) P4 550 (booster) Target drone
106 (sustainer)
IRFNA (b)/JP4 (a) . Aerobee 100 2600 (total) “ , Sounding rocket
sustainer
lRFNA (b)/aniline- Aerobee 150 and 4100 (totzd) “ Sounding rocket
furfuryl alcohol 150A sustainer
IWFNA (g)/turpentine Emeraude 62,700 Space booster
N*04/N~H4– Apollo service 100 - Reaction control
UDMH (C) (50-50) module RCS
Ullage rocket 1750 Saturn V, S-IVB Ullage Control

(continued)
 L 41

Table 3 (continuation)
Engine System,
Common Thrust Level,
Propellant System, Designation lbs Application Area

N*04/N*H4– AJ1O-131 2200 General purpose space engine

UDMH (C) (50-50) F750 L2.2K 2200 Multiple restart space engine
Lunar module 3500 Lunar module liftoff (moon)
ascent engine
F720 L8.OK 8000 Multiple restart space engine
Transtage 8000 Upper stage propulsion
N204/N2H4– Lunar module 1050–10,500 Lunar landing engine
UDMH (C) (50-50) descent engine
Apollo service 21,900 Space propulsion
module
YLR113-AJ-1 50,000–150,000 Rocket sled
Titan II 430,000 Space booster, ICBM
(lst stage)
100,000
(2nd stage)
N204/MMH (h) Advanced Syncom 5 Reaction control
RCS
Gemini RCS 25 (two 8-engine Reaction control
sets)
Transtage ACS 25 (4 engines) Attitude control .4
45 (4 engines)
Apollo command 93 (two 6-engine Attitude control
module sets)
N200/MMH (h) Gemini OAMS 25 (8 engines) Orbital change
85 (2 engines)
100 (6 engines)
Radiomic 85–100 General purpose attitude control

a) RP- 1, JP-4 & JP-5: Kerosene Fractions

b) IRFNA: Inhibited Red Fuming Nitric Acid
c) UDMH: Unsym Dimethyl Hydrazine
dl MAF-1 : 50.5% DETA, 40.5% UDMH, 9% CH3CN
e) MAF-3: 80’ZODETA, 20% UDMH
f) MAF-4: 40% DETA, 60% UDMH
g) IWFNA: Inhibited White Fuming Nitric Acid
h) MMH: Monomethyl Hydrazine
 L 42

4} Performance Charactm”stics of LP. Additional computational results are given in

Specific impulse, Is , probably the most ac- Table 2 which also shows major exhaust gas pro-
cepted measure of 1 P performance, was de- ducts. Parametric charts of rocket performance
fined in Sect 1 and tabulated in Tables 1 & 2. for specific missions are given by Jortner (Ref 17,
The thrust, F, of a rocket is given by p 47 1). Further data on rocket performance from
the point of view of weight and volume limited
F=rnc systems are presented by Mellish & Gibb (Ref 17,
P 447)
where rnand c were also defined earlier. Typical At the high combustion and exhaust temps
thrust levels for “practical” LP systems are shown in Tables 2 & 4, many of the combustion
given in Table 3. For an ideal rocket other products will dissociate (eg C02 = CO+%02; Hz =
performance parameters are: Tc = adiabatic 2H, etc). The effects of product gas dissociation
combustion temperature; TE = exhaust gas constitute the greatest source of inaccuracy in
temperature; C* = characteristic velocity; CF = the above ideal rocket analysis
thrust coefficient; ME = mean molecular weight Additional departures from ideal behavior re-
Of exhaust gases;v = average ratio of specific sult from:
heats of exhaust gases a) Conical divergence of the exhaust jet;
According to Summerfield (Ref 12, p 442): b) Surface friction and flow disturbances in
“The ideal rocket motor analysis rests on the the exhaust nozzle;
following simplifications: (a) the proplnt gas c) Constriction of the exit area due to boundary
obeys the perfect gaslaw; (b) its specific heat is layer build up;
constant, independent of temp; (c) the flow is d) Jet detachment;
parallel to the axis of the motor and uniform in e) Heat loss from the hot gas to the cold
every plane normal to the axis, thus constituting motor walls;
a one-dimensional problem; (d) there is no fric- f) Suspended liquid or solid particles in the
tional dissipation in the chamber or nozzle; (e) exhaust jet; and
there is no heat transfer to the motor walls; (f’) g) Pressure drop in the combustion chamber
the flow velocity in the chamber before the nozzle due to heat release.
entrance is zero; (g)combustion or heat addition They are discussed in detail in Ref 12, pp 464–71
is completed in the chamber at constant pressure A detailed description of LP Rocket Systems
and does not occur in the nozzle; and (h) the pro- is beyond the scope of this article. An excellent
cessis steady in time.” account of many of the facets of LP rockets, such
With these simplifications typical computed as combustor design, cooling, pressurization prior
values of LP rocket performance (according to to combustion, and pump systems, is given in
Ref 12, pp 453–64) are given in Table 4 Ref 12, pp 475–516

Table 4
Typical Performance Characteristics

Performance
parameter Ordinary range High range

Tc 2000–3000 K 3000–5000 K
C* 4000–5500 ft/sec 5000–8000 ft/sec
CF 1.3–1.5 1.5–1.6
Isp 200–270 lb-see/lb 270-400 lb-see/lb
‘E 20–25 8–20
7 1.15–1.25 1.15–1.20
 L 43

5) Sensitivity and Hazards of LP. Some mono- 16, p 1074) make the interesting suggestion that
proplnts and some well-mixed biproplnts exhibit instability in amine/nitric acid biproplnts is as-
detonation characteristics typical of Liquid Ex- sociated with the production of intermediates,
plosives (See Sects 4 & 5 of article on Liquid such as amine-nitrates, which decompose explo-
Explosives in this Vol). However, biproplnts sively on rapid temp and pressure rises
usually do not sustain complete detonation, ie, The compatibility of LP with materials that they
a rather small portion of the biproplnt undergoes may contact can create hazard problems. Hollister
something akin to detonation and the remainder (Ref 19) reviews the compatibility of several LP”
deflagrates (Ref 26). Of course even this partial systems in contact with elastomeric materials
detonation can be very dangerous and destructive. Farber (Ref31) points out that LP rocket
LP are also subject to another phenomenon which destruct systems (specifically Saturn V) can ini-
is potentially destructive (at least to the rocket), tiate dangerous secondary explosions in the dis-
namely combustion instability (Refs 16& 22) charged fuel/oxidant mixture
The two stage explosion process of most bi- Specific tests of the detonation sensitivity of
proplnts, ie, “detonation” followed by deflagra- LP are not very different from those used with
tion, manifests itself in the explosion fire-ball and liq explosives, but the interpretation of LP sensi-
the impulse delivered by such explosions. Both tivity tests is subject to large uncertainties. This is
fireball and impulse (at least close to the explo- so, because practical considerations dictate that
sion) for typical biproplnts are larger than for the relatively small amounts of LP be tested, but for
same weight of TNT, but shock pressure is con- many LP systems the increase in sensitivity with
siderably less. Thus the main hazard of a distant increasing test sample amount is not known
biproplnt explosion are its thermal effects. Nearby, Tamenbaum & Beardell (Ref 30, p 344)
this explosion can also be destructive to organisms suggest the following “routine” tests:
and structures that are affected by impulse and a) A modified Trauzl lead block test (See
large low-velocity fragments. It has been suggested Vol 1 under Physical Tests) with a 0.5 to 2g LP
that the nautre of a biproplnt explosion is pri- sample and a No 8 blasting cap initiator;
marily the result of “poor” mixing (on a molecular b) Bureau of Mines drop-weight test;
scale) of the biproplnt fuel and oxidizer, and that c) Adiabatic compression test in which a piston
turbulence created by the “detonation” disrupts rapidly compresses a gas bubble above the test liq;
further mixing and extinguishes the “detonation”. d) Self-heating test in which the sample is
In liq explosives, by way of contrast, the “oxidizer” heated in a bomb and the sample and heating bath
and “fuel” are generally contained within the same temps are monitored;
molecule and there is no mechanism for extinguish- e) Card-gap test (See Vol 1 under Physical
ing detonation (Ref 26) Tests to test shock-sensitivity); and
Combustion instability in LP results from f) Critical diameter established by measuring
pressure oscillations during combustion. If these detonation velocity in columns of decreasing
oscillations are of low frequency, eg, as a conse- diameter
quence of fluctuations in the proplnt flow rate, Glatts (Ref 20) tested four monoproplnts for
the resulting instability is called chugging. At sensitivity to fire and bullet impact. Hydrazine,
high oscillation frequencies, leading to what is Hydrazine Nitrate solution, PrN03, and ethylene
sometimes referred to as screaming, longi~dinal oxide were all tested in 1-gallon ahrminum con-
waves are set up in the combustion chamber as tainers (half of them ffled to zs~. and half to 95%
well as cylindrical wave motion. Above a criticrd capacity) by being subjected to oil and wood
amplitude, these cylindrical motions can increase bonfires, and 20-mrn incendiary, 20-mm HE in-
enormously and damage the chamber cendiary, and 0.30-caliber rifle fire. Aviation
Levine (Ref 22, p 1083) has studied high fre- gasoline was tested in the same manner. In the
quency combustion instability of LP via high speed bonfire tests, all four monoproplnts generally
gave equivalent explosion intensities regardless
photography and pressure-time measurements. of the type of bonfire or the amount of liq in
Crocco has examined these phenomena theoreti- the test container. Occasionally, however,
cally (Ref 22, p 1101). Bernard & Dufour (Ref with the first 3 monoproplnts, anomalous re-
 L 44

suits occurred: there was either no explosion 20) G.S. Glatts, NASA Doc N62-I0432 (1962)
or an explosion of above average intensity. &CA 60, 10465 (1964) 21) E. Ring,
Ethylene oxide more nearly approximated the “Rocket Propellants and Pressurization Systems”,
behavior of aviation gasoline than did the Prentice-Hall, Englewood Cliffs, NJ (1964)
other monoproplnts. In the rifle-fire tests, 22) 10th SympCombstn (1965), 1083 & 1101
PrN03 was the most bullet-sensitive. It was 23) T. Urbafiski, “Chemistry & Technology of
exploded by rdl three types of ammunition. Explosives”, Pergamon Press, NY, Vol 3 (1967),
Hydrazine and Hydrazine Nitrate solution were pp 291–321 24) J.P. Hardey, “Advanced
exploded by the HE ammunition but not by Solid and Monoliquid Gas Generators”, Report
incendiary and HE incendiary ammunition RMD 6055-3, Thiokol Chemical Corp, Reaction
Motors Div, Denville, NJ (1968) 25) R.K.
Written by J. ROTH
Lund, “Encapsulated Liquid Monopropellant
Refs: 1) K.E. Ziolkowsky, Science Survey Ammunition Feasibility Study”, Eglin AFB
Russ) (1903) 2) R. Esnault-Pelterie, Soc- Tech Rept AFATL-TR-61-27 by Thiokol
Astronornique de France, Paris (1928) Chemical Corp, Wasatch Division, Brigham
3) R.H. Goddard, Smithsonian Inkt Mist Col- City, Utah (1968) 26) R.F. Fletcher, Ann-
lections 95 (3)” (1936) 4) F.J. Malina, NYAcadSci 152 (1), 432 (1968) &CA 70,
JFranklinInst 230,433 (1940) 5) M.W. 69711 (1969) 27) M.V. Dobrovol’skii,
Nesbitt, JAmRocketSoc 68, 1 (1946) “Zhidokosnye Raketnye Dvigateli” (Liquid
6) J.H. Wyld, JAmRocketSoc 17 (70), 2 (1947) Rocket Propellants), Mashinostroenie, Moscow
7) M.J. Zucrow, “Principles of Jet Propulsion (1968) &CA 71, 126715 (1969) 28) J.N.
and Gas Turbines”, Wiley, NY (1948) Bradley, “Flame & Combustion Phenomena”,
8) R.C. Truax, JAmRocketSoc 18 (74), 62 Methuen &Co Ltd, London (1969), pp 163–7
(1948) 9) G.P. Sutton, “Rocket Propulsion 29) R.F. Gould, Edit, “Propellant Manufacture
Elements”, Wiley, NY (1 949) 10) S.s. Hazards & Testing”, Advances in Chemistry,
Penner, JChernEd 29, 37 (1952) 11) J.B. Series 88 American Chemical Society, Washing-
Goldman, “Liquid Monopropellants and Their ton, DC (1969), pp 312 & 344 31) E.A.
Application”, General Dynamics/Astronautics Farber, EngProgrUnivFlaTechPapSer 1969, p
Bibliography, San Diego, CaIif (1959) 448 &CA 72, 45640 (1970) 32) Anon,
12) O.E. Lancaster, Edit, “Jet Propulsion EncyclBrittanica 18, 629 (1971) 33] Anon,
Engines”, Princeton Press, Princeton, NJ (1959), “Monopropellant Hydrazine Propulsion Systems”,
10–23, 23–26, 439–41, 442, 440–44, 453–64, Chemicrd Propulsion Information Agency Pub-
464–71 & 475–516 13) S.S. Penner & J. lication 228 (IV), JANNAF Propulsion Meeting,
Ducarme, Edits, “The Chemistry of Propellants”, New Orleans, La (1 972) 34) M.J. Russi,
Pergamon Press, NY (1960), pp 25–228 “A Survey of Monopropellant Hydrazine
14) J. Ducarme et al, “Progress in Combustion Thruster Technology”, Aerospace Corp, San
Science & Technology”, Pergamon Press, NY, Bernadine, Calif (1974) 35) R. Meetin &
Vol 1 (1960), pp 183–217 (Chapt on Ignition J. Newton, Final Rept Proj AF-3058, Edwards
in LP Rocket Engines) 15) R.E. Wiech & AFB, Calif (1974)
R.F. Strauss, “Fundamentals of Rocket Pro-
pulsion”, Reinhold, NY (1960), Chapt 5
16) 8th SympCombstn (1962), pp 1035, 1074 Liquid TNT. See under Drip Oil in Encycl 5,
& 1140 17) L.E. Bolliiger et al, Edits, (1972), D1546-R to D1 547-L
“Progress in Astronautics & Rocketry”, Aca-
demic Press, NY (1960), pp 447 & 471
18) Yu.Kh. Shaulov & M.O. Lerner, “Goreniye Litharge. See Lead Monoxide in this Vol
v Zhidkostnykh Raketnykh Dvigateliakh”
(Combustion in Liquid Rocket Fuel Motors),
GosIzdatOboronProm, Moscow (1961) Lithium-Aluminum Hydride. See ~um~um.
19) W.A. Hollister, USDeptCommOfficeTech- Lithium Hydride in Encycl 1,(1 960), Al 54-R
Serv, D275279 (1962) &CA 60, 10465 (1964) to Al 55-L, and under Hydrides in this Vol
 L 45

Lithium Nitrate. LiN03, mw 68.95, colorless Lithorite. A Belg mining expl used at the end
delq granules, mp 261°, d 2.38g/cc; sol in w of the 19th century. It consisted of K nitrate
and ale. Used in pyrotechnics as an oxidizer 50.0, Na nitrate 16.0, sulfur 16.0, nitrated saw-
to color burning compns red (Ref 2), and in dust 8.0, Amm picrate 3.5, K ferrocyanide 3.0
rocket proplnts (Ref 1a) & charcoal 3.5%
Refs: 1) Gmelin, Syst Nr 20 (1927), 98ff ReE Daniel (1902), 410
la) D.R. Stern, USP 2949006 (1960) & CA
55,4964 (1961) 2) EngDesHdbk, “Pro-
perties of Materials Used In Pyrotechnic Com- Little David. An experimental rifled mortar
positions”, AMCP 706-187 (Ott 1963), 179:80 (914mm mortar Tl) of 36”diameter developed
3) CondChemDict (1971), 525-L in the USA during WWII. This mortar and its
special ammo were secretly developed for re-
ducing Ger fortifications; however, this proved
Lithium Perchlorate. LiC104, mw 106.40, colorless to be unnecessary. The mortar weighed 172900
delq trysts, mp 236°, d 2.429g/cc; sol in w and lbs; its proj weighed 3650 lbs of which 1589 lbs
ale. Decompn starts at about 400° and be- was HE. It was fired by a max propelling charge
comes rapid at 430°, yielding LiCl and 02. It of 218 lbs of proplnt, and had a range of about
has more available 02 on a vol basis than liq 9000 yards
02, and is thus used in “oxygen candles” Refi J. Quick, “Dictionary of Weapons and
(Ref 2, p 237). It is used as an oxidizer in solid Military Terms”, McGraw-Hill, NY (1973),279
rocket proplnts and in pyrotechnics to color
burning compns red (Refs 1 & 2)
Refs: 1) EngDesHdbk, “Properties of Materials Livens Projector. Invented during WWI by
Used in Pyrotechnic Compositions”, AMCP Capt J. Livens of the Brit Army. It was a
706-187 (Ott 1963), 181–2 2) Ellern (1968), crude form of a trench mortar, consisting of
124, 237, 271 & 337 3) CondChemDict a smooth bore tube (8” ID, 37.5” long) which
(1971), 525-L was used to project Livens Drums by means of
a proplnt charge ignited by an electric primer.
The drums were e~ipsoidal-like containers
Lithoclastites. Dynamites patented in Fr by (7-5/8” diam, 20” long) filled with either
Rota in 1884 contd NC mixed with hydro- gaseous agents or incendiary materials, and
carbons and other substances contained a burster charge. The filled drum
Ref Daniel (1902), 690 weight was about 61 lbs, and its range was
between 910 and 1450 yards.
From 400 to 800 projectors were covertly
Lithofracteur. Brit mining expl manufd between installed in a specially prepd trench, whose
1882 and 1899. Its approx compn was NC 54, front wall was cut at a 45° angle. Their only
Ba nitrate 15, kieselguhr 17, wood flour 2, bran mou,nting was a simple metal base placed to
1, sulfur 4, Mn dioxide 2 & soda ash 2% (Refs prevent the tube from being driven into the
1 & 3). A Ger version, called Lithofracteur ground on discharge. The projectors were
Krebs, contd NC 52, pulverized coal 12, sulfur held in place by earth filling. They were
2, Na nitrate 4 & kieselguhr 30% (Ref 4). Cody electrically connected in sets of 25, and on
(Ref 2) lists a Lithofracteur Dynamital which firing of 800 projectors simultaneously, a
contd saltpeter, sulfur, sawdust and bran. He charge of 11 tons of phosgene gas would be
also lists a Lithofracteur of Newton, known as deposited over 50 to 100 square yard area
Poudre Newton, which consisted of Ba nitrate without prelirninarj warning to the enemy
77, K nitrate 2 & charcoal 21% Refs: 1) Anon, “History of Trench Warfare
Refs: 1) Daniel (1902), 409 2) Cody (1 907), Materiel”, ArmyOrdnHandbook No 154, US-
173 3) CondChemDict (1942), 290 GovtPrintingOffice, Washington (1920), 170–81
4) P6rez Ara (1945), 331 2) A.B. Ray,, IEC 13, 716–17 (1921)
3) C. Wachtel, “Chemical Warfare”, Chemical
 L 46

Publishing Co, Brooklyn, NY (1941), 288 bonded expls (PBX). These are exactly what
4) Anon, -’’Livens Projector”, US War Dept the name implies, and like plastics can be ob-
Tech Manual TM 3-325 (1942) tained in many different forms. Hence, PBX’S
are available for casting, pressing, or extruding.
They vary from rigid to rubbery consistencies
LOADING AND FABRICATION OF EXPLOSIVES depending on the type of plastic used as the
Process Selection. binders – thermoplastic or thermosetting –
Most solid high expls are manufd by pro- and the degree of polymerization permitted.
cessesthat yield granular material. Their bulk High mechanical strength and high thermal
densities are generally somewhat less than stability are possible (Ref 10)
1 g/cu cm. They are used in military applica- Other considerations for process selection
tions as solids of well defined configurations, include fabrication facilities and suitability of
usually at densities between 1.5 and 1.7g/cu cm the explosive for its intended application
The two principal loading techniques are (Ref 13)
casting and pressing. All expls in common Casting.
military use can be pressed, however, those Projectile Preparation
that are castable are usually cast because of As part of the manufg process, the interior
the greater convenience and flexibility of this wall “of the proj is sprayed with paint or varnish,
process. As a rule of thumb, main bursting primarily to prevent rusting of the proj in storage.
charges of large cal munitions are cast while The requirements of the coating are that it be
small explosive components (initiators to compatible with the expl, adhere well to the
boosters) are pressed proj wall, and offer a good bonding surface
More pounds of military expl are cast than for the expl. The latter requirement is necessary
are loaded by all other processes. Essentially, to prevent rotation of the charge relative to the
the casting of an expl involves only melting it spinning proj. The finished coating at the base
and pouring it into a charge case or mold. In of the proj should be thin enough to assure
practice, like most firndamentally simple pro- thorough drying and be sufficiently smooth to
cesses,the procedures necessary to cast charges eliminate irregularities that could otherwise form
of the quality needed for acceptable perfor- air pockets
mance and safety can become quite elaborate. The molten expl is usually poured thru a
A suitable pour viscosity is of over-riding im- funnel-former. This tool is specially designed
portance to furni:~ the desired surface contour upon re-
The most common procedure for pressing moval apd to hold a sufficient reservoir of mol-
powd expls is that of pouring the powd into a ten expl to replenish the shrinking, cooling mass
mold and pressing it with a ram that fits snugly. beneath it. .A thin film of silicone grease is
The pressure most frequently specified for charges applied sometimes to the former to aid in its
used in military items is 10000 psi. Charges release when the ex~l. has solidified
may be pressed directly into their containers or Effect of Casting Procedure On Charge
pressed.into molds and ejected as pellets. Where Characteristics. -,
they are pressed into containers of lengths 1) Porosity and Cavitation
greater than the diameter, the explosive is The porosity of an expl charge is usually
usually loaded in increments introduced by two principal causes, entrained
After pressing or casting, it ,is sometimes air bubbles and dissolved gases, and shrinkage
necessary to machine explosives, either to provide that occurs as the charge solidifies and cools.
a smooth surface or a fuze cavity at the filling The higher the temp of casting and the more
hole, or to produce complex contours required fluid the melt, the larger is the fraction of the
for some specialized prirposes. In some cases, entrained air that forms into bubbles and floats
mating contours of two charges are cemented out of the charge. On the other hand, these
together. Cavities are also formed using a conditions maximize cavitation due to shrink-
special tool on final pressing age. The most serious effect of shrinkage is
Of increasing importance are the plastic that known to metal founders as “piping”.
i.
 L 47

The casting solid~les from the outside and con- must, of course, remain liq and in communica-
sequent shrinkage is that of an isolated mass at tion with the center of the charge. When the
the center where no additional material is filling hole is large enough, convective heat
available to fill the volume left by the shrink- transfer maintains such conditions. In other
age. The result is a single large void at the instances, however, such conditions can be
center of the casting maintained only by means of steam heated
In a cast charge (unlike in a pressed charge), funnels, steam finger, or hot probes
both density and pore or cavity size are deter- Where the maintenance of a clear channel
mined by the casting procedure. Both of these between sprue and the slowest freezing part of
factors must be considered by the designer in a charge is impractical, cavitation is avoided by
terms of their effects upon safety, reliability, casting charges in layers, each of which is al-
and performance lowed to “crust over” before pouring the next
2) Cystal Size TNT melts at 81°. It forms eutectics with
The trysts of TNT in cast expls may vary RDX, Tetryl (680), PETN (760), and other
from microscopic size to a substantial fraction “impurities” in the mix and makes these ma-
of the size of the charge, depending upon terials more soluble at higher temps. Thus,
casting conditions and procedure. The approach there is a general tendency for the solid content
known as cream casting results in very fine and, hence, the apparent viscosity of most cast-
trysts. In mixed expls, which usually are cast able mixts to decrease as the temp is increased.
in the form of slurries, the solid particles tend However, a reversal of the tendency toward the
to inhibit tryst growth, although TNT trysts reduction in viscosity has been noted in Comp
sometimes apparently grow around the particles B when it heated above 100°
of the slurry. The effects of particle size on From the eutectic or mp, the composition
initiation sensitivity, failure diameter, and per- of the liq portion and its viscosity vary as heat
formance characteristics also have been observed is removed. It has been recommended that the
to apply to crystal size in cast TNT heat content of any expl be reduced, before
3) Uniformity of Compositwn. pouring, to the minimum compatible with the
Most castable expls are poured as slurries avoidance of air entrainment
of RDX, Al, etc, in molten TNT. The instant : TNT may be cast after it has cooled to a
a charge is poured, the particles of higher den- point where a fairly large fraction of it has
sity than TNT start to settle, and those that are solidified to form a slurry of very small trysts.
lighter start to rise. As a result, by the time the Such a slurry is obtained by stirring it as it
material solidifies, its compn varies from point cools. TNT cast in this m;mer is labeled by
to point within the charge. Another cause of some as creamed TNT. Some have applied the
nonuniformity of compn is the tendency of term creamed to all expls that are cast after *
TNT to form essentially pure trysts, leaving stirring until the last possible instant. Extreme
other components of the mixt at grain boundaries caution must be taken to avoid air entrapment
and in the center of the charge that usually during stirring. This technique has the ad-
solidifies last. The most serious production vantage of resulting in less shrinkage on cooling
problem of this kind is the settling of Al in and solidification because a large portion of the
larger charges of aluminized expls. The use of TNT is already solid befor~ casting
Al and other additives in very fine particle Some Special Casting Techniques.
sizes can help to alleviate this problem but 1) Pellet Casting.
rdso tends to increase pouring difficulties be- For very large charges, cooling time, is re-
cause of the higher viscosities of the melts duced and shrinkage minimized by use of pre- “
Standard Casting Procedure cast pellets. The best pellet casting technique
The most common procedure for filling a is that of pouring a quantity of molten expl
proj or bomb case is to do so in a single pouring into the case, and then pouring in pellets,
(Ref 7). In loading projs, a funnel or sprue pro- slowly enough so that they are not in con-
vides a reservoir of molten expl to fti the volume tact with one another to avoid entrapping in-
left by the shrinkage. The expl in the funnel terstitial air (Ref 7). Although pellet casting
 L 48

reduces the total amount of shrinkage voids, it the mold, pouring, and cooling takes over forty
makes it nearly impossible to maintian channels hours (Ref 2). At the other extreme is the use
to the pockets of molten material. The most of strategically placed insualtion to cause a
important advantages of pellet casting is the charge to cool in the approximate desired
reduction of cooling time and minimizing of pattern
shrinkage in large charges. Pellet casting is not 5) Extrusion
used in loading artillery projs because of the Extrusion may be “considered a form of
development of cavities casting under pressure. In applications where
2) Vacuum Melting and Casting. cylindrical charges are required, some plastic
Entrainment of air may be avoided by bonded explosives can be extruded into the
melting and casting under a vacuum. Vacuum desired shape and then placed or pressed into
melting is a fairly straight-forward procedure the ammunition housing. Conventional extru-
in the vacuum kettles that are maintained by sion tools are employed for this process
many loading facilities. Vacuum casting re- 6) Liquid Explosives
quires specially designed molds or a vacuum From the standpoint of casting, the pouring
chamber large eno,ugh to contain both kettle of liq or shrrry expls is handled in the same
and mold. The definite increase in the cast manner as that of molten expls. The process
density should indicate without question the is simpler in that pouring takes place at ambient
advantage of vacuum melting, namely, an in- temp. However, care must still be taken to
crease in viscosity of the vacuum melted ma- avoid entrapment of air. Liq filling can be
terial. Nevertheless, a divergence of opinion speeded up by pumping. If slurries are to be
exists regarding the value of vacuum melting gelled in the ammo, the gelling agent is intro-
followed by pouring in air. Some investigators duced just ahead of the cavity (Ref 12)
report results nearly as good as those obtained Pressing.
with complete vacuum melting and casting. Standard Procedures.
Others maintain that so much air is entrained 1) Measurement of Explosive Charges
in the casting process that the value of vacuum For small test quantities or for some pre-
melting is negligible. A possible explanation mium quality production, direct reading one-
for this difference of opinion is the difference pan balances are used. They are faster than
in techniques that can be applied in various analytical balances and provide an accuracy
types of operation within one percent. Automatic weighing ma-
3) Vibration, Jolting and Centrifugal Casting. chines are rdso available
Accelerating of a cast charge after pouring The desire is always to load a specific
but before solidification will often expedite weight of expl. This objective can be achieved
the movement of air bubbles to the surface to a sufficient degree of accuracy for many
(Ref 4). Vibration and jolting often break the purposes by volumetric control, as in com-
surface tension that causes bubbles to cling to mercial blasting caps and squibs. The two most
surfaces (Ref 7). Centrifugal acceleration, of common volumetric measuring devices are
course, also accelerates the settling of denser scoops and charging plates. Scoops (Fig 1)
components of mixtures (Ref 7). This has been
used to advantage in loading ‘HEAT ammo where
it is desirable to have a richer composition of
the more energetic compounds (RDX and CUP
CONO
HARD
HMX) around the cone in cyclotol or octols
4) Controlled Cooling.
If an expl charge can be induced to cool
from the bottom up, maintaining a nearly
plane interface between liq and solid, den-
sities well in excess of 99% of maximum the-
oretical are attainable. In a complicated pro-
grammed cooling, the thermal cycle of preheating Fig 1 Scoop Loading
 L 49

lerances similar to those used for gages. Where

casesare made by processes such as forging,
drawing, and extrusion, which use most of
the tolerance in lot-to-lot variation, some load-
ing activities have found it worthwhile to main-
tain a series of loading tools of graduated di-
mension, using those giving the best fit possible
with each lot of cases
Production loading tools should be hardened
(60 Rockwell C is common). The die should
be ground, honed, and lapped or polished to
an 8 or 16 rms micro-inch finish. Some “claim
better results if the final operation involves
(9) [email protected] OF CNARGS longitudinal rather than rotary motion
The friction between the expl and the walls
Fig 2 Charging Plate Loading causes a gradient of press, and hence density,
decreasing from the face of the ram. The slope
of this press gradient, of course, is proportional
are fdled and leveled against a robber band. to the coeff of friction between the expl and
Careful scooping is accurate within 4%. Charg- the walls, which varies with both expl and case
ing plates (Fig 2) lend themselves to produc- material and also with the interior finish of
tion rates. After filling holes in the top plate the case. As a general rule, the density varia-
and scraping off the excess, plates are aligned tions due to these gradients are kept within
with cup holes. Since expl quantities are reasonable bounds by adherence to the general
ususally specified by weight, it is left to the
loading plant to adjust the volume measured
so as to take into account bulk density. There
are now several automatic volumetric loading
devices for production loading of primer mixes
and lead azide used in initiators
2) Direct Pressing in Case
A large proportion of expl charges are loaded
by direct pressing of expl charges in cases (Fig
3). Fits and tolerances of expl charge cases
Q u
LOAOING RAM

and loading tools are determined by reconcilia-

tion of three opposing factors: 1) production
costs of components rise sharply as tolerances
are reduced; 2) powdered expls tend to flow
into the clearance bet ween ram and case. In
addition to creating a hazard, the expls wedged
in this space can increase the frictional resist- NATOR
ance to ram movement, and substantially de-
crease real loading press; and 3) interference
between ram and case results in binding (which
may be so severe as to prevent any pressing of
the expl), damage to the case, inclusion of IL
chips of case material in the expl, or all of
these (Ref 1)
The cost of a set of loading tools may be
distributed over a large numbe: of items. For
this reason, they are often made to fits and to- Fig 3 Detonator Loading Tool

I
 L 50

rule-of-thumb that the length of an increment 3) Stop vs Pressure Loading

after consolidation should not exceed the diameter In production, “it is possible either to press
of the cavity (Ref 2) a controlled quantity of expl to a controlled
The usual loading press of about 10000 psi height (called stop loading) or to apply a given
is well beyond the bursting strength of charge load to a loading ram of a given diameter
cups of any material that can be economically (called pressure loading). The inherent varia-
deep drawn. Hence, cups are supported by tions in production material introduce a certain
close fitting loading tools whale being pressed. amount of error in the density obtained by
Most of the difference between the cup diameter either method
before and after loading is accounted for by the The relationship between loading press and
expansion of the expl component, relieving re- charge density for commonly pressed expls is
sidual stresses,as it is pushed out of the tool. given in Table 1 (Ref 1). An approximation of
For this reason, loading tools should be made to the loading densities of six commordy used ex-
fit the maximum outside diameter of the cup, plosives is shown in the nomograph, Fig 5
within a few ten-thousandths of an inch. (Ref 3). The pressure-density relationship
Standard dimensions and tolerances of cups are varies somewhat from lot to lot. In addition,
listed in MI L.STD-320 (Ref 11). Bore finish loading density is affected by such factors as
and hardness of the bushing are important ram clearance and increment length
factors in trouble-free ejection of finished cups. From the usual cup tolerances, it has been
Lapped or honed bores are often specified. calculated that the cross-sectional area of the
Where cases are heavier or where expls are to expl column of a detonator may vary by two
be loaded directly into fuze cavities, the in- or three percent. In normal production, a
teractions of case and tool tolerance$ which reasonable weighting tolerance for initiator
may be sufficient to cause interference between charges is three or four percent. Thus, in stop
the ram and any of the boxes thru which it loading, assuming that the height of an increment
passes, should be considered carefully. In some is exactly reproduced, the density may vary as
situations, where expls are to be loaded directly much as seven percent
into fuze holes, the most practical way to at- The implication of the foregoing, that
tain alignment is to use a pin or dowel, similar densities are more readily controlled by the
to the loadng ram, to hold the component in control of loading pressure than by stop loading,
alignment with the ram guide while it is being has been borne out by experience. However,
clamped in place. It is best to use an align- the production advantages of stop loading are
ment pin a thousandth of an inch or so larger sufficient to outweigh any theoretical disad-
than the loading ram. Fig 4 shows a set-up vantages. It is important for stop loading to
for hand loading of leads making use of an specify dimensions, quantities, and tolerances
alignment ram and a mandrel such that the max press is within limits im-
posed by tool strength. When items so loaded

w“’’=”” are used, safety and reliability determinations

should take the effects of variable charge den-
sity into account. In either type of loading, a
check of the loading density for each production
E
NGER
lot is highly deisrable
When density is determined by pressure
loading, variation in press, cross-sectional area,
and charge weight each has an effect upon the
column-height. Usually, the length tolerances
specified cannot be held merely by holding the
various quantities mentioned within their toler-
ances. The weight of expl must be adjusted to
compensate for the other variables, Commonly,
Fig 4 Tool for Direct Loading of Component the last charge loaded is adjusted to fit the space
 L 51

TABLE 1

LOADING DENSITY OF VARIOUS EXPLOSIVES

pressed [pressure kpsi) Crystel

Explosive 3
— .
5
—10 —12 15
— —
20 cast Densitv

Composition A-3 1.47 1.61 1.65

Cornposition B 1.59 – 1.67
Cyclonite (RDX) 1.46 1.52 1.60 1.63 1.65 1.68 1.82
EDNA (Haleite) 1.39 1.46 – 1.51 1.55 1.71
Explosive D 1.33 1.41 1.47 1.49 1.61 1.64 1.72

Lead Azide 2.46 2.69 2.98 3.05 3.16 3.28 4.68

(2 specimens) 2.62 2.71 2.96 – 3.07
Lead Styphnate (Norm.) 2.12 2.23 2.43 2.47 2.57 2.63 3.1
Pentolite, 50-50 1.59 – ~ 1.65 —
PETN 1.48 1.61 – 1.76

Picric Acid 1.4 1.5 1.57 1.59 1.61 1.84 1.71 1.76
Picratol, 52/48 1.62
Tetracene 1.05 1.22 1.33 1.37 1.41 1.48 4.72
Tetryl 1.40 1.47 1.57 1.60 1.63 1.67 1.73
TNT 1.34 1.40 1.47 1.49 1.52 1.55 1.59 1.65
(Densities are in g/cc)

I ,0 -
- 50,000
— 40,000
— 30,000
– 25,0CKI
— 20,000
TNT
.
1,5 15,000
- T“’”\l
/-p’TN
ROX
10,000
u //z
u .- .
h /“ :
>. 2.0 – ,/’
~ ,0 0“
(n LEAO S; YPi4NATE
R 0“ 5,000
0 ,/
o 4,000
z ,/’
E ,0 M
,~ LEAO AZIOE — 3,000
; 2.5 —
,/ - 2,500
/“
,/ - 2,000
/0/
/“ 1,500

3.0
t-
i- 1,000

F
A STR41QHT LINE THROUGH THE POINT SHOWN FOR
A PARTICULAR EXPLOSIVE WILL INTERSECT THE TWO SCALES TO
SHOW THE LOAOING OENSITY RESULTING FROM ANY GIVEN LOAOING
3.5 PREsSURE.
500
EXAMPLE : THE OENSITY OF LEAO AZIOE PRESSEO AT
10@OpSl IS ASOuT 2.9 g/cm2
i

E USE WITH CAUTION AT HIGH PRESSURES

Fig 5 Nomograph of Loading Pressure and Density

 L 52

remaining for it and the weight is specified as formance, may adversely affect the handling
“approximate” properties of pellets. Pellets consolidated
In addition to the pressing properties of the from powders at low densities tend to be weak
expl as such, the relationship between loading in two ways; their resistance to body fractures
press and density is affected by such factors as is often less than desirable, and they may crumble
ram movement, clearances, increment size, and at corners and chalk off at surfaces. On the
the coeff of friction between expl and case. other hand, some materirds become brittle and
The movement of the ram affects the relation- develop residual strains at high densities
ship in two ways The effect of density variation on mechani-
The first effect may be very serious. Where cal properties of pellets may cause difficulties
a balance or dead weight is used to determine even though the variation in expl properties is
the loading press, a rapid ram movement can tolerable. On the other hand, the general
result in a force due to acceleration of the superiority of the finishes of pelleting molds
massesmoved which may vary from a substan- over those of charge cases and the use of double
tail fraction to several times the force due to acting loading equipment result in somewhat
gravity. Analyses of some loading operations smaller density gradients in pellets than in
have revealed that the true loading press was direct loaded explosives. The result of these
three or four times that intended counterbalancing trends is that the one-to-one
The second effect of ram movement usually limiting ratio of length to diameter which applies
works in the opposite direction (slower ram to iricrement loading also applies to pellets. For
speeds plus a dwell at the peak press may some materials, somewhat shorter pellets are
cause.an increase in density). This effect is desirable, particularly in larger sizes
due to the fact that, at loading pressures usually The diameter of a pelleting die may be
used, expls are stressed beyond their yield maintained to ahnost any tolerance specified.
points and creep or flow plastically. This Similarly, the distance between the top and
effect, of course, becomes more important at bottom punches of an automatic pelleting
vary high pressures, such as those used for de- machine, or the punch-to-heel distance in a stop
lays. In addition to increasing the density, pressing tool, can be held to any desired toler-
slower speeds plus dwell of the ram result in ance. Thus, the dimensional variations are
a more uniform density essentially the variations in expansion of the
4) Pelletizing material, during and after ejection from the die.
Most powdered expls that are to be pressed The immediate expansion upon ejection for a
are prepressed into pellets. The die of the typical expl used for pressed pellets is about
loading tool permits closer tolerances and 0.3%. Pellet-to-pellet variations are usually
better finishes than are reasonable for cases less than 0.1 % but the expansion continues
that are loaded by direct pressing. Exceptions with storage at a rate that varies appreciably
are primer mixes, PETN, and LA, although LA with conditions as well as with the compn of
is pelleted in Canada on a production basis the expl. Pellets of an expl of known expansion
Altho@h pellets for exptl use are loaded characteristics, which are to be inserted into
by single operation methods in which weighed cups within a few hours after pelleting, may be
charges are pressed either by stop loading or by held to dimensional tolerances of the order of
controlled pressure techniques, quantity pro- O.1% or less. However, tolerances of 0.3 to
duction of pellets is accomplished in automatic 0.5% are more practical
pelleting machinery, in which the explosive is Variations in density reflect variations in
metered volumetrically by the controlled move- dimensions with those of the bulk density and
ments of punches. Single stroke presses of the flow characteristics of the expl, and those of
types used for expls produce about 90 pellets the measured volume. With frequent pellet
per minute while rotary presseshave rates of density determinations and occasional adjust-
about 700 pellets per minute ment of the pelleting press, expls with good flow
The density gradient resulting from wall properties can be pressed into pellets repro-
friction, in addition to its effects on expl per- ducible in density to 1% in an automatic pel-
leting press
 L 53

S) Reconsolidation during pressing

Frequently, when it is desirable to attain Fig 6 is a diagram of a vacuum loading tool.
the close confinement and continuity charac. First, lower and top punches are advanced to a
teristic of expls loaded directly into their cases, prepress position to compact the powder slightly.
it is difficult or inconvenient to do so. In such After evacuating to 1 mm Hg? full press is ap
instances, pellets are inserted into the cavities plied. Production of extremely high quality
and reconsolidated by pressing. In d$signing charges of TNT (pressed at elevated temp) and
for reconsolidation, consideration must be given Composition A-3 (both at,elevated and room
to the tolerances and variations of hole dimen- temp) has been reported. Density spreads
sions, pellet weight, and pressure-density re- within 6-in diameter charges are 0.005g/cc “
lationship that enter into tie determination of (Ref 2)
the relative location of the surface thru which
the reconsolidation pressure is applied. Where
vALVE ACTUATOR
this dimension is critical, the reconsolidation
is done to a stop so that the tolerances appear
in the density of the reconsolidated pellet.
When reconsolidation is specified, the effects
of these variations upon performance should
be considered

Special Procedures “k+

1) Vacuum Pressing
In the usual pressing operation, in which a m ~0-RING

granular expl is pressed from a bulk density of

about half the crystal density to about 95%
of the crystal density, the press rise in the inter-
VACUUM PORT
stitial gases(assuming isothermal compression
and no leakage) may be in the neighborhood
of 200 psi. The air may be presumed to diffuse

T
out of the pellet, thru the continuous pores,
quite rapidly after the pellet is ejected or the
TOP PUNCH !22! ACUUM POPPET
VALVE

ram is removed, if it has not already leaked

thru the clearance between ram and cavity
O-RING
during pressing
When densities reach 99% of tryst density,
the calcd press of the interstitial gases rises
rapidly, limiting attainable densities. When
under conditions of pressing, the expl or some
component of it is caused to flow plastically,
the pores may be closed into individual bubbles
in which the compressed gasesare retained to
cause excessive growth after press removal or
pellets that pop open when ejected from the
die. In an open pore material, the relatively LOWER PU”NCH ~ k~ O-RINGJ \

mobile gasestend to increase density gradients N 4340 SLEEVE J

by distributing press without a correspondingly

even distribution of the solid expl. For these .
three reasons, vacuum pressing is used where Fig 6 Vacuum Pressing Apparatus
very high or uniform densities are required,
or where significant plastic flow is anticipated
 —.
L 54

2) Hot Pressing
The unique props of plastic bonded expls
are realized most fully if they are pressed at
elevated temps. Appropriate temps, of course, ——/.,----
— ‘\ \ ——

! Pi:
.— / \
are detd by the props of the plastic bonding
agents used and limited by the thermal insta-
bility of the expls. Temps as high as 130°
/_(’
/—————
/—— \\
‘\, --
—..—
/———
have been used (Ref 9). When heated to temps / f
approaching their melting points, expls and ad- /
/
ditives used in expls, like most solids, are more / —
/
prone to plastic flow. Equipment required for /
——
hot pressing of PBX has been found useful in / I ~ ~1 7,, /,,/,,,/
///////1/
the production of high density charges of con- l!
ventional expls. TNT is pressed routinely to a RUBSER
DIAPHRAGM IJ LIOUID AT
HIGH PRESSURE
density of 1.62g/cc at 70° in the vacuum press-
ing process previously described, whereas cast Fig 8 Isostatic Press Principle
densities this high are unusual (Ref 2). Pre-
heating of the expl is more efficient than nates the gradients which result from wall
waiting for it to heat in the mold but cannot friction, some directionality of compression
be used when therrnosetting resins serve as remains which can result in anisotropic struc-
binder ture and residual strains. In isostatic pressing,
3) Hydrostatic and Isostatic Pressing the explosive is placed in a rubber bag (Fig 8)
When an expl is pressed in a die by means that is surrounded by the pressurizing fluid so
of a ram, the friction of the walls tends to that the compression is essentially three di-
cause press and density gradients. In addition, mensional
the one-dimensional compression can result in In addition to the production of high
an anisotropic structure and produce pellets quality charges, hydrostatic pressing and iso-
with residual strains. Where dimensional static pressing can be used to consolidate expls
stability, uniformity and high density are es- which are so sensitive that frictional contact
sential to performance, hydrostatic pressing with the walls of a conventional mold creates
and isostatic pressing have been used. In both a hazard. Materials like pure RDX, of which
of these processes, the expl is compressed by it is difficult to make firm pellets except in
the action of a fluid, from which it is separated small sizes, can often be pressed hydrostatically
by a rubber (or other elastomer) fdm or isostatically (Ref 9)
In hydrostatic pressing, the expl is placed on Hydrostatic pressing and isostatic pressing
a solid surface and covered with a rubber dia- are usually applied to expls that have been
phragm (Fig 7). Although this process elimi- evacuated, frequently at elevated temps. Temps
up to 130° and pressures up to 30000 psi
have been used. The surfaces where pressure
— .— is applied thru elastic membranes are, of course,
of relatively poorly defined form and dimensions.
/J —— /
Hence, these pressing processes must almost in-
/ /
/ —. variably be followed by machining
/
/ 4) Pulsating Pressures
/ Expts have shown that pressures which
/ pulsate with an amplitude of a few percent
of the static press and at a frequency of about
+/// 60 Hz, when used with conventional molding
nbbaER tools, make it possible to produce pellets four
DIAPHRAGM HIGH PRESSIJRE
or five diameters long with negligible density
gradients. The interesting possibilities of this
Fig 7 Hydrostatic Press Principle technique in production of explosive charges
have not yet been exploited
 L 55

Finishing Operations considered justification for dry machining

1) Machining where needed. The water keeps expl dust
It has been found that the most uniform out of the air and cools the cutting operation
densities and compositions are attained by 2) Cementing of Compound Charges
pressing or casting relatively large charges, Expl charges made of more than one expl,
and reaching the charges needed from selected in which the contour of the boundary is an
segments. Similarly, high quality charges can important design parameter, often are fabri-
be made by isostatic or hydrostatic pressing, cated from cast, pressed, or machined compon-
which also must be followed by machining ents that are cemented together
operations. All standard machine shop opera- Cements that harden by the loss of solvent
tions including milling, drilling, sawing, boring, generally are to be avoided because the solvent
and turning – are applied in this work can be lost only be diffusion thru the expl.
Many cast loaded items are ftied thru the Diffusion may be slow and the solvent may
same hole as that into which the fuze is to be modify the properties of the expl. Two types
inserted. After casting, the sprue is broken of cement that have been used for this purpose
off. Although it is a good plan to design the are catalytic setting cements, like epoxy resins,
funnel to form a core for the fuze cavity, the and contact cements. Compatibility of the
problem of funnel extraction limits this prac- materials to be used should be checked. Com-
“tice to some extent. At best, then, the bottom patibility of epoxy resins with most explosives
of the fuze cavity is a rough, broken off surface depends upon the catalyst or hhrdener used
and, generally, the cavity is not as deep as de- (Ref 8). Data regarding bond strengths and
sired. The boring of fuze cavities to the spe- other pertinent properties also have been com-
cified depth and surface finish is a routine piled (Refs 5 & 6)
operation of production Both surfaces to be cemented should be
Profde lathes and forming tools may be clean and fit accurately to one another. A
used to form almost any desired surface. of minimum continuous layer of cement should
revolution. The special forms required for be applied to each surface to be joined. Where
detonation wave shaping and other specialized catalytic resins are used, provision should be
output are often generated by such means. made to hold the members in firm contact for
Expls may be machined to the same tolerances the curing period. When contact cements are
as metals. Turning and milling to a thousandth used, mechanical means are desirable to assure
of an inch is not difficult with a good machine. that the elements are in the proper position
However, the practical applicability of such ~nd orientation when they make the first
precision is limited by the dimensional instability contact
of most expl materials Written by S. M. KAYE
Safety is an important aspect in reaching
explosives. Since the sensitivity of an expl has Refs: 1) Anon, “Ordnance Explosive Train
meaning only in terms of the specific initiating Designers’ Handbook”, Report NOLR1111 ,
impulse, the practice of machining each expl NOL (April 1952) 2) E. James, Jr, “Charge
material by remote control is most desirable Preparation for Precise Detonation Studies”,
(Ref 2). On the basis of test data it is con- 2nd ONR SympDeton, Vol 1 (1955), pp 1–17
sidered safe to machine Composition A-3, 3) Anon, “Explosion Effects Data Sheets”,
Composition B, and TNT at 200 ft/min sur- NAVORD Rept 2986, NavOrdLab, Silver
face speed Spring, Md (June 1955) 4) G.D. Clift,
Cut-off tools and small drills are more “Centrifugal Casting of Explosive Charges for
hazardous because of the poor cooling condi- HEAT Shell”, PATR 2381 (1956) 5) M.J.
tions. These operations, if necessary, should Bodnar, “Bonding of Explosives to Metal with
be performed at low speeds with intermittent Adhesive”, PATR 2412 (1957) 6) M.J.
cutting and frequent flushing. Water should Bodnar, E.R. Kelly and W.J. Powers, “Adhesive
be used wherever practical as a coolant, although Bonding of High Explosives to Metals”, PATR
tests at high speed under dry conditions are 2538 (1958) 7) M.J. Margolin & E.A.
 L 56

Skettini, “Ammunition Loading Techniques”, USP 1329566 (1920) (Loading of shells with a
ExplsDevSectRept 43, PicArsn (1958) mixt prepd by dissolving PA in TNT and then
8) M.C. St. Cyr, “Compatibility of Explosives adding TNX while maintaining the temp of
with Polymers”, PATR 2595 (1959) 9) Cc. the mixt above the mp of TNT) j) F.
Misener, “Capabilities of Explosive Loading Hawkes, ArOrd 2, 208–11 (1922) (Loading
Group of the Chemical Engineering Division of shells with TNT and Amatol) k) J.P.
(WE)”, NAVORD Rept 6873, NavOrdLab, Madden & L. Fisher, USP 1420637 (1922) &
Silver Spring, Md (April 1960) 10) D. Kite CA 16, 2993 (1922) ( A portion of TNT. is
Jr, A.K. Behlert & E. Jercerzewski, “Plastic melted and, then mixed with about 2.5 parts of
Bonded Explosives for Use in Ammunition”, solid TNT to form a plastic mixt for filling)
PATM 2-2-62 (1962) 11) Anon, “Terminology 1) Anon, BritP 181030 (1922) & CA 16, 4349
Dimensions and Materials of Explosive Compo- (1922) (To facilitate loading of shells with
nents for Use in Fuzes, Ml L-STD-320 (July TNT or like expl under press, part of the TNT
1962) 12) S. Levmore, “Principal Charac- is first melted and heated to about 850, and the
teristics of the Gelled Slurry Explosive DBA- remainder is then added dry and well stirred
22M”, PATR 4237 (1971) 13) Anon, Eng to form a plastic dough, which is forced into
DesHdbk, “Explosive Series–Explosive Trains”, the shell) m) W.A. Gibbons, USP 1453933
AMCP 706-179 (Jan 1974), 10-1 to 1O-19 (1923) (Cast loading by partially filling a shell
Addnl Refs: a) C. Claessen, GerP 243981 with solid HE, followed by pouring the HE in
(19 10) (Double-walled steam heated funnel liq form to fill the cavities) n) G.C. Hale,
for shell loading with molten expls) b) C.E. ArOrdn 5, 838–40 (1925) (Ger methods for
Bishel, GerP 227635 (1910) (Cast loading of loading HE shells) o) J.P. Harris, ArOrdn
expls under press to increase their d) 7, 40–8 (1926) (Loading of ammo at PicArsn)
c) Anon, GerP 244034 (1911) (to Deutsche p) H.H. Olmstead, USP 1670689 (1928) & CA
Sprengstoff A-G) (High d is achieved by main- 22, 2467 (1928) (Molten expls are poured into
taining a feeding head full of liq expl and sub- shells in successive layers, each about ‘%” in
jecting it to press during charge solidification) thickness, and allowed to cool for about 30
d) Anon, GerP 255096 (1911) (to Dynamit minutes before adding the next layer)
A-G) (A cold rod of HE is introduced into q) O. Matter, USP 1903594 (1933) (A soln of
the main axis of a molten charge to increase HE is gradually added to a liq in motion which
the rate of cooling, and thus prevent cavity is miscible with the solvent in any proportions,
formation) e) W. Fairweather, BritP 24960 but does not dissolve the expl. The pptd expl
(191 1) (Molten HE is poured into a shell and is melted to form a fluid mass contg unmelted
subjected to mechanical press while the upper granules in suspension, and the resulting broth-
part is kept liq by heat, and the lower part is like mass is cast) r) C,R, Dutton, ArOrdn
allowed to solidify by cooling with w) 20, 389–93 (1940) (Filling of bombs with a
f) Anon, GerP 279526 (1913) (to Deutsche molten PA/TNT mixt) s) H. Shaler, USP
Sprengstoff A-G) (Cavity-free HE charges of 2195429 (1940) & CA 34, 5283 (1940)
high d are obtained by casting into cases and (Loading of expls into ammo is done by intro-
subjecting them to centrifugal forces) g) ducing an increment of molten expl, and ro-
Colver (191 8), 10, 3 19; 442-483, 671 (Va- tating the ammo on its axis until the increment
rious methods of obtaining high d casts of HE has solidified. This operation is then repeated
are reviewed, eg, direct or press casting, chilled with successive expl increments) t) M,A.
molds or shells, cold core expl, and centrifu- Cook & C.O. Davis, USP 2353147 (1944)
gation) h) Anon, ChemAge 1, 385–6 & (High d HE charges are obtained by heating
407–8 (1919) & CA 13, 3318 (1919) (Loading a mixt of two solid ingredients, one being a
of TNT & Amatol by melting an,d pouring, nitrated organic compd, to a temp at which
pouring shaped charges into blocks with sub- one of the compds melts. A dispersing agent
sequent loading into shells, pressing block is included in the mixt) u) L.A. Quyale,
charges and fitting into shells, stemming, and MechEngrg 67, 599–606 (1945) (Volumetric
direct hydraulic pressing) i) C.A. Woodbury, pouring machine for filling mines, bombs &
 L 57

shells) v) H. Bernstorff & A. Allendorfer, that deal with (1) design and development,
USP 2390052 (1945) (Device for stirring expl acquisition, storage, movement, distribution,
melts) w) H. Graham et al, Canad Chem & maintenance, evacuation, and disposition of
Process Indus 3Q 37–41 (1946) (Bomb filling materiel; (2) movement, evacuation, and hos-
with 80/20 Amatol) x) A.N. Campbell & pitalization of personnel; (3) acquisition or
E.J. Pritchard, CanJRes 25B, 183–97 (1947) construction, maintenance, operation, and dis-
& CA 41, 4647 (1947) (It was hypothesized position of facilities and (4) acquisition and
that cavitation & shrinkage in expl charges furnishing of services. It comprises both
could be eliminated if it were possible to slow planning, including determination of require-
crystallization so that the melt would remain ments, and implementation
liq for a while at RT. Attempts to prepare Refi OrdTechTerm (1962), 180
expl mixts with such properties were un-
successful) y) I.E. Aske, USP 2439443
(1948) (Casting app for vibrating molds) Long Tom. Popular name for US 155mm
z) P. Campbell & W.H. Maxwell, USP 2439450 self-propelled gun used during WWII. Extremely
(1948) (App compensating for shrinkage of accurate, it fired a 95-lb proj a distance of
cast expls) aa) L.F. Audrieth & D.D. Sager, 25700 yds. It weighed 15 tons and had a
USP 2482089–91 (1949) (A cast expl obtained barrel length of about 23 ft. During the as-
by pouring a suspension of RDX or EDNA in- sault on the Siegfried Line these guns assisted
to a liq melt of TNT contg Tetryl or PETN) in the destruction of 120 pillboxes, obliterating
bb) A.R.V. Steele et rd, BritP 765210 (1957) one with each round fired from a range of
(A head of liq expl held in a hollow former 300 yds
provides a flow of expl to compensate for any The name has also been applied to the US
contraction as solidification occurs) cc) J.G. 155rnm self-propelled gun M-53, currently
Holmes, Ordn 42, 193–4 (1957) (Application used by the Army and Marine Corps. It is
of single-pour controlled cooling to filling bombs full tracked to provide mobility for the gun
and other expl ordnance) dd) S.D. Stein & and protection for the crew of six in offensive
M.J. Margolin, “Proposed Shell Loading Stan- combat
dards Based on a Statistical Study of Setback Refi J. Quick, “Dictionary of Weapons and
Sensitivities”, PATR 2563 (1958) Military Terms”, McGraw-Hill, NY (1973), 281

Loading Expressed as percentage, is

Factor. Loss of Weight Stability Tests. Expls are
the weight of HE fiil of an ordnance item di- heated at some predetd temp and the loss of
vided by the total weight of the item, multi- weight is measured periodically. Usually, the
plied by 100 greater the weight loss, the less stable is the
expl
In Ger, 10g samples of industrial blasting
Lobbe Explosive. Mixt patented in Eng in 1861 expls were placed in loosely covered weighing
contg Na nitrate, sawdust and lime bottles and heated at 75° for several hours
Rejl Daniel (1902), 411 (Ref 2). Guichard (Ref 1) devised an automatic
balance to eliminate removing the expl sample
from the const temp oven for cooling and
Locust-gum. Proposed as a waterproofing coat- weighing
ing for AN grains in so-called “water-resistant” See also Heat Tests in Vol 1 of Encycl, p XV
expls Refs: 1) M. Guichard, BullSocChim (Fr) [4],
Ref W.J. Taylor, USP 2654666 (1953) & 39, 1113 (1926) & [5], 3, 115 (1936); Ann-
CA 48, 3692 (1954) Chim (Paris)9, 324 (1938) 2) Reilly (1938),
93

Logistics. Those aspects of military operations

 ,

L 58

Lovelace. Invented a priming expl consisting grade. This avoids any requirement of covering
of K chlorate, PA & MF, and an expl powd the cord with earth or sand when used in popu-
contg K chlorate, PA & charcoal lous areas (Ref 1)
Rejl Daniel (1902), 411 See also Cord, Detonating in Vol 3 of Encycl,
p C529-R
Refs: 1) S. Fordham, “High Explosives and
Low Detonation Pressure Explosives. Most Propellants”, Pergamon Press, NY (1966),
expl materials in wide use today may be char- 134–5 2) Blasters’ Hdbk (1969), 107–8
acterized by deton pressures ranging from approx
150–350 Icilobars. Proplnt materials, on the
other hand, exhibit comparatively low press Low Explosive (LE). An expl which when used
typical of deflgrn reactions. The difference in in its normal manner deflagrates or burns
pressures exhibited by these two classes of ma- rather than detonates; that is, the rate of ad-
terials leaves an interesting gap, the exploration vance of the reaction zone into the unreacted
of which may yield valuable information on material is less than the vel of sound in the
the propagation and kinetic limitations of detong unreacted material. Low expls include proplnts,
materials certain primer mixts, BlkPdr, photoflash pdrs
The reliable generation of deton press under and delay compns.. Whether an expl reacts
100 kilobars Should offer advantages from an as a HE or LE depends on the manner in which
engineering viewpoint in applications where it is initiated and confined. For example, a
higher pressures are neither needed nor desired. double base proplnt when initiated in the usual
Certain plastic/expl formulations described reamer is a LE. However, this material can be
(Ref 1) offer these advantages in addition to made to deton if the proplnt is initiated by an
others, such as the capability of being extruded intense shock. Conversely, a HE like TNT,
or injection molded into difficult configurations under certain conditions, can be ignited by
and then polymerized in place. Expls included flame and will burn without detonating
superfine PETN, acetone fine RDX, dextrinated Refi OrdTechTerm ‘(1962), 181-R
LA and Thallous Azide
Refs: 1) M.T. Abegg, H.J. Fisher, H.C. Lawton
& T. Weatherill, Explosivst la No 2, (Feb Low-Explosive Devices for Performing Me-
1970), 25–31 2) Anon, Expls&Pyrots 3 chanical Functions. Known as actuators or
(9), 1970 cartridge actuated devices (See Encycl 2 (1962),
C70–C72) low-explosive devices are small
parts in which a proplnt is ignited to produce
Low Energy Detonating Cord (LEDC). When gas. The gas generated performs such me-
detong cord is not required directly to initiate chanical functions as closing switches, actuating
HE, but solely to transmit deton from one valves, cutting cables, severing bolts, dispensing
place to another, it is advantageous to use a fluids, inflating bags, or starting engines
cord with very low charge weight. LEDC Basically, the devices are of two types,
consists of an extremely small core load “of HE, small actuators like dimple, bellows, or piston
one or two grains per ft, which is contained in motors and larger pressure cartridges and gas
a small continuous lead tube. The lead tube is generators. They are compact, efficient, re-
protected by wrappings of paper or cotton cord liable, inexpensive, and deliver a burst of
and an outer jacket of plastic. The countering mechanical work in a short period of time.
provides good tensile strength and unlimited Actuators provide a force over a small distance
w resistance. LEDC has a vel of deton of while gas generators exploit the energy of ex- .
24000 ft/see, slightly faster than standard de- panding gas
tong cord (Ref 2) Refi G. Cohn, “Low-Explosive Devices’ for
When used for laying above ground to con- Performing Mechanical Functions”, Proceed-
nect shots in civil engineering, quarrying and ings of the New Mexico Section of the ASME
open-pit operations, LEDC has the advantage (Behavior and Utilization of Explosives in
of producing much less noise than the normal Engineering Design) (2–3 March 1972)
 L 59

Low Freezing Dynamites (LF Dynamites). The most noticeable effect of low temp upon
See under Dynamite (Freezing of Dynamites stable deton results from a shrinkage in vol.
Containing NC) in Encycl 5 (1972), D1 588-R Because of the higher d at low temps, deton
to D 1593-L velocities, and consequently deton pressures,
are higher. These increases are too small to
have practical significance. Where propagation
Low Melting Ammonium Nitrate Explosives. time is critical, and must be synchronized with
See under Ammonium Nitrate Blasting Explo- a process that is independent of temp, this
sives, High Explosives and Propellants (AN effect, now accentuated by reduction in dis-
High Explosives) in Encycl 1 (1960), A346-R tance, can be a source of difficulty (Ref 2)
to A348-L, A352-R Refs: 1) L.V. Clark, SS 28, 345–8 (1933)
(In English) &CA 28, 1191 (1934) 2) G.V.
Horvat & E.J. Murray, “Propagation of Detona-
Low Order Burst. Functioning of a proj or tion in Long Narrow Cylinders of Explosives
bomb in which the expl fails to attain a high at Ambient Temperature and at –65°F”, PATR
order deton. Usually evidenced by the break- 2389 (1957) 3) Anon, EngDesHndbk, “Ex-
ing of the container into a few large fragments plosive Series–Explosive Trains”, AMCP 706-
instead of a large number of smaller fragments 179 (1974), 4–11
Ref.’ OrdTechTerm (1962), 181-R i

Lubrication
Low Order Detonation. See under Detonation, Fuzes. A lubricant is expected to perform
High-, Low-, and Intermediate Order, Velo- the jobs of minimizing friction, wear, and
. cities of, in Encycl 4 (1969), D384-R to galling between sliding or rolling parts. It
D389-R must do these jobs under two types of condi-
tions: (1) those which are inherent in the com-
Low Temperature Effect on Explosive Properties. ponent ,element itself –, such as load, speed, geo-
Tests conducted at temps of –80° and –1 83° metry, and frictional heat – and (2) those
with expls commordy used in detonators showed which are imposed from external sources —
that the vel of deton and Trauzl lead block ex- such as temp and compn of the surrounding atm,
pansion values were practically unaffected, nuclear radiation, inactive storage, vibration,
while brisance, as indicated by the lead plate and mechanical shock. The imposed conditions
test, was greatly reduced. The performance of are usually the more restrictive ones for lubri-
detonators, as judged by an initiation test on cant selection
unconfined cartridges contg LOX (qv) expls, Mechanical fuze components contain ele-
was also greatly reduced. Only detonators ments which undergo a variety of sliding and
contg Mannitol Hexanitrate, when immersed rolling motions, and combinations of the two.
in LOX expls for 3 minutes at –1 83°, resulted For example, a mass translating on guide rods
in complete deton (Ref 1) involves linear sliding only, the balls in a ball
Burning, and the initiation, growth, and bearing involve essentially all rolling motion,
propagation of expls are often retarded or pre- and meshing gear teeth surfaces experience
vented by very low temps. Tests of blasting both rolling and sliding motions. For any given
caps at liq nitrogen temps showed much de- type of motion, the lubricant found to be satis-
creased sensitivity (Ref 3) factory in one case will not necessarily be suit-
The effect of low temps upon the sensi- able for another if loads, speeds, etc, are not
tivities of initiators is usually quite small be- similar
cause the change from room temp is only Selection of the proper lubricant requires
a small fraction of the rise associated with not o~y knowledge of the specific function
initiation. However, systems that are marginal which the lubricant is required to perform in
with respect to growth or propagation of expl the device being lubricated but also considera-
reaction will usually fail in low temp testing tion of the interactions include chemical pro-
(Ref 3) cesses– such as corrosion of the metal parts
 L 60

by components of the lubricant, eg, corrosion Descriptions of available lubricants – oils,

due to oxidation of MoS2 in the absence of greasesand solid – with summaries of their
suitable inhibitors, or solution of copper alloys properties are contained in Ref 5
during lubricant oxidation processes; or physi- Space Applications. All known liquid lubri-
cal interactions, eg, attack by active organic cants and fatty acids evaporate, and they are,
materials on synthetic elastomers and plastic therefore, unsuitable for space conditions.
structural members. In addition, the inherent Tests showed that liquid lubricants do not
stability of the lubricant must be considered. even provide adequate lubrication in the lower
Stability is of particular importance if storage vacuums of space simulators. Solid lubricants,
for long periods of time with or without .ele- ~” such as molybdenum disulfide, tungsten di-
vated temps (which speeds up oxidation rate) ‘ sulfide, and the soft metals have given better
is involved. (In general, lubricants are inhibited results. However, the known data about ‘space
against oxidation by appropriate additives, but lubricants are results of simulator measure-
since temp is an important parameter, the oxi- ments made in the pressure range of 10’5 to
dation stability characteristics of the lubricant 10“6 torr which does not simulate real space
should be taken into account in connection conditions, and therefore, these available data
with the expected storage life and pertinent cannot be considered completely valid. It
temps of the mechanism being lubricated). can be expected that definite data on lubri-
Oxidation of fluid or semi-fluid lubricants may cant performance in a vacuum will be obtained
lead to thickening of the lubricant with con- by conducting tests in a simulator that reaches
sequent increased forces being required for the low 10-10 torr range. At this press level,
operation, or corrosive attack on the materials the monolayer formation time is increased to
of construction at least several hours which will result in a
A wide variety of fluid and semi-fluid lubri- sufficient time span for observing the metal
cants is available covering a wide temp range surfaces (Ref 6)
of applicability, a range of compatibility with
organic and inorganic structural materials, Explosives. Lubricants are utilized in HE’s to
and a range of other properties which may be minimize compn adherence to dies used for
pertinent, eg, nonspreading, lubricity, etc. ” In pelleting and press loading operations. Typical
addition, both dry powdered and bonded solid- of materials used with Tetryl have been graphite,
fflm lubricants are available. The choice of a stearic acid, Ca, Ba and Mg stearates (Refs 1,
lubricant depends on the totality of functions 2 & 3). Forchielli (Ref 4) reported on the
which the lubricant must perform, and the beneficial effects of the metallic stearates
structural and functional features of the me- (Ca, Li, Co, Zn & Cr) and talcum pdr with
chanism being lubricated. For example, a very Composition A-3
severe nonspreading and low vapor pressure Refs: 1) E.F. Reese, “Develop Process for Re-
requirement k connection with long term stor- clamation of Tetryl Scrap Containing Stearic
age may lead to a choice of a Wlid lubricant; Acid”, PATR 1131 (1941) 2) G. Weingarten,
whereas adhesion problems with bonded lubri- “Develop Improved Lubricant and Binder for
Pelleting Tetryl”, PATR 1261 (1943)
cants at high loads or with thin fdms associated
with low mechanical tolerances may compli- 3) Ibid, “Use of Calcium Stearate in the Pel-
leting of Tetryl”, PATR 1337 (1943)
cate the use of dry film lubricants. In fuzes
4) A.L. Forchielli, “Desensitization of High
subject to high rates of spin (above 25000 rpm),
Explosives by Waxes, Semi-Plastic RDX Com-
fluid and semi-fluid lubricants tend to be dis-
positions”, PATR 1787 (1950) 5) Anon,
placed by centrifugal force causing loss of lubri-
“The Lubrication of Ammunition Fuzing Me-
cant and possible contamination of other fuze chanisms”, Journal Article 49.0 of the JANAF
parts. Requirements for corrosion protection Fuze Committee (May 1967), AD 829-739
may require additives not accessible with dry 6) K.O. Bauer, “Handbook of Pyrotechnics”,
lubricants Chemical Publishing Co, NY (1974), 313
In simpler fuzes, choice of proper materials,
plating, and finishes can obviate a separate lubri-
cant
 L 61

Luck and Cross. Prepd, in 1898, proplnt powds Lundholm and Sayers. Proposed in 1899
by adding aq solns of Pb and Zn acetates to (BritP 10376) methods for the manuf of
NC as stabilizers. This addition could be con- several expls, eg, mixts of NC with nitro-
ducted in the presence of 30–50% acetone, aromatic compds, mixts of oxy- or hydro-NC
after which the mixt was dried with various organic compds, etc. They also
Ref Daniel (1902), 412 proposed charging projectiles by introducing
expls in layers ‘ -
Ref: Daniel (1902), 413
Luck and Durnford. Proposed, in 1896, to
prepare proplnt powd from nitrated hydro-
cellulose which had been treated with aq Lunge, Georg. (1 839– 1923). Ger chemist,
starch soln. This allowed the material to be noted for work on technological analytical
compacted into grains, blocks, leaflets, etc methods. Inventor of the nitrometer (See
Refl Daniel (1902), 411-12. below); author of nu~erous publications, among
them (in collaboration with E. Berl), “Chemisch-
technische Untersuchu’ngsmethoden”, a classic
Luck Powder. A proplnt proposed, in 1900, work on technical analysis
for use in shotguns. It consisted of NC powd Refi Hackh’s (1944), ~01-R
in which the NC was replaced by either cellu- ,,1
lose acetate, butyrate or benzoate. This wb-
stitution permitted the prepn of sporting powds Lunge Nitrometer. An app designed by G. Lunge
with a slow rate of combustion for the detn of nitrogen in either organic or
Refi Daniel (1902), 413 inorganic nitrates. It i: so designed that the
nitrate or nitric ester is dissolved in coned sul-
furic acid and the soln, without entrained gas,
Luminous Phenomena. See Detonation (and is afterwards admitted to a reaction vessel. The
Explosion) Luminosity (Luminescence) Pro- nitric oxide gas from the reaction is measured
duced on, in Encycl 4 (1969); D425-L to in a mercury audiometer in cc at atm press, a
D434-L; Flash and Flame in Encyci 6 (1974), barometer and thermometer are read, and the
F74-R to F75-L, and Fluorescence, Luminescence wt of nitrogen in the nitric oxide and the per-
and Phosphorescence, F 124-R to F 125-L centage of nitrogen in the sample are calcd
Adclrd Refs: 1) A. Michel-Ll-vy & H. Muraour, (Ref). This app was subsequently modified ,’
CR 206, 1566–8 (1938)&CA 32, 5629 by the DuPont Co, and is known as the DuPont
(1938) (Luminosity of expls) 2) H. Muraour, Nitrometer (See Encycl 1 (1960), A373-L to
A. Michel-IXvy & J. Rouvillois, CR 208, A377-L for description of use)
508–10 (1939) & CA 33, 3157 (1939) (Lu- Ret Davis (1943), 270–1
minosity of expls) 3) H. Muraour, Chim&lnd
(Paris) 47,3-15 (1942) &CA 37,6461 (1943)
[Luminosity has its origin in the shock waves Lupersol DDM. A proprietary catalyst of
generated by expls, and not in emitted gas as Wallace & Tiernan, Inc, Buffalo, NY, contg
claimed by Lafitte, CA 20; 1324 (1926)] 60% methylethylketone peroxide in dibutyl-.
4) A. Michel-L@ & H. Muraour, CR 224, phthalate, used as the hardener in Laminac (qv)
695–6 (1947) & CA 41, 5723 (1947) (Origin Refs: 1) OrdTechTerm (June 1962), 183-R
of luminosity which accompanies the firing of 2) Anon, EngDesHdbk, “Military Pyrotechnics
expls in untampe~ drill holes. It is not a func- Series, Part ,Three – Properties of Materials
tion of the gas evolved, but of the amt of air Used in Pyrotechnic Compositions”, AMCP
in the hole) 5) L. Deffet & P. vanWouwer, 706-187 (Ott 1963), 183–4
Chim&Ind (Paris) 69, 1086–7 (1953) &CA
49, 6608–9 (1955) (Luminosities produced
by expl shock waves)
 L 62

LX Explosives. A code employed by the ‘ than the others

Lawrence Livermore Laboratory, Univ of LX-11 is like LX-04, but intentionally de-
California (Livefrnore), USA, to designate graded in energy by adding an addnl 5% binder
formulations in production. A specific code LX-13 is a variant of the LASL expl XTX-8003
designation is assigned to an expl when the Ref B.M. Dobratz, “Properties of Chemical
state of development of its formulation has Explosives and Explosive Stimulants”, Lawrence
reached the point where a set of reasonable Livermore Laboratory, Univ of California (Liver-
manufg specifications can be written, the more), UCRL-51319b(l 5 Dec 1972), pp 3-3,
evaluation of the material’s chemical, physi- 3-4, 17-1, 17-2
crd, expl props and sensitivity is essentially
complete, and the material has a definite ap- ,,
plication Typicrd LX formulations are given in the fol-
This code consists of the two letters. LX lowing table:
followed by a dash, two digits, a second dash, Formulation
and finally a single digit. The first pair of Explosive Ingredient Weight % Color
digits is merely an arbitrary serial number
LX-01 Nit romethane 51.7 Clear
assigned in sequence, while the last digit de- Tetranitromethane 33.2
notes a subclass in the series. Thus, LX-01-0, l-Nitropropane i5.1 ~
LX-02-1 . . . . . LX-05-0, etc. The last digit
provides for small changes in manufg specitl Lx-02-i PETN 73.5 Buff
cations. For example, when LX-04-O has Butyl rubber 1.7.6
undergone a revision of expl particle size, new Acetyltribut ylcitrate 6.9
lots, manufd under the revised specification, Cab-O-Sil * 2.0
are identified as LX-04-1 LX-04- 1 HMX 85.0 Yellow
LX-01 is a liq material, characterized by a Viton A ** 15.0
wide liq range (–65° to +165°F), moderate LX-07-2 HMX 90.0 Orange
energy release, and good stability and sensiti- Viton A 10.0
vity props. Cirution: The TNM component is
LX-08 PETN 63.7 Blue
moderately volatile and highly toxic
Silicone rubber 34.3
LX-02 is a material of putty-like texture
Cab-O-Sil 2.0
characterized by ability to propagate in very
small diameters : LX-09-1 HMX 93.3 Purple
LX-04 is a solid expl characterized’ by ex- p-DNPA 4.4
%./ FEFO *** 2.3
cellent mechanical and compatibility props, an
energy release about 9% less than LX-09 and LX-10-O I-IMX 95 B1-grn spots
sensitivity props much superior to LX-09 Viton A 5 on white
LX-07-2 is a modification of LX-04 with a
LX-1 1-0 HMX 80 White
higher energy release (5% less than LX-09-0),
Viton A 20
obtained at the expense of some degradation
in mechanical props (less elongation, etc) and LX-13 PETN 80 Green
in sensitivity Silicone rubber 20
LX-08 is an extrudable, curable expl de-
veloped for use in Dautriche timing tests * Cab-O-Sil — trademark for colloidal silica particles
LX-09 is similar to the LASL expl PBX- ** Viton A — trademark for a synthetic rubber de-
9404, but with significantly improved thermal
rived from vinylidene fluoride and
stability and slightly poorer physical props
hexafluoropropylene
LX-10 is in the same energy class as LX-09 *** FEFO — bis (2-fluoro-2,2-dinitroethyl) formal
and PBX-9404, but utilizing HMX and Viton A
like LX-04, and having excellent thermal
characteristics. It also exhibits high creep re-
sistance, but may be somewhat more sensitive
 L 63

Lycopodeum (Club-Moss or Vegetable Sulfur). Lysol and Nitrated Derivative

Fine yellow powd consisting of flammable Lysol. Brown, oily liq; creosote odor; poison-
spores of Lycopodeum clavatum, which grows ous. A mixt of alkali compounds of the higher
in North America, Asia and Europe (Ref 3). phenols with fat and resin soaps. Obtained by
It has been used in pyrotechnic formulations, boiling a mixt of heavy tar-oils, fats and resin
eg, in green stars: Ba perchlorate 70.5, Mg with alkali. Sol in w, ale, eth, chlf & benz
powd 11.8, shellac 11.8 & lycopodeum powd (Ref 4). A registered trademark of Lehn &
5.9% (Ref 2). It is also a constituent of some F@k Products Co, Bloomfjeld, NJ, for a cresvlic
expls (Ref 1), eg, in Leonard’s smokeless powds disinfectant and antiseptic (Ref 3). On nitra-
(qv) tion it yields an expl
Refs: 1) Daniel (1902), 405 ‘2) Davis Nitrolysol (Nitrated lysol). Mp about 64°.
(1943), 86 3) CondChemDict (1971), 530 Prepd by one-stage nitration of lysol. It has
been proposed for use as an additive to reduce
the “mp of other expls such as PA. It is also
Lyddite. Br expl, similar in compn to the Fr suitable for the manuf of plastic expls, and for
Melinite (qv). The name was derived from the coating hydroscopic substances such as Na
town of Lydd, near which @ expl was manufd nitrate, to protect against moisture (Refs 1 & 2)
and tested. It contains either PA alone, or in Refs: 1) E. Raynaud, FrP 449785 (1912) &
admixture with about 10p o~ other aromatic CA 7, 2687 (1913) 2) Colver (1918), 692
hydrocarbons, added principally to lower the 3) Hackh’s (1944), 503 4) CondChemDict
mp of the PA. Lyddite was adopted in 1888 (1950), 409; not found in later editions
for charging torpedo warheads, and later during
the South African war, for HE projectiles
Refs: 1) Daniel (1902), 414 2) Colver
(1918), 14 3) Bebie (1943), 95 4) Davis
(1943), 166