N NWSC/CR/RDTR-595

co
OR SURVEY OF MILITARY PYROTECHNICS

DR. BERNARD E. DOUDA

NAVAL WEAPONS SUPPORT CENTER

ORDNANCE ENGINEERING DEPARTMENT
CRANE, IN 47522-5050

24 MAY 1991

APPROVED FOR PUBLIC RELEASE; DISTRIBUTION IS UNLIMITED.

PREPARED FOR:

COMMANDER
NAVAL AIR SYSTEMS COMMAND
WASHINGTON, DC 20361-5404

91-06001
 I Form Approved
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24 MAY 91 FINAL
4. TITLE AND SUBTITLE 5. FUNDING NUMBERS

SURVEY OF MILITARY PYROTECHNICS

6. AUTHOR(S)

DR. BERNARD E. DOUDA

V PERFORM.NG ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION

REPORT NUMBER

NAVAL WEAPONS SUPPORT CENTER

ORDNANCE ENGI,4EERING DEPARTMENT
CRANE, IN 47522-5050 NWSC/CR/RDTR-595

9. SPONSOORING'MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSORING /MONITORING

AGENCY REPORT NUMBER

COMMANDER
NAVAL AIR SYSTEMS COMMAND
WASHINGTON, DC 20361-5404
11. SUPPLEMFNTARY NOTES

PREPARED FOR PRESENTATION AT THE 16TH INTERNATIONAL I0511/07A

PYROTECHNICS SEMINAR, JONKOPING, SWEDEN, 24-28 JULY 1991.
12a [ISTRIBUTION'AVAILABILITY STATEMENT 12b. DISTRIBUTION CODE

APPROVED FOR PUBLIC RELEASE;

DISTRIBUTION UNLIMITED.

13. ABSTRACT (Mi,m mn.?u words)

About twenty-five activities from fourteen different countries contributed

information about ongoing pyrotechnic projects and concerns. This
information is summarized to provide an idea of the type and scope of the
work underway. Although the survey is not exhaustive, an overall impression
can be formed to indicate the focus and thrust of the pyrotechnic efforts.

4 1;7,1,i"T RK7 15. NUMBER OF PAGES

41
PYROTECHNICS 16. PRICE CODE

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S IRITY (-tASS 'CTtON 18 SE(URITY (LASSIFICATION 19 SECURITY CLASSIFICATION 20 LIMI1ATION OF ABSTRACT
i)f 1D PORT OF tiS PAGE OF ABSTRACT
UNCLASSIFIED UNCLASSIFIED UNCLASSIFIED UL
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 SURVEY OF MILITARY PYROTECHNICS
Bernard E. Douda
Naval Weapons Support Center
Crane, Indiana 47522-5050 U.S.A.
ABSTRACT

About twenty-five activities from fourteen different countries contributed

information about ongoing pyrotechnic projects and concerns. This
information is summarized to provide an idea of the type and scope of the
work underway. Although the survey is not exhaustive, an overall
impression can be formed to indicate the focus and thrust of the
pyrotechnic efforts.
A major concern expressed by the contributors is the environment, health,
and safety associated with pyrotechnics. Governmental regulations have
emphasized the ecological, toxicological, and safety aspects of
pyrotechnics. This encouraged many of the countries to become involved in
development of insensitive pyrotechnics to increase the margin of safety
associated with these devices. With respect to health, the toxicology of
heavy metals, hexavalent elements, and battlefield smoke and aerosols is
being evaluated. Efforts are being directed to replace chromates in delays
and to find replacements for hexachloroethane smokes to reduce human
exposure to these health threatening materials. Environmental conditions
related to the production of pyrotechnics as well as their eventual
disposal through the demilitarization process are also addressed. Major
projects are reported which deal with ecologically acceptable processes for
demilitarization and disposal of all categories of pyrotechnics.
New equipment for preparing pyrotechnic compositions is reported. The
focus of these efforts is not only to achieve homogeneous mixtures but also
to improve the safety of the process. For example, a fluid-bed machine for
blending, granulating, and drying is described in which a large number of
different pyrotechnic mixtures have been processed. A twin-screw extruder
is being evaluated for infrared composition processing. A disc granulator
is under evaluation for processing compositions such as boron-potassium
nitrate.

To a large degree, reliability and safety are the motivation for

considerable effort in the study of laser ignition of pyrotechnics. Both
diode and gas lasers are being evaluated to initiate combustion of
compositions such as zirconium-potassium perchlorate, boron-potassium
nitrate, and titanium subhydride-potassium perchlorate. A number of
ignition research projects emphasize ignition theory in general as well as
the determination of mechanisms directly related to laser ignition.

Several projects are reported which deal with infrared decoy flares.
Research on and simulation of the combustion process is being conducted.
An air-gun is described which is used to ground test the performance of
flares in flight in order to simulate some of the dynamic parameters
associated with the launch of a decoy from an aircraft. A number of
agencies report development of improved decoy devices designed to deal with
advanced infrared threats. A decoy simulator for training use is reported.

There are a substantial number of projects which address a special or

peculiar problem. Some examples are work to understand and improve whistle
compositions, development of riot control and explosive ordnance disposal
devices, degradation and stability studies, training device and simulator
development, evaluation of coatings for ingredients, development of a
hydrogen burn-off igniter, and development of a non-toxic training
smoke/obscurant.

iii
 INTRODUCTION
Dr. Jan Hansson suggested the preparation of this paper as an Overview or
Survey of Military Pyrotechnics. To meet the objectives of such an effort,
it was immediately apparent that the scope would need to be limited.
First, there would be a presentation time and publication space limitation.
Secondly, there would be sensitivity constraints related to some projects
which could not be reported in this forum. Thirdly, the scope of this
paper would need to be limited to information about energetic materials
projects which were neither primarily explosive nor propellant in nature,
consistent with the limited definition of pyrotechnics. And finally, in
the preparation time available, it would not be possible to contact all
pyrotechnicians worldwide in order to obtain contributions. Nevertheless,
it was decided to compile as much information as could be made available
within the stated constraints. The result is that projects could not be
described in detail. All information was summarized. To compensate,
references to published data were included quite liberally.
About twenty-five activities from fourteen different countries contributed
information about ongoing pyrotechnic projects and concerns. These are
presented herein by country in alphabetical order.

MILITARY VS CIVILIAN PYROTECHNICS

Except for one digression, no great effort will be made to show the strong
relationship and similarity between the military and civilian pyrotechnics.
However, it is worthy to recall that pyrotechnics is not a recent art or
science. The Chinese, as Dr. Ding reminded us at the Fifteenth
International Pyrotechnics Seminar, purified saltpeter about 300 AD,
reported gunpowder not later than 850 AD and fireworks about 900 AD. Ever
since that time, civilian pyrotechnics (fireworks) were used for personal
pleasure and celebration.
One such event took place in Antwerp on 17 April 1635. A spectacular
fireworks display was presented from the belfry of the Notre Dame Cathedral
to celebrate the joyous entry of
Prince-Cardinal Ferdinand of Austria,
Governor of the Southern Netherlands. -

Figure 1 shows the event as recorded

by Theodoor Van Thulden; painter, W,
engraver and pupil of Peter Paul Rubens.'
Without prior knowledge that this was a
joyous occasion, one might imagine that
the cathedral was on fire from a military
action. Fortunately, this was not the
case. The cathedral still stands in the
center of Antwerp.

Figure 1: Fireworks from the belfry of

Notre-Dame Cathedral in Antwerp, Belgium
in 1635. Built around 1400. A copy of
this engraving was graciously made
available by Dr. Guy Hendrickx.
 AUSTRALIA
CONTRIBUTOR: Mr. Leo DeYong, Materials Research Laboratory

Pyrotechnics work at the Materials Research Laboratory (MRL) may be broadly

broken into three areas; namely materials, initiation systems, and device
development. Descriptions of work in these areas follows.

MATERIALS

Delay Systems - The development of gasless delays opened up a new area of

delay chemistry. But, although gasless delays are frequently used for many
reasons they generally suffer from one major drawback - the oxidants are
usually highly toxic. For example a common delay system comprises boron
and barium chromate. Barium chromate is virtually insoluble in water and
chromates, as a general class of chemical, cause severe health problems (it
is a documented human carcinogen).
Several years ago MRL developed a low toxicity (no chemical is non toxic)
delay composition based on boron and red iron oxide. This work has been
further extended to look at a series of delays based on this fuel/oxidant
combination (and variations with additives) with a reciprocal burn rate
ranging from 0.4 to 4.0 seconds per centimeter. An added feature of those
compositions is that they have excellent priming characteristics i.e., they
are easily ignited without the use of a priming system.

Illuminating Flares - Illuminating flare compositions have been developed

for two naval signal systems. Both compositions are designed to function
under heavy sea conditions (up to sea state 6) and be visible at distances
of up to 9km in daylight for up to 80 seconds. Flares have been developed
based on the standard magnesium/sodium nitrate/binder formulation which
achieved those requirements.

Smokes - Conventional white smokes contain zinc and hexachloroethane which

form chlorides and oxides of zinc as reaction products; both of these are
highly toxic. White smokes are used for fire fighting training in enclosed
spaces which exacerbates the health problem. We have been looking at the
development of new white smoke compositions based on terephthalic acid and
cinnamic acid.

Smokes as obscurants may also be generated by fibres rather than as a

chemical particulate. We have undertaken to participate in a collaborative
program of work with laboratories in USA, UK and Canada to study the
obscuration effect of fibres with particular emphasis in the millimetre
waveband. This work includes not only the choice of the fibre, but also
the dissemination of the fibres.

Primers - A gasless percussion primer developed at MRL several years ago

based on boron, lead oxide and tetracene has caused problems in production
due to poor flowability. This has entailed hand-filling of primer cups
with resultant increased cost and reduced operator safety. A programme of
work has been undertaken to improve the flowability of this composition
whilst still retaining its performance and sensitivity. This involved
granulation with a range of solvents, addition of binders and/or addition
of flow modifier agents.
We also have a strong work program on the development of conducting
composition caps for rapid fire weapon systems. Conducting composition
caps have the advantage of enhanced electrical characteristics which enable
them to pass stringent RADHAZ requirements. Currently conducting
composition caps are being developed for the N43 primer.

2
Photoflash Compositions - Photoflash compositions based on magnesium or
aluminum and potassium perchlorate (and a flow modifier) have often been
used as a sound producing composition for battle effect simulators and for
grenades for special forces. They also have application as a spotting
charge for mortar rounds but this requires a higher filling density for
efficiency reasons. Current work involves modification of the composition
for application to 81mm mortar rounds. Solvent granulation and binder plus
granulation modifications are being conducted to fulfill this requirement.

The use of this composition for special forces is less than ideal as the
smoke signature produced is considered excessive. Work is ongoing to
examine the effect of additives and changes in the oxidant and/or fuel to
reduce the smoke signature to an acceptable level.

Magnesium Powder - Magnesium is one of the most common fuels used in

pyrotechnic compositions. Although it has a high combustion temperature
and large heat of combustion, it suffers from degradation on storage.
Moisture readily attacks magnesium powder, generating hydrogen gas which
presents a serious problem in sealed stores. The reaction decreases the
amount of available magnesium thus reducing the efficiency and performance
of the pyrotechnic composition. These effects are somewhat reduced by
coating the magnesium powder with various organic binders but problems are
still known to occur.
A program of work has been undertaken and recently completed in which the
coating efficiency of several binder systems have been evaluated for
magnesium powder. The success or otherwise of the coating was examined and
evaluated using Scanning Electron Microscopy, Gas Evolution, Weight
Changes, Surface Energy Analysis, FTIR and performance measurements of
flares based on magnesium and sodium nitrate.
Thermites - Extensive evaluation of the MRL developed plastic thermite is
being undertaken to determine its potential use for Explosive Ordnance
Disposal (EOD) applications, particularly evaluation against both thick and
thin cased munitions. At the same time, we are looking at new formulations
for thermites based on the traditional Goldschmidt reaction and also novel
intermetallic systems.

Insensitive Compositions - A program of work has been completed to examine

the implications of the US Insensitive Munitions (IM) policy (and possible
adoption of IM guidelines by the Australian defence forces) for pyrotechnic
formulations. This has involved thermal analysis of a range of
compositions (DSC, DTA, TGA) and assessment of the response of compositions
to both fast and slow heating rates. This has concentrated on the use of
the SSCB (Super Small Scale Cookoff Bomb) and the RARDE cookoff bomb, both
of which were developed for assessing the response of explosives to thermal
stimuli.

IGNITION STUDIES
Laser Initiation - Work is underway to use high power lasers to initiate
pyrotechnic compositions and to study the characteristics of both the laser
and the pyrotechnic that are required for reliable and sustainable
ignition. Work has initially focussed on the use of a 1kW carbon dioxide
laser but further developments using laser diodes and fibre optics are
planned.
Slapper Initiation - Many pyrotechnic and related explosive devices use
direct initiation from electro-explosive devices. Most of these require
protection from induced RF energy and electrostatic discharge. Slapper
detonators are increasingly being seen as a means of achieving these
requirements for high explosives. Slapper initiation of pyrotechnics could
be a suitable initiation system for higher hazard pyrotechnics. Initial
studies using 0.25mm flyer plates succeeded in initiating several low gas

3
pyrotechnic compositions. Microscopic examination of the pellets of the
pyrotechnics which failed to ignite showed evidence of ignition but failure
of the reaction to propagate.
Infrared Compositions - This work involves the development of improved
infrared decoy flare compositions and systems to protect both aircraft and
naval vessels from advanced infrared guided missiles. The specific work
involves enhancing the performance of flares operating in the 3Mm - 5Am
region by the production of specific molecular emitters. Similar work is
being undertaken in the 8Mm - 14Mm region. Included in this work is an
extensive computer simulation exercise of the thermochemistry of flare
combustion.

DEVICE DEVELOPMENT
Visual Mine Firing Indicator (VISEM) - Concepts for a visual mine indicator
have been proposed for an exercise mine. VISEM is a device connected to a
submerged mine which releases a pyrotechnic payload to provide an
indication on the ocean surface that the mine has been "triggered" during
an exercise. The visual output comprises both a colored smoke and a
colored flare.

Thermite Torch - A thermite torch is being developed for use in Explosive

Ordnance Disposal (EOD) applications. The torch has been engineered to
provide an enhancing effect to the thermal output of the pyrotechnic
payload which results in a better cutting action.

Marine Marker - A submarine launched marine marker has been developed at

MRL over the last few years. The marker is launched to the surface from a
submerged submarine and deploys either a parachute flare or a surface
payload comprising a flare, a smoke and a dye marker.

BELGIUM

CONTRIBUTOR: Dr. Guy Hendrickx, EUG. HENDRICKX, S.A.

PHOTOMETRIC TUNNEL VERSATILITY

All producers of military and/or commercial pyrotechnic devices require a

test capability such as a photometric tunnel if light measurement is to be
performed. A photometric tunnel, built primarily for measurement of the
photometric output of pyrotechnic illuminating devices, is equipped with
radiation measurement instruments. The structure, as well as its
instrumentation, can be put to a variety of uses in addition to its primary
function. This versatility and capability is an important asset for the
producer. It allows static testing of various devices such as flares,
signals, tracers, incendiaries, delays and igniters. These static tests
are useful to simulate the much more expensive dynamic performance tests.
In this way, complete round destructive testing can be minimized.
Production variation can be monitored. As will be shown, while the data
produced in the tunnel can be quite useful, careful analysis is always
necessary before taking any conclusions.

Light measurement: Testing in a photometric tunnel is a widespread method

to measure the output of a pyrotechnic flare, signal, tracer, etc.
Unfortunately, no two photometric tunnels conform to the same standard.
They differ in structural size, shape and materials and are equipped with
differing measurement instruments. All presumably are calibrated to an
absolute standard. Nevertheless, the measured output data from different
tunnels do not always compare. To overcome this condition, correlation
factors between tunnels are established to allow tunnel-to-tunnel
comparisons. Sometimes, this also needs to be done for equipment-to-
equipment comparison.

4
An example of tunnel-to-tunnel variation follows. The same Minolta
photometer containing a silicon cell was used to measure the luminous
intensity, in candela (cd), of 81mm HI mortar flares in three different
tunnels. The following data, based on a limited sample size, show the
RARDE, UK and MEPPEN, Germany tunnels to be comparable but that data from
the Eugene Hendrickx Deurne (EHD), Belgium tunnel are somewhat less.

RARDE BWB
EHQ BelaiUM Fort Halstead. UK MEPPEN. Germany
816,052 cd 902,838 cd 865,873 cd
756,269 852,996 863,953
804,833 884,703 867,639
To show equipment-to-equipment comparability, the output from a 40mm
illuminating flare was simultaneously measured in the Naval Weapons Support
Center Crane (NWSCC) tunnel using NWSCC instruments and the Minolta
photometer described previously. For a sample size of 10 units, the mean
with the NWSCC instruments was 134,710 cd and with the Minolta was 126,650
cd, about a six percent difference.

A second experiment was conducted similar to the above but with a different
flare, the MK 1 MOD 2 illuminating hand grenade, and a 15 unit sample size.
The mean with the NWSCC instruments was 134,900 cd and with the Minolta was
123,890 cd, about an eight percent difference.
The MEPPEN equipment was compared to the Minolta in the BWB MEPPEN tunnel.
Thc flares were 81mm mortar round units. Comparable data were observed as
follows:

MEPPEN eauipment MINOLTA

818,000 cd 865,000 cd
833,000 863,000
832,000 867,000
When the same experiment was conducted at RARDE Fort Halstead, UK, the data
observed were:
rARDE euipment
MINOLTA

762,000 cd 902,838 cd
734,000 852,996
750,000 884,803
The data from the RARDE equipment are about fifteen percent lower than
those from the MINOLTA.

The above experiments and data serve to support the caution to interpret
the data carefully. There are instrumental as well as tunnel differences
which remain unexplained.

Other Tunnel Uses:

A. An example of other uses of the facility and the instrumentation is the

testing of a base bleed igniter. When only the output curve shape is
important, but not the light intensity, the igniter reaction time and
burning time can be determined during static test using a photometer.
Figures 2 and 3 are examples of the measured data of a base bleed igniter
lit with a squib but not in the closed vessel bomb.

5
 T 7 I_7777

H I

Figure 2: Igniter output Figure 3: Igniter Output

The information can be submitted to additional statistical analysis to

provide a better description of the igniter behavior and the production
process. The base bleed igniter ingredients are barium peroxide, magnesium
powder, aluminum powder, graphite, calcium resinate, and shellac. The
latter three aid the granulation and pressing processes. Similar
procedures are applied to determine performance of pyrotechnics such as
tracers and rocket motor igniters.

B. To simulate dynamic firing and functioning of the base bleed igniter,

the igniter is static fired in a closed vessel bomb as shown in Figure 4.
A propellant powder, ignited inside the bomb, generates the pressure which
simulates conditions inside the gun
barrel. A rupture disc
allows the internal
pressure to develop 7--
to the desired value
(=2300of
leads b).a squib
The igniter
are fed_
through a small hole in____________________________
the rupture disc. The Fgr3 gnitrup
squib and black powder to itinasaisicl|nlyist
ignite the
powder propellantni
(=175 g) whichhite andth production
in turn ignites the base tme
bleed ignitero A piezo- igniters
electric gage measures as s
the pressure. Once
again burning time is .,
determined with theinsdethegu
photometer. Figures 5
and 6 are examples of
pressure-time curves of
base bleed igniters. Figure 4: Closed vessel bomb.

squiband
lack owde

Figure 5: Pressure vs Time. Figure 6: Pressure vs Time.

The pressure, combined with reaction time and burning time data, taken
together, provide valuable information about the igniter performance.
After analysis of the static data, these data are correlated with dynamic
firing data. A good correlation provides assurance that the static tests
are suitable for assessing the regularity in production and in functioning.

C. The same general procedures, facilities and equipment can be used to

evaluate performance of rocket igniters, squibs, delays and related
materials.
CANADA

CONTRIBUTOR: Mr. Guy Couture, Defence Research Establishment, Valcartier

SOME PYROTECHNICS AT DREV

MARINE LOCATION MARKER (Mr. D. Sanschagrin, principal investigator):
Capable of producing both smoke and flame outputs, the marine location
marker is a day and night device specially designed for marine operations
including search and rescue, and anti-submarine warfare. This project was
initiated at the Defence Research Establishment, Valcartier (DREV) to
modify the current marker in the following four aspects to enhance its
versatility and improve its performance. A fresh water battery was
required to allow the marker to function in fresh water as well as sea
water; a scuttling feature was required to prevent the markers from washing
ashore; a new optimized smoke and flame formulation was introduced in the
new marker; and finally the arming mechanism of the new marker had to be
redesigned.
Fresh Water Battery: The original salt-water-activated battery was
replaced by a new one, able to function also in fresh water. However, this
new battery incorporated a cellulose separator which deteriorated after
four years of storage. The electrolyte appears to attack the separator
which turns brown and crumbles easily. For this reason, a new battery
incorporating a polypropylene separator was introduced.

Smoke and Flame Formulation: The new marker contains a new patented C-55
smoke and flame formulation, containing Taktene, a polybutadiene binder.
The new formulation is more rubbery and provides a better performance. It
has a higher red phosphorus loading of 71 percent, compared to 51.5 percent
for the current formulation. The formula is 71 percent red phosphorus,
15 percent sodium nitrate, 8 percent aluminum flakes, 1 percent calcium
carbonate, 1 percent titanium isoproxide and 4 percent polybutadiene.
Arming Mechanism: Another major improvement over the current marker is the
new reversible arming mechanism. It is based on the movement of a piston
which, when rotated, is pushed out by a spring. Actual arming is obtained
by further rotating the piston to establish the contact between the water
activated battery and the squib. The battery is then fully exposed and the
mechanism is locked in its armed position. Manually rotating the mechanism
counterclockwise, returns the marker to the original safe.

Scuttling Feature: The scuttling capability was achieved by removing a

fraction of the rigid foam, providing a ballast compartment that is filled
by water through small openings of 0.5 mm in diameter made in the outside
casing. These holes are permanently open and initiate the scuttling
process as soon as the marker is immersed. This allows the marker
sufficient time to function completely but also ensures scuttling of those
that fail to ignite.

HIGH PERFORMANCE TRACER COMPOSITIONS (Mr. P. Bri4re, principal

investigator) Over the years, DREV has acquired expertise in tracers and
has built a tracer evaluation facility that allows the quantitative
characterization of tracer compositions using high speed air turbines

7
capable of spinning 7.62 mm and 5.56 mm bullets at 100,000 rpm and 300,000
rpm respectively. This computerized facility is equipped with a radiometer
and a photometer to provide instant data reduction of the luminous
intensity and energy of each round.
Major improvement to the luminous output of tracers has been obtained by
various means. Laboratory measurements also confirmed the influence of
factors such as the rotational speed and the orifice diameter of a bullet.
The rotational speed has a significant effect on the burn rate and on the
luminous efficiency of a tracer composition. In the case of 7.62 mm and
5.56 mm tracers, the luminous efficiency was observed to increase
substantially above a certain speed and tend towards a maximum at the
rifle-firing rotational speed.
The orifice diameter of a bullet is also a factor. A larger orifice gives
a higher luminous efficiency. In the case of the 5.56 mm tracer,
substantial trace intensity improvements were obtained by lessening the
boat tail angle at the rear of the projectile. The required ballistic
match of the tracer round with the ball round however limits the extent of
this modification.
Formulation Improvements: With the acceptance of 5.56 mm ammunition as the
NATO standard for small-arms ammunition, most tracer bullets are barely
able to meet all user requirements. The physical size of the bullet, along
with its high muzzle velocity, led to a relatively low brightness of the
tracer bullet during flight. The development of improved tracer
compositions, therefore, was initiated.

Previous work showed that a fluoroelastomeric binder produced tracer

bullets with higher luminous output than those containing the standard
carnuba wax. A further investigation of various polymers demonstrated that
rubbers with a high fluorine content provided tracer compositions with the
highest luminous output. This study also indicated the importance of the
processing techniques used in the preparation of the compositions. Various
processing methods were studied including dry processing, wet processing
and a combination of both depending on the solubility of the binders.
Kynar 9301, Viton A and Kynar 461 were used as they contain more than
60 percent by weight of fluorine; the Kynar 461 was used only in dry
processes because it is not easily dissolved in common solvents. The best
two methods were as follows. The first involves a dry process in which the
magnesium is mixed with the binder in one step and the strontium nitrate is
mixed with the magnesium carbonate as a separate premix; then both premixes
are blended together. The second is a wet process in which only the
magnesium powder is coated by the binder via a co-precipitation process.
The polymer is dissolved in a solvent (acetone), adding the magnesium while
stirring, then adding a nonsolvent (hexane) to cause precipitation of the
polymer onto the magnesium. However, the best results are obtained when
about half of the nonsolvent is added followed by the addition of the other
ingredients while the binder is in a gel state. The precipitation is
completed by adding the remaining nonsolvent. This technique allows
complete coating of the magnesium powder and adhesion of the other solids
to the gel surface.

Luminous intensities exceeding 3 times that of the standard Canadian

5.56 mm bullet were ibtained with the new compositions. However, because
of the high heat generated, a fairly large number of rounds became unstable
at 550 m as a result of the deformation of the thin wall of the 5.56 mm
bullet. Such compositions however should function properly in larger
projectiles or bullets, offering thicker walls and lower rotational speeds.
Further development led to optimized formulations containing a chlorinated
rubber (Alloprene) as a cooling agent. The following BT-L252 formula is
typical of the new compositions that are especially adapted for the 5.56 mm
ammunition. It is 38.1 percent magnesium, 45.6 percent strontium nitrate,
4.7 percent magnesium carbonate, 1.9 percent shellac, 6.0 percent

8
chlorinated rubber and 3.7 percent Viton A binder. Some tracer
characteristics are:

Attribute BT-L-252 Canadian Standard

Specific Luminous Efficiency 2526 915
(cdoseg' at 270,000 rpm)
Impact sensitivity (J) 10 15
Friction sensitivity (N) 160 160
Heat of combustion (cal/g) 2331 179
Temp. of ignition (0C) 618 568
CASTABLE WHITE SMOKE POTS (Mr. Guy Couture, principal investigator) The
objective of this project was to design and develop a family of castable
white smoke pots of various durations, incorporating as much as possible
available hardware from current devices and producing a reduced toxicity
white screening smoke. Three- and five-minute durations were selected for
the first phase of that program as it was thought that minor modifications
could turn a three minute smoke pot into a five minute one and vice versa,
both being of the same dimension and using the same ignition train.

Design: The prototype design of a five-minute smoke pot contains 1.2 kg of

a castable composition. It uses a firing mechanism and ignition train
whose efficiency has been demonstrated in current stores such as colored
hand smoke grenades.
Characterization of combustion products: To identify predominant reaction
products and to assess the health effects of the compounds, five-minute
smoke pots were submitted to a contractor for an environmental evaluation.
The following optimized smoke compositions were selected for the
evaluations.

Main Comp. Ignition Comp.

Ingredients % of Weight % of Weight
Cinnamic acid 50 34
Potassium Chlorate 23 35
Sucrose 6 9
Iron Oxide 1 2
Binder (HTPB-IDP-DDI) 20 20
A smoke sampling technique was adapted from standard methods used to
measure the pollutant emission rates from flue gas and involves continuous
analysis of combustion gases (CO, C02, 02, SO2 , NO.) and total hydrocarbons.

The following table shows the components released from a five minute smoke
pot.

Total Amount
Component Released (g)

Particulate Material ... ........... .. 143

Sulfuric Acid ..... ............... 8.79
Hydrogen 3romide ..... .............. ND
Hydrogen Chloride .... ............. 6.15
Hydrogen Fluoride .... ............. 0.01
Nitric Acid ..... ................ 2.04
Nitrous Acid ...... ................ ND
Phosphoric Acid ....... .............. 0.01
Styrene ......... .................. 4.87
Benzaldehyde ..... ................ . 1.97
Phenols and Cresols ...... ............ 1.05
Chloroethenyl Benzenes ..... ........... 1.13
Aliphatic Hydrocarbons .... ........... .. 26.96

9
 PAHIs . . . . . . . . . . . . . . . . . . . 8.90
Cinnamic Acid ..... ............... .30.11
Other Oxygenated Hydrocarbons .. ....... .14.32
Hydrogen Cyanide .... ............. ... 0.07
Ammonia ....... .................. 0.20
Potassium ...... ................. . 6.71
Iron ........ .................... 0.60
Calcium ....... .................. 0.19
Zinc ........ .................... 0.14
Silicon ....... .................. 0.11
Tin ........ .................... 0.05
At first sight, the components of most concern are potassium, hydrogen
chloride, sulfuric acid, ammonia, tin, calcium, nickel and nitric acid. It
should be noted, however, that sulfuric acid seems abnormally high and this
is being re-examined during additional evaluations. Chlorinated aromatic
compounds, such as dioxins and furans will be considered since these
components are found during relatively low temperature combustion processes
involving organic components and chlorine. Finally the health effect of
the compounds will be assessed. A field dispersion model will be developed
to predict smoke concentrations at various distances from the source and to
assess the risks for the users.

FRANCE

COMPOSITION DEGRADATION

CONTRIBUTOR: ICA J.-C. DEPEIGNE, GERPy

The main subject of recent activities at Group d'Etudes et Reserches de

Pyrotechnie (GERPy) has concerned the degradation of munitions due to their
ageing. For a number of years, extensive studies have been performed on
the behavior in time of nitrocellulose based gun propellants. Results of
these studies have permitted development of new tests to allow a better
classification of the powders (calorimetry, chemiluminescence). On the
other hand, the effects of moisture on munition degradation mechanisms are
now being taken into account, especially by the elaboration of a code based
on a mathematical model. 23. It is expected that after correlation with
experimental results, this code will allow an improvement of life duration
determination for pyrotechnics devices under moisture attack.
SOME PYROTECHNIC PROJECTS AT SNPE

CONTRIBUTORS: M. J.-P. BRIGNOLLE and M- E. SOULETIS, SNPE

In the area of ordnance pyrotechnics, there is an effort to examine laser

initiation to obtain functioning (ignition) times of less than 50 ns. SNPE
is using its knowledge and formulation capabilities to establish a new
secondary explosive which meets not only the safety but also the low-level
laser initiation requirements which are consistent with accepted
transmission train concepts. SNPE is developing a short functioning time
combustion to detonation transition booster, loaded with a secondary
explosive, which is adaptable to different inputs such as from a
laser/optical fiber, shock tubes, etc. A wide range of delays can be
incorporated into the device.

SNPE is also developing submunition ejection systems based mainly on

propellant gas generator and air-bug technologies. These projects take
advantage of the solid propellant grain expertise at SNPE.

A third pyrotechnic project area is infrared countermeasures. In order to

improve low detectability, increasing stealth, decreasing probability of
reaching fighting platforms after detection, reducing damage due to war

10
hazard, and survivability, SNPE uses its knowledge and its formulation
capabilities to study, develop and manufacture conventional and advanced
infrared countermeasure concepts such as: adapted trajectory decoys,
infrared adapted signature decoys and infrared/electromagnetic coupled
products.

GERMANY

CONTRIBUTOR: Dr. Uwe Krone, NICO-PYROTECHNIK

GERMAN PYROTECHNICS INDUSTRY

General: In Germany, the expression "Pyrotechnik" includes only pure

pyrotechnic applications. These are fireworks (toy and display), pyro-
ammunition (signalling, simulating and training devices operating mainly
with pyrotechnic compositions), smoke ammunition (hexachloroethane (HC);
NICO-TRITTAU/smoke (NT); potassium nitrate/magnesium (KM); red phosphorous
(RP) and related mixtures] and technical devices such as air-bags, tracers,
delays and a variety of smoke and smoulder devices for different purposes.
"Pyrotechnik" does not include priming caps, propellants, primary or
secondary explosives.

In Germany, old traditional fireworks factories are still in operation but

are decreasing from decade to decade. Plants with a well known name and
with only fireworks production (mainly display but toy also) are WECO,
PIEPENBROCK PYROTECHNIK GmbH (formerly MOOG-NICO), OSKAR LUNIG, ZINK and
SAUER. Plants having both, military/technical and fireworks production are
today of course NICO, PIEPENBROCK PYROTECHNIK GmbH (formerly FEISTEL),
COMET, and BUCK, the latter only in the military/technical field. From the
former GDR, 2 or 3 rearranged plants, with so far unclear relationships to
the above-mentioned factories, are moving in. These are SIBERHUTTE, RIESA,
and SACHSENFEUERWERK.

The main fields of research, development and production of the second group
of pyrotechnic plants in Germany are the following:

NICO: 1. Smoke devices for screening and signalling, e.g., the first
training smoke (KM) having passed the tests (OECD-guidelines)4 for
environmental compatibility; HC-, NT- and infrared (IR) smokes for
screening. 2. Subcalibre training ammunition for all anti-tank weapons
and for mortars for all calibers (introduced in the US-Army).
3. Signalling and illuminating 26.5 and 40mm cartridges and tracers for
tank ammunition. 4. Fireworks.

PIEPENBROCK PYROTECHNIK GmbH (formerly FEISTEL): 1. Signalling and

illuminating 26.5 and 40mm cartridges. 2. Training and simulating
devices. 3. Fireworks.
COMET: 1. Training and simulating devices. 2. Signalling and
illuminating 26.5 and 40mm cartridges. 3. Fireworks.

BUCK: 1. Smokes for screening (RP, HC). 2. IR-decoys. 3. Incendiary

devices. 4. Demilitarization of pyro-ammunition.

There are also some pyrotechnic activities in plants like MBB, DYNAMIT
NOBEL, DIEHL and BAYERN CHEMIE which are however mainly engaged in
explosives and the like.

ENVIRONMENTAL AND HEALTH CONSIDERATIONS

The main field of research in Germany these days, as regards to our

industry, is to find pyrotechnic compositions or reactions which are able
to replace toxic and environmentally no longer acceptable pyrotechnic
ammunitions like e.g., hexachloroethane (HC) or phosphorous smokes, heavy

11
metals containing compositions or devices which contain halogenated
hydrocarbons or deliver aerosols with dyes or organic compounds with a
proven or estimated health risk. Since February 1990, there is a federal
law in Germany which forces every new chemical or chemical mixture before
being allowed on the market to undergo environmental compatibility
evaluations following the relevant OECD 4 guidelines. This obligatory
testing procedure is a mix of toxicity tests regarding the aquatic, soil
and aerial life of our environment. Due to this, new developments of pyro-
ammunition for our armed forces will be adopted at least only if the life
cycle is known and methods are tested (and offered with the tender) to
recycle and/or dispose of the materials properly and in accordance with the
law.

This effort must be seen especially with regards to the 300,000 tons of
ammunition of all kinds of the former GDR-Army and the additional 400,000 -
600,000 tons (!) of ammunition the Soviets are going to leave here. It is
obvious, that for the next two or three decades the German military
industry will be more engaged in destroying and demilitarizing ammunition
rather than producing it. You may imagine how these tasks now are taking
over our development technology centers.

NONTOXIC SMOKE SCREEN

An example of a pyrotechnic mixture for producing a nontoxic smoke for

screening which was developed by NICO is made from 15% magnesium, 30%
potassium nitrate, 15% calcium carbonate, 32% potassium chloride and 8%
azodicarbonamide.' 7 This smoke producing composition provides a smoke
screen which is particularly suitable for training purposes. The smoke is
composed of a nontoxic aerosol which is unable to produce a toxic effect on
humans and animals and is compatible with the environment. The smoke from
the above formula is primarily composed of macronutrients suitable for
plants.

ISRAEL
CONTRIBUTOR: Dr. Arie Peretz

P 4OTECHNICS AT RAFAEL
Most pyrotechnic Research, Development and Production activities in RAFAEL-
Armament Development Authority (ADA) take place in RAFAEL's Electro-
Explosive Device Center, which is a part of the Weapon Systems Division.
The Center offers comprehensive services ranging from research, design and
development to production, testing and delivery of advanced pyrotechnic
products. The activities rely on well equipped laboratories for
thermochemical and thermal analysis (with emphasis on calorimetry and
TGA/DTA) of pyrotechnic compositions, as well as chemical and ballistic
testing facilities for pyrotechnic compositions and items. In addition,
use is made of the broad infrastructure of RAFAEL. Besides high-quality-
control production (99.9% reliability at 95% confidence level), development
of modern nonconventional pyrotechnic items is emphasized.

Typical products of the EED Center are: a. Squibs and initiators

(conventional-size and miniaturized), b. Pressure cartridges of various
sizes, c. Gas generators, d. Igniters for various rocket motors,
e. Pyrotechnic delays, f. Special ignition formulations, g. Pyrotechnic
smoke compositions, h. Explosive bolts and cable cutters, i. Through-
bulkhead initiators (TBIs) and j. Pyrotechnic compositions and devices for
simulation of various military events.

The finished products undergo simulated environmental tests in RAFAEL's

most advanced testing facilities All products are tested and qualified
according to the latest U.S. Mil. Standards.

12
 JAPAN

CONTRIBUTOR: Dr. Naminosuke Kubota, Japan Defense Agency

COMBUSTION OF BORON/POTASSIUM NITRATE

Ingredients for rocket igniters and pyrotechnics are of continuing

interest. Specifically, the reaction process of boron (B) with potassium
nitrate (PN) is under investigation. A thermochemical analysis of the
composition was conducted. The oxidation temperatures and rate of
oxidation were examined as a function of particle size and weight fraction
of the boron mixed within the B/PN mixture. Yanol observed that the
oxidation of boron starts from the surface of each boron particle and forms
an oxide shell around the surface. This prevents penetration of the
oxidizer through the oxide shell toward the interior portion of the
particle. For small particles (0.15gm), the oxidation reaction terminates
when the thickness of the oxide shell is about 0.0041gm and for large
particles (5.0Mm), it is about 0.387Mm.

Yano also observed that the reaction process consists of a three-stage

gasification reaction. In the first stage, the mixture of B and liquified
PN reacts to form KBO 2 and NO with significant heat evolution. In the
second stage, the remaining PN decomposes to form gaseous oxidizers. In
the third stage, the KBO 2 produced in the first stage starts to decompose
and produces K20 and B20 3.

Yano and Kubota 9 continued to study the thermochemical properties of B/PN

and made burning rate measurements. The burning rate depends largely on
the weight fraction of B in the mixture. At 60% and 80% boron, the burning
rates are pressure insensitive below 100 kPa. At a pressure of 0.5 MPa,
the burning rate reaches a maximum of about 38 mm/s for fine particle boron
with weight fractions between 0.2 and 0.4 where stoichiometric is 0.25.
For large sized boron, the burning rate is lower (maximum about 18 mm/s)
than that of the small sized boron, but the rate characteristics appear to
be the same, i.e., the weight fraction versus burning rate profiles are
similar in shape.

They concluded that the burning rate is highly dependent on the weight
fraction of boron and the particle size of boron at a constant pressure.
In addition, the burning rate is dependent of pressure. Further extended
experiments are planned in order to understand the detailed physicochemical
process of the B/PN combustion.

SMOKELESS IGNITERS
In order to reduce the amount of smoke from a double base propellant when
burned at low pressures below 3 MPa, one percent of metallic nickel (0.1Mm
in diameter) was added to the propellant grain. The nickel acts as a
catalyst to promote the gas phase reaction of double base propellants at
pressures below 2 MPa.10

The flameless burning stage becomes flame burning and the gas phase
temperature increases. The catalytic action improves ignitability and
reduces smoke generation due to more complete combustion. The catalyzed
grains were compared directly to B/PN igniters, the latter exhibiting about
four times as much smoke attenuation for a grain weight of 40 g.

CONCEPT AND THE USE OF NEGATIVE MIXTURES

CONTRIBUTOR: Dr. Takeo Shimizu, KOA Fireworks Co.

In 1986, the concept of "negative explosives" was introduced. These are

mixtures of a fuel, such as magnesium, and a substance such as sulfates,
oxides, carbonates, etc.70 Whether or not a mixture is called negative or

13
positive depends on the oxygen value. The latter is the amount of positive
or negative oxygen in grams per 100 grams of mixture. When the fuel is
mixed with a substance such as a nitrate, chlorate, perchlorate, etc., the
mixture is generally a "positive explosive". This work showed that
relatively inert substances such as oxides would act as active materials
when mixed with fuels with a large reduction capacity, such as magnesium.
Fifty types of negative mixtures were studied, including magnesium as the
oxygen acceptor and water (H20) as the oxygen donor.

The concept to use water as the oxygen carrier was studied further.7 1 A
proposed application is a marine emergency flare. A mixture of 95%
magnesium and 5% cryolite (Na3AlF6 ) is placed in a cardboard tube sealed by
a 0.02mm vinyl chloride film. Ignition is with a fuse, the end of which is
coated with four grams of a 92% lead oxide and 8% ferrosilicon mixture.
Styrene foam 10mm cubes are mixed into the charge to make the item buoyant.
The flare containing about one kilogram of the magnesium mixture is lit by
the fuse and thrown into the water. The luminous intensity was 430,000 cd
and the burning duration was 150 s. There is 24.7 kJ of heat produced for
each gram of magnesium.
The oxygen values were studied of 59 mixtures with both positive and
negative values to determine combustion effects. One purpose was to find
mixtures suitable for use as a non-illuminating delay charge. The latter
denotes a mixture that produces no visible flame or sparks when viewed from
a distance.
It was determined that the following mixtures were best suited as non-
illuminating charges for the transition layer of color-changing stars:
calcium nitrate 84% 86% (% by weight)
sulfur 8% 7%
Paulownia charcoal 8% 7%
oxygen value +5.16 +9.47
(g per 100 g of mixture)
combustion speed (mm/s) 2.8 2.2
It is not advisable to use these mixtures with paper tubes since a visible
flame is formed because of the excess oxygen value. It is necessary to add
some binding material such as rice starch to the transition layer.
However, too much binder will result in too little oxygen to produce a
visible flame.

PEOPLES REPUBLIC OF CHINA

CONTRIBUTOR: Professor DING, Jing

At the Fifteenth International Pyrotechnics Seminar," Professor DING

presented a paper on the discovery of "huo yao", gunpowder in China. The
purification of saltpeter was reported about 300 A.D.; the gunpowder was
used not later than 850 A.D., and fireworks about 900 A.D. The development
of gunpowder was certainly one of medieval China's greatest achievements.
Investigations of energetic materials have continued there throughout the
ages.

In pyrotechnics and related technologies, current investigations include

the a. study of properties of whistling compositions for use in military
sound signal devices and in civilian fireworks, b. theoretical analysis of
extinction efficiencies and coefficients of spherical particles for
obscuration of visible and infrared radiation, and c. the development of
failure rate equations for bridge wire ignition systems which take into
account factors associated with degradation of performance.

14
HUANG and LI are continuing to study properties of whistling
compositions." .13 They report that a combustion response function can be
used as a characteristic parameter of whistling compositions. That
function relates the formula and properties of the composition with the
whistle frequency. While direct computation is not yet possible, they
provide an experimental method to determine the function for mixtures of
potassium hydrogen phthalate and potassium perchlorate (35:65) and for
potassium benzoate and potassium perchlorate (30:70). Also see 6ztap.6

LI and LAO are conducting theoretical analyses of spherical particles for

the purpose of understanding their relationship to the maximum extinction
coefficient and extinction efficiencies, K.14 In terms of the extinction
efficiency from Mie theory, they proposed a relative function K/x for
practical analysis where x is the size parameter which is directly
proportional to the radius and is inversely proportional to the incident
wavelength. From their calculations, they report for a given material that
there is an optimal particle size corresponding to the maximum extinction
coefficient and that optimal particle size is always smaller than the size
related to the peak value of the extinction efficiency. Their initial
studies treated spherical particles formed from water droplets, carbon and
iron powders. Their plans are to extend the studies to particles of other
shapes.
For a bridge wire electric ignition system, SHEN and DAI reported static
failure rate equations which relate the hygroscopicity of the composition,
chemical compatibility and chemical corrosion." They relate each of these
to a failure rate for the system. The parameters of the static failure
rate equations relate to manufacturing technology and the system structure.
The equations have been compared to experimental results. Moisture
absorbed in the ignition composition is the principal factor which causes
the system to fail. The relative humidity of the composition is inversely
proportional to the ignition temperature and ignition temperature rate of
change. These data can be related to deterioration of the device during
storage under varying conditions of temperature and humidity. It will be
necessary to introduce other factors into the equations to treat ignition
systems other than those with a bridge wire.

SOUTH AFRICA
CONTRIBUTOR: Mr. John Crewe, Swartklip Products (PTY) LTD
Military pyrotechnics in South Africa really began in 1971 when the
Armaments Corporation of South Africa (Armscor) took over the Ronden
Manufacturing Company, situated near Cape Town in what was then open
country. This company had previously made some military products in
addition to display fireworks and other commercial items but the facilities
were very limited although the actual site was extensive. The new company
was called Swartklip Products and the capital available enabled full
utilization of the site, which now occupies 700 acres and provides
employment for 1,000 people.
New buildings were erected in brick or reinforced concrete and plant and
equipment were provided so that a wide range of products could be
manufactured and tested, both in test houses and on a proving ground.
Since the objective of the company is to provide pyrotechnics products to
meet requirements by all three services the variety has been immense,
especially as pyrotechnic sub-systems, such as tracers, are manufactured
for other members of the Armscor group.

Meeting the requirements for new products has meant a high Research and
Development effort with the emphasis very much on development. With South
African forces being involved in combat duties it was often important that
new items were available at short notice, but at least this also gave the
opportunity for field evaluation. In order to use our research and

15
development resources most usefully, work has been directed toward a.
Enhancement of existing products, b. Technology transfer, c. Reproduction
or modification of designs being used elsewhere, and d. original designs
where nothing suitable was known.
Since the opportunities for technology transfer have been very limited, we
have been very involved in copying or adapting items already in use.
However, because of unique environmental conditions and particular
requirements dictated by the type of operation, we have been involved with
a number of original designs - probably the most publicized South African
military product is the 155mm gun system for which Swartklip Products
manufactures a variety of carrier rounds. These are only superficially
similar to rounds in use elsewhere and are the result of a major
development effort especially as field-fitted base-bleed is a standard
feature.
One area in which we have done a considerable amount of original work is in
the formulation and manufacture of compositions containing red phosphorus.
Previously white phosphorus had been used in a number of items for both
smoke and incendiary use and we were anxious that it should be
discontinued. The formulations developed fall into two categories:

a. Compositions which are rubbery in nature, such that they could

be extruded and granulated. These can be made into discrete particles of
controlled size and burning characteristics, which would normally be
dispersed by detonation. Grenades and mortar bombs are being manufactured
and, besides the uses already mentioned, we have found that they are being
used as position markers.

b. Compositions which can be formed into precise geometric shapes

but take on good mechanical properties such that they could be used in
bombs and shells. Much attention was given good combustion properties but
also to the problems of ensuring safety both in manufacture and use.
Swartklip has also been closely involved in manufacturing equipment for
riot control. This has involved not only the development of non-lethal
weaponry but also in techniques for disseminating lacrimatory agents. This
is an area where there is considerable opportunity to apply new techniques
to cope with civil unrest wherever it may occur. Currently efforts are
being directed more towards commercial applications for pyrotechnics,
ranging from conventional distress signals to new techniques for controlled
blasting in quarries.

SWEDEN

CONTRIBUTOR: Dr. D. Loyd, Linkoping University and Institute of

Technology; Linkoping

A method to analyze the burning rate of a slow-burning pyrotechnic delay

composition is being developed. This composition is used to delay the
ignition of, for example, an illuminating composition. Generally the delay
of ignition is short and the burning rate of these delay compositions is
very high. For such compositions (fast burning rate), the delay is mainly
determined by the properties of the pyrotechnic compositions and by the
geometry of the case. In this case, the heat transfer to the surrounding
structure and fluid is of minor importance. On the other hand, for slow
burning rate delay compositions, which are the subject of this research,
the heat transfer from the compositions has great influence on the burning
rate. The reaction products are mainly solids. The initial temperature,
the heat flux transfer to the case and to the surrounding structure and
fluid are of great importance for the burning rate of such compositions.
It is thus necessary to include heat transfer in the calculation of the

16
burning rate. The hardware design, containing the delay composition is
complex. For these reasons, both experiment dnd numerical calculations are
needed.'6

Some of the properties of this slow-burning delay composition and its case
are as follows. The heat of combustion of the pyrotechnical composition
used in the test example is 2.15 MJ/kg and the ignition temperature 2000 C.
The density of the composition is 1600 kg/M 3 , the specific heat
1600 J/kg*K, and the thermal conductivity 0.30 W/meK. The heat of
combustion corresponds to an energy of 72.9 J. The composition studied
here does not melt before ignition and the composition gives mainly solid
reaction products. The case and the housing are made of steel; density
7800 kg/m , specific heat 460 Wes/kg*K, and thermal conductivity 48 W/mOK.
The numerical calculations are based on the finite element method, FEM.
The influence on the burning rate
of the initial temperature, of the
heat flux to the case, of the heat CM10"0
of combustion, and of the thermal
properties of the composition
is shown in a test example. See C -O.
Figure 7. The example chosen
is a slow-burning pyrotechnical CASE
delay composition used for delay-
ing the ignition of illuminating
compositions. The test equipment r.... i •.....
c
is designed to promote a large
heat flux to the case and the Figure 7. The extension of the
surrounding material, reaction zone at time 8.0 seconds.

It is shown in reference 16 that the burning rate can be studied

numerically with good agreement between calculation and experiment. The
numerical result is also of great value for planning the laboratory
experiments. A combination of computer experiments and laboratory
experiments reduces the number of tests as well as the cost.

THE NETHERLANDS
CONTRIBUTOR: Dr. N. H. A. van Ham, Prins Maurits Laboratory

GRANULATION AND COATING OF PYROTECHNICS MIXTURES

Granulation: Some years ago, the Pyrotechnics section of the Prins Maurits
Laboratory started a small research program in order to develop and build a
disc granulator for the processing of pyrotechnic compositions. Efforts
were put into the underlaying theory needed to understand and optimize the
performance of the disc granulator. After this, a laboratory scale disc
granulator was designed and built at the Prins Maurits Laboratory.

It was shown that pyrotechnic mixtures of solids with roughly the same
particle size (although not too small, otherwise particles start to "stick"
together) can be granulated with a suitable dissolved binder. It seems
that boron/potassium nitrate mixtures can be granulated easily using
Viton-A® (dissolved in acetone) as binder. The obtained granules showed a
good homogeneity. The only disadvantage that occurred was the rather high
porosity of the granules. More experiments are needed before detailed
characteristics of this disc granulator can be given.

CoatinQ: A pyrotechnical mixture is a suitable combination of reductor(s)

and oxidizer(s). Quite often the reductors are reactive metals like
magnesium, aluminum and boron. During storage these mixtures give rise to
undesirable side reactions. The reactivity of these compositions can be
decreased by coating the fuel.

17
The Pyrotechnics section of the Prins Maurits Laboratory has started a
research program irn order to gain some practical experience in coating
techniques, to understand more about the mechanisms and to establish a
suitable coating for especially magnesium. A coating should be:
effective, firmly bonded, (relatively) environmental friendly and should
not alter the burning characteristics.

The metals in pyrotechnic mixtures are mostly used as powdery materials,

therefore, it is impossible to use the well known electrochemical reduction
processes. The metal particles have to be coated in-situ; a so-called
electroless plating process.

Satisfactory results have been obtained by using several methods.

These are a. Non-catalytic displacement plating; a more noble metal (zinc)
is being exchanged with magnesium at the surface of a magnesium particle,
and b. Non-catalytic reduction plating; nickel ions are reduced at the
magnesium surface with the aid of a suitable reduction-chemical.

The corrosion resistance and further characterization of these coatings is

under examination at the moment. In addition, some efforts are directed
towards finding a coating system for boron and aluminum.

UNITED KINGDOM
CONTRIBUTOR: Mr. James Queay, Royal Armament Research and Development
Establishment, Fort Halstead
SOME PYROTECHNICS IN THE UK

The question is often asked of pyrotechnics "What is new in pyrotechnics,

they have been around for 3000 years, there is nothing more to be learned?"
The answer has to be "consider the requirements placed on the performance
of pyrotechnics over the past 3000, 1000, 100 or even last 10 years". This
is nowhere demonstrated better than in the defence area, for who would have
thought 100 years ago that pyrotechnics would be functioning in the
environs of space. The space shuttle contains some 135 applications for
pyrotechnics in manual, emergency or mission abort functions. Also modern
gun systems are very searching of pyrotechnic igniters. For instance
considered the igniter for the extended range carrier shells.

ZXTENDED RANIGE CARRIER SHELL:" Artillery officers require that ammunition

has an extended range and this can only be achieved by increasing the
launch velocity or by reducing the drag during flight. Increases in launch
velocity is unlikely. Future work on extended range shells will
concentrate on reducing the retardation along the trajectory. When a shell
is fired from a gun it first experiences high pressures in the breach but
when it leaves the barrel, the pressure at the rear of the shell reduces to
low values. It is this low pressure region which gives rise to base bleed
drag. The means of overcoming base drag is to fit a base bleed unit which
ejects hot gases of low molecular weight into the low pressure region thus
reducing the base drag. Although the base bleed propellant can be ignited
from the hot gases by the burning gun propellant, it is usually
extinguished by the rapid pressure reduction at the base of the shell as it
exits the barrel. A pyrotechnic igniter has been formulated capable of
being ignited from the gun propellant and staying ignited through the rapid
changes in pressure then finally igniting the base bleed propellant.

IR COUNTERMEASURES: The simplest answer to defeating a heat seeking

missile is to use a flare which produced a point source of radiation
greater than the target thus seducing the attacking missile. With the
development of more sophisticated electronics in the missile head, a more
sophisticated decoy is needed to counter the improvements. A missile head
can be designed which is capable of distinguishing between the target and
the decoy by considering the distance between them and if this is

18
increasing then it will ignore the decoy and continue towards the target.
The obvious answer to this is to keep the decoy flying alongside the target
until the missile is locked onto the decoy.

Two flare types are being investigated in this context, an aerodynamic

flare and a propulsive flare. When a flare is deployed from an aircraft it
becomes ballistically unstable, starts to tumble and rapidly loses speed.
However, by weighting one end it becomes more aerodynamic and when deployed
maintains target. A similar effect can be achieved by incorporating into
the flare design a propellant which propels the flare in the direction of
the aircraft.6 The UK is currently trialling their own versions of
propelled flares.

MODELLING OF FLARE PERFORMANCE: A model has been proposed" to predict the

variation of radiant intensity with time for burning pyrotechnics and
assumes that the radiant intensity at any time is proportional to the mass
flow of composition which in turn is calculated in terms of the surface
area of the pellet, the combustion rate and the efficiency of the
composition radiating in any given waveband. The model has been expanded
to give radiance values when the flare is subjected to different air
speeds. Work has continued to refine the model as more experimental data
becomes available.

SPONTANEOUS IGNITIONS OF IR FLARE COMPOSITIONS: Spontaneous ignition with

magnesium/teflon/viton (MTV) compositions continues despite much work to
understand the problem. Studies of dielectric breakdown within small
pellets has shown that breaklown occurs at relatively low field values and
is a function of sample thickness. Application of a dc voltage across
samples caused ignition at an energy of 20J, far lower than previously
reported values. It has also been shown in samples of MTV compositions the
formation of "trees" and that the formations of these "trees" enhances the
susceptibility of materials to ignitability in electric fields. A
theoretical capacitor model for dielectric breakdown with MTV compositions
is under examination.

PRODUCTION OF PYROTECHNICS BY VAPOUR DEPOSITION: The manufacture of

pyrotechnics systems by vapour deposition of materials onto substrates have
been given at two previous seminars." ,9 Two different manufacturing
processes have been described. One is the continuous coating of magnesium
onto polytetrafluoroethylene (PTFE) sheet. The second is the putting down
of multi-layers of material to produce patterns in the same way as a
printed circuit board. The coated magnesium/PTFE sheet is being
investigated as a energy transfer medium in modular gun propellant systems
to improve ignition and to replace the primed cambric. Initial results
from trials are promising with improved times to reach maximum peak
pressure being achieved. Most of the time since the last papers has been
spent in procuring and installing new equipment which gives better control
of the deposition process.

EXPLOSIVE CORDS: There are two types of explosive cord, disruptive and
non-disruptive. Disruptive cards are used for cutting or breaking up
munitions. One example is the use of miniature detonating cord (MDC) for
disruption of an aircraft canopy when a pilot has to eject from his
aircraft. Another example is the break-up unit fitted to missiles and
munitions when they are test fired so that the trial can be aborted should
the trial go wrong. A mitigation device has been designed based on
disruptive detonating cord which can be attached to rocket motors whilst in
storage. Should the motor then be involved in an accidental fire
situation, at a prescribed temperature, the mitigation device is activated
thus opening up the motor and reducing the risk of a catastrophic
explosion.

Non-disruptive detonating cords have been used as time delays in warheads.

An advantage is that explosive energy can be transferred from one explosive

19
event to another, giving a required time delay. Another advantage is that
the transfer of the explosive energy can take place within confined spaces
without damage to the surrounding area which may contain sensitive
components such as electronic equipment.

UNION OF SOVIET SOCIALIST REPUBLICS

CONTRIBUTOR: Professor Yu. V. Frolov

PYROTECHNICS IN THE USSR

In the USSR, anti-hail rockets have been developed ("Alazagne Crystal")
which are designed to induce changes in clouds with the purpose of hail
prevention. These rockets are characterized by the safety level of 0.9995,
have high efficiency and use pyrotechnic compositions which ensure release
of large amounts of active crystallization nuclei.

For the exploration of physical processes going on in the atmosphere of the

earth, pyrotechnic systems have been worked out which permit the creation
of artificial luminous and ionized clouds. The pyrotechnic devices can
ensure the formation of one or several spherical clouds, of a long
continuous or interrupted trace. The long continuous trace cloud consists
of one reagent but gives the appearance of the other.

New systems of gaseous fire-extinguisher have been offered, these on the

basis of pyrotechnic mixtures which generate technically pure nitrogen
during combustion.
According to the requirements of the International Convention on People
Salvation at Sea, in the Soviet Union a set of facilities has been
developed and put into serial production - for sea boat equipment, which
consists of firecrackers, sound and smoke rockets, luminous and
luminous-smoke bobbers.

The Soviet industry has mastered the production of high-altitude night

fireworks (105, 195 and 310 mm calibre) of more than 60 denominations. The
fireworks broadly vary in colour, possess high characteristic colour
purity, great safety and a lot of spectacle effects.

UNITED STATES OF AMERICA

CHEMICAL RESEARCH, DEVELOPMENT, AND ENGINEERING CENTER,

Aberdeen Proving Ground, MD
CONTRIBUTOR: Mr. Joseph A. Domanico
SMOKE AND RELATED PROJECTS

A number of efforts are underway which utilize terephthalic acid as the

smoke producing agent. The high interest in this material derives from its
relative nontoxic property which may make it acceptable for use for both
training and combat. Terephthalic acid along with a form of ammonium
chlcride are being evaluated as a screening agent replacement for
hexachloroethane (HC) for use in combat and as a training variant.

Terephthalic acid in a special white smoke formulation is being developed

for use in the Pyrotechnic Smoke Simulator, a training device. The unit
produces high volume, high smoke density clouds. A terephthalic acid based
smoke system is being developed to protect underground storage areas. The
pyrotechnically generated smoke provides an instantaneous white cloud of
long duration (hours).

Training versions of the 76mm self-protection grenades are also under

development. The units are being filled with titanium dioxide and an

20
explosive booster. These materials are expected to have a lesser
environmental impact than the current load materials.

As a part of smoke materials technology base studies, an effort is

currently underway to examine several candidate configurations to enhance
the 2.75" rocket's screening capability. The current red phosphorous smoke
warhead has been improved to prevent corrosion damage during long term
storage and storage at elevated temperatures. Wafers containing a
phosphine absorbing chemical are placed between the one quarter circle
wedges and have been successful in preventing damage to the internal metal
parts. Also, work is currently underway to improve the reliability of red
phosphorous pellet ignition by means of a combination expulsion/ignition
charge. However, several designs which were successful in igniting the
pellets did not always meet safety requirements. Other solutions are being
explored.

New materials are being investigated for use as signalling and marking
smoke warheads for the 2.75" rocket. These materials must possess a unique
signature on the battlefield, whether in size, shape, color, or wavelength.
Screening smoke materials will provide smoke which will expand the U.S.
Army's ability to screen increasing areas of the electromagnetic spectrum.
Near infrared, mid-infrared, far-infrared, and beyond are some areas of
interest.
A gap tester, of Australian design, is being evaluated to determine its
ability to determine the sensitivity of certain pyrotechnic mixes to
various thermal influences. By using this device, the best and most
efficient ignition system can be developed along with new pyrotechnic smoke
formulations. This device can not only be used to determine the actual
pyrotechnic mixture to use, but also can be used to enhance the current
knowledge in how the ignition train functions. This should result in a
much shorter development time and higher initial choice reliability for the
smoke/igniter system under development.
NAVAL ORDNANCE STATION, MD
CONTRIBUTOR: Mr. Frank J. Valenta

INTERMETALLIC COMPOSITIONS FOR IGNITION/DELAY APPLICATIONS

There is currently a renewed interest in intermetallic compositions as
possible replacements for conventional pyrotechnic delay and ignition
compositions. Factors driving the community in this direction include the
fact that, in the delay area, intermetallics are non-toxic and non-
carcinogenic while most conventional delays currently in use (at least in
the U.S.A.) are not. For example, the U.S. Navy's approved delays include
those based on metal fuels such as tungsten, boron, manganese, and alloys
of zirconium and nickel with oxidizer systems based on insoluble hexavalent
chromates (e.g., lead chromate, barium chromate, calcium chromate, etc.).
Historically, chromates were chosen for the applications because, when
properly formulated, they form solid slags and release little gas when
combusted. In recent years, though, there has been increasing concern
about their use in pyrotechnic delay systems. Besides being toxic, recent
studies (followed by governmental regulation) have identified the family of
"insolvent hexavalent chromates" (to which all the chromates used in
pyrotechnics belong) as being "suspected carcinogens". A similar problem,
though not quite as pervasive, exists in the ignition composition area.

Intermetallic compositions, based on binary or ternary mixtures of metals

such as zirconium, molybdenum, tungsten, titanium, graphite/carbon, boron,
etc., have the advantage of not using an oxidizer. As such, they are, in
general, non-toxic and non-carcinogenic. Intermetallics offer the
advantage of long term chemical stability and lower delay time shift/
degradation. Intermetallics react through an exothermic alloying reaction

21
which is only begun at very high temperatures. In comparison, conventional
pyrotechnic delays react in a oxidation-reduction reaction which are often
initiated at much lower temperatures and can (for some systems) slowly take
place even at ambient service temperatures.

Research on intermetallics has been widely reported by scientists (such as

Y. Maksimov) in the Soviet Union, but perhaps best known in the U.S.A. is
the work of Dr. Alex Hardt. Intermetallics have been used in the U.S.A.
for at least the last 25 years. The first widely used intermetallic
material was a system based on aluminum-palladium. It was used in delay,
ignition and release applications.

Approaches for formulating intermetallic materials have included

coextrusion of one metal onto another, vapor deposition, cladding; and
mechanically mixing fine powders of the several materials. Besides the
interest in intermetallics for pyrotechnic applications, intermetallics
have also been studied in the area of self-propagating high-temperature
synthesis for the production of dense refractories.
The only known U.S. currently active effort, directed at pyrotechnic
applications, is the evaluation of mechanically mixed intermetallic delays
in pressed columns. This work is being performed locally by Mr. J. Rose.

LASER IGNITION OF PYROTECHNIC MATERIALS

Laser ignition technology is only now reaching the level of maturity

required to be considered a viable candidate for new or upgraded military
applications. Recent advances in materials, electronics and optics are
beginning to make the size, weight, cost and reliability of laser systems
compare quite favorably to conventional pyrotechnic ignition systems.
Laser based ignition systems are attracting a lot of interest because of
the recent emphasis on ordnance safety. Being a non-explosive and non-
electrical ignition stimulus, the laser has obvious advantages in adverse
electrical and thermal environments.

A laser ignition system generally consists of a laser rod or laser diode, a

stored energy supply to fire the laser, a switching or distribution system
to properly direct the output, a fiber optic transmission system and an
optically initiated pyrotechnic device. Packaging and selecting/
interfacing the various components continue to pose occasional "engineering
challenges" when developing the laser ignition system for a specific
application.

In recent years, laser ignition/initiation systems have been developed for

applications such as strategic ballistic missiles, aircrew escape systems
for high performance military fighter aircraft, aircraft stores separation
systems, and arm-fire devices (AFDs) for air 'aunched rockets and missiles.
Both discrete rod lasers and the newer high power laser diodes have been
used for these similar applications. The choice of which to use is
dependent on the application, interface requirements, etc.

In most of these systems, the pyrotechnic component being initiated by the

incident laser radiation is either zirconium-potassium perchlorate or
boron-potassium nitrate. Some developers have added glass microbeads to
these compositions to act as small lenses. This approach increases the
radiant ignition sensitivity of the pyrotechnic materials (and therefore
its reliability at a given input energy level) without lowering the
autoignition temperature. Work in laser ignition of pyrotechnic materials
is continuing.

22
NAVAL RESEARCH LABORATORY, Washington, DC
Contributor: Dr. H. D. Ladouceur
Ladouceur is developing a computer code to numerically simulate combustion
of magnesium and polytetrafluoroethylene. The objectives are to identify
important gas-phase combustion species, determine parameters which control
the burning rate, and understanding how to increase the conversion
efficiency of chemical energy to mechanical and/or radiative energy. The
kinetic model utilizes a SANDIA code 7 for a perfectly stirred reaction and
data concerning the chemical species involved, thermodynamic properties,
kinetic mechanism and rate constants.
Figure 8 shows species predicted in the 1500K reaction between magnesium
and polytetrafluoroethylene.
Mg CeF 4 AT 1500 K

EQUILIBRIUM VALUES
-, MOLE FRACTIONS

Ag CF2 7.923 9
CF3 5.8180.9
Cf4 1.8747-4
4gF -,2F4 4.3799)2
.5'.F 3.788 10
-MGF2 1.1370-8
C(S) 5.0000-1
qKGF21S1 4.9981. 1

C
__ 4 FROM NASA-LEWIS CODE

CuD 5 -I 5 2Q
T' e (A seccr s )

Figure 8: Thermodynamic equilibrium species predictions.

Polytetrafluoroethylene decomposes to form C2 F4 which, in less than a
millisecond, dissociates to CF2. Contrary to previous reports, 8 the
predominant reactive chemical species with magnesium is probably CF2.
Ladouceur concludes that the direct reaction of magnesium metal or vapor
with free fluorine is unlikely inasmuch as predicted levels of elemental
(F) and molecular (F2) fluorine available in the present reaction mechanism
are several orders of magnitude below CF2 . The predictions are limited by
the lack of reliable kinetic rate constants. In addition, preliminary
calculations indicate that about 80% of the heat of combustion is utilized
in decomposing the polytetrafluoroethylene. One might recall its
application as a heat shield. Analysis of this characteristic in t!he
context of a Burke-Schumann'92 0 solution of the diffusion flame is in
progress.

Another conclusion is that the combustion of polytetrafluoroethylene with

oxygen produces a considerable amount of CF4 . This product has a high heat
capacity which tends to lower the effective flame temperature and ties up
the available fluorine as a nonreactive species. Oxygen may effect the
ignition process in magnesium-polytetrafluoroethylene by providing a
channel to produce CF4 . The latter being nonreactive, it contributes to
delay of ignition.

23
NAVAL SEA SYSTEMS COMMAND, Washington, DC
CONTRIBUTOR: Mr. D. M. Porada

NAVY INSENSITIVE MUNITIONS PROGRAM

The U.S. Navy experienced a number of high cost and dead'.y ordnance
accidents aboard aircraft carriers and other ships. For example: USS
FORRESTAL 1967; USS ENTERPRISE 1969; USS NIMITZ 1981; USS ORISKANY 1966 and
USS BADGER STATE 1969. The incident aboard the USS ORISKANY was associated
with the MK 24 Aircraft Parachute Flare, a pyrotechnic illumination device.
These incidents led to a major analysis on how to minimize these events.

In 1984, an insensitive munitions policy was set forth which stated that
all Navy munitions will a. be designed to minimize effects of unplanned
stimuli, b. incorporate least sensitive materials, c. meet or improve
upon published insensitivity standards and d. meet performance standards.
The goal was to have inventory transition by 1995.

Tri-Service management organizations have been established to implement

service objectives The U.S. Navy objective is to develop and demonstrate
technology needed to reduce vulnerability of Fleet munitions by reducing
the severity of reactions from fast and slow cook-off, bullet impact,
fragment impact and sympathetic detonation. Efforts are being focused on
a. all new weapon developments, b. 15 designated munitions for priority
forward fit and c. low-cost back fit alte- - ves. A military standard,
MIL-STD-2105A (Draft) sets out requirem2 ts concerning the stimulus to be
applied to the munition and passint criteria. Some related information is
provided in references 21, 22 aisd 23.

All Services want less sens-tive Ad insensitive munitions. The payoff is

increased survivability and combat eifc:ti .ess, improvement in storage
density and a number of shore-based benefits such as less vulnerability to
terrorist attack and safer land-based munitions transportation. Not only
are insensitive munitions a U.S.A. concern, but also, they are an
international concern. To further exchange of information, the NATO Pilot
Insensitive Munitions Information Center (Pilot NIMIC) was created in 241987
as an active means of speeding up the interchange of NATO information.
Pilot NIMIC was organized as an off-shoot of the Chemical Propulsion
Information Agency (CPIA) at the Johns Hopkins Applied Physics Laboratory.
The staff of Pilot NIMIC comes from different NATO countries. The intent
is to make technical information on explosives and propellant hazards, test
procedures, and test results available to all NATO nations so that uniform
standards will eventually be adopted. Pilot NIMIC finished a three year
trial at the end of 1990. By May 1991, the entire organization will become
operational at NATO, Brussels.
NAVAL WEAPONS CENTER, China Lake, CA

CONTRIBUTOR: Dr. Russell Reed

SUMMARY OF SMOKE PROJECTS

Compositions are being developed which contain a liquid curable binder, a

halogen source and a powdered metal which, when burned, give copious yields
of dense metal halide smoke clouds. Various hydroxyl terminated binders
were used including polybutadiene, polyether and azido polyether (GAP).
GAP is a glycidyl azide polymer. The GAP binder produced smokes having
higher burning rates and denser smoke clouds than were attained with the
other binders. The GAP may enhance the combustion of metals by the
formation of metal nitrides.

Halogen sources were organic chloro and bromo compounds. Dechlorane,

Dechlorane Plus, and the diol derived by the reaction of

24
tetrachlorophthalic acid with ethylene oxide were used to provide chlorine
for the formation of metal chlorides. Bromine sources included
pentabromodiphenyl (a liquid plasticizer) and decabromodiphenyl oxide (a
powder). Ammonium iodate and iodine pentoxide were used as sources of
iodine as well as oxygen. A number of powdered metals were used including
aluminum, bismuth, magnesium, manganese, zirconium, hafnium, titanium, and
zinc. The compositions exhibited a wide range of burning rates. Smoke
colors attained were white, yellow, orange and orange-red.

NAVAL WEAPONS SUPPORT CENTER, Crane, IN

CONTRIBUTOR: Dr. B. R. Hubble

DEVELOPMENT OF INSENSITIVE COLORED SMOKE COMPOSITIONS

This project addressed a shortfall exhibited by conventional colored smoke

pyrotechnic devices in that they fail to meet slow cook-off Insensitive
Munition test requirements. In the slow cook-off test, the item is
subjected to a uniform heating rate of 3.30C/hour until a response or
reaction occurs. To pass the slow cook-off test, the response of the test
item in essence cannot be more severe than burning. The response of
pyrotechnic devices containing colored smoke compositions, which consist of
sugar, potassium chlorate, dyes and additives, was deflagration.

In this project, it was demonstrated that an acceptable colored smoke

composition with respect to meeting the Insensitive Munition slow cook-off
test requirements results when a commercially available flame retardant
material is used as an additive to the pyrotechnic smoke compositions. The
flame retardant material chemically is 2,4,6-tribromophenol. Additive
concentrations between 1 and 15 weight percent have resulted in smoke
compositions meeting the slow cook-off test requirements.

The chemistry surrounding the use of 2,4,6-tribromophenol in the slow

heating environment associated with the slow cook-off test has been shown
to involve two contributions. The major contribution results in the
sucrose undergoing a caramelization reaction and as a result removing the
availability of sucrose to subsequently react with the oxidizer. A smaller
contribution is the result of the 2,4,6-tribromophenol undergoing a
polymerization reaction with the result that the polymer coats the surface
of the potassium
26 chlorate particles which inhibits its subsequent reaction
with sucrose.25 .7
USE OF SMOKE AT SEA

This project evaluates the effectiveness of using smoke screening to

protect small Navy craft, for example patrol boats, in a combat
environment. Tests were carried out both at sea as well as in a harbor to
evaluate the effectiveness of different smoke generation technologies. The
smoke generation technologies were (a) pyrotechnic smoke blocks which
generated zinc chloride aerosols, (b) a pulsed jet generator (U.S. Army
model M3A3E3), and (c) a turbine exhaust smoke generator. 2 The latter two
technologies are based on the use of conventional fog oil. S
A total of 21 at-sea tests were performed in the Atlantic Ocean. In
addition, tests werc performed in the harbor at Ft. Eustis in Virginia to
evaluate the feasibility of using smoke generators on small craft to
provide smoke protection for a harbor.

The at-sea test results indicate that small craft, when appropriately
equipped with proper smoke generating devices, can quickly and efficiently
produce smoke screens that effectively reduce susceptibility to small arms
fire. The turbine type smoke generator was found to be especially suited
for use aboarl small naval craft. For example, smoke generation for only
30-60 seconds produced a smoke cloud that persisted for over five minutes.

25
The cloud was over 1220 meters long. In comparison, the pyrotechnic blocks
produced a zinc chloride smoke cloud for a duration of three minutes. The
cloud also was about 1200 meters long but had thin spots where the naval
craft were not obscured. Finally, it wab not possible to get the pulsed
jet smoke generator to operate consistently in the ocean environment.
Equally promising results were obtained in the harbor tests. In general,
the results of these tests indicate screening smoke has the potential to
significantly enhance the survivability of small naval craft in a combat
environment.
INFRARED DECOY FLARE SIMULATOR

Large numbers of infrared decoy flareE, which are used to counter infrared
missile threats, have been expended during past training exercises of Naval
combat pilots. In an effort to maintain a current level of training using
the most cost effective manner, a low cost training simulator was desired.
The deployment of relatively low cost simulators in place of decoy flares
during training exercises will be a savings of nearly 90% of the cost of
the expendables used.2'
The Simulator, Tactical Use, Flare (STUF) was developed for use as a
training substitution for IR decoy flares as shown in Figure 9. The
purpose of this round is complete visual simulation of an expendable decoy
flare. The main composition, which produces white smoke and flame as does
an infrared flare, is a mixture of magnesium, sodium nitrate, and a binder.
Ignition is achieved with a red lead-silicon mixture.
O-RING

CARTRIDGE RETAINER
FIBERGLASS SCREEN

FOAM SPACER-
O-RING -- CASE CANDLE

END CAP

Figure 9: Simulator, Tactical Use, Flare (STUF).

The unit was designed with the intention to meet certain criteria which
would make the unit more desirable for the end users. The unit must a. be
safe to handle, b. be compatible with the CCU-41 and CCU-63/B impulse
cartridges, c. have visible signature within 250 milliseconds after
ejection, d. produce visible signature for approximately 5 seconds,
e. eject at a velocity of approximately 100-200 feet/second, f. be
functional out of ALE-29, ALE-39 and ALE-47 dispenser systems, and g. be
constructed from components which are easily manufactured. All of these
design goals were met or exceeded. STUF meets the primary requirement of
an inexpensive item which can be used instead of decoy flares for training
purposes. Simple components molded or cut from stock materials, a pressed
candle composition made from inexpensive materials, common assembly
procedures and minimal acceptance testing helped minimize development as
well as production costs.

26
 PYROTECHNIC PRODUCTION ASSURANCE ENHANCEMENT

Magnesium metal in particulate form is a fuel used in many different

pyrotechnic compositions, e.g., illuminating flare formulations. This
study addresses the chemistry associated with the undesired degradation
reactions that the magnesium metal can undergo either while in a storage
environment or while being processed on the pyrotechnic composition
production line. The laboratory technique of microcalorimetry is used to
characterize the reactions of magnesium with water vapor and air. In both
these reactions, surface reaction product films are formed which retard the
remaining magnesium from subsequent chemical reactions, i.e., degrades the
performance of magnesium in a subsequent pyrotechnic reaction.
We used a LKM Model 2277 Multi-channel Microcalorimetry system.
Microcalorimetry, originally developed by Professor Ingemar Wadso and
Dr. Jack Suurkuusk of the Thermochemical Laboratory in Lund, Sweden,0 has
been used extensively in the energetic materials area.31-

In this project it has been shown that for every 1% degradation that the
powdered magnesium undergoes, there is a 10% decrease in the performance of
a pyrotechnic composition which incorporates the degraded magnesium.
However, the degradation reactions are relatively slow, e.g., at 700C and
100% relative humidity, 1% degradation requires approximately 15 hours of
reaction time.
In this study, the degradation of the powdered magnesium has been shown to
be strongly moisture and temperature dependent. For example, at 250C in
air, the chemical rate of the degradation process is an order of magnitude
higher at 25% relative humidity than at zero percent humidity and increases
another order of magnitude when the relative humidity is increased to 75%.
The dependence on temperature is equally strong in that the degradation
chemistry rates increase exponentially with temperature.

ECOLOGICAL DISPOSAL OF PYROTECHNICS

CONTRIBUTOR: James E. Short, Jr.

Ecologically acceptable procedures have been developed for the

demilitarization and disposal of pyro-echnic munitions. The thrust of this
work was to dispose of or reclaim the energetic materials and chemical
components of the devices. After the experimental procedures were
validated one-tenth scale pilot plants were built and operated to evaluate
the process further. These were built for the preponderant pyrotechnic
categories; namely compositions for illumination, colored flames,
photoflash, tracers, infrared decoys and those containing red phosphorus.
Information about these efforts are contained in references 35 to 49. The
processes are also suitable for disposal of production line waste and
scrap.

PYROTECHNICS CONTROLLED-AIR INCINERATOR

CONTRIBUTOR: Mr. Curt Stephenson

Construction of a pilot scale Controlled-Air Incinerator (CAI) has been

completed at Los Alamos National Laboratory. The State of New Mexico has
approved a test burn. Because of cold weather (freezing weather would
hamper the startup and test) the test burn has been delayed until March of
1991.

The pyrotechnics pilot plant is a specially designed incinerator for the

thermal destruction of Navy colored smoke, flare and dye materials. The
waste material is slurried with #2 fuel oil, water and a polymer wetting
agent and pumped into the combustion zone of the incinerator. Off-gas
clean-up is by wet scrubbing techniques. The pilot plant has been

27
configured into three modules which can be transported on conventional
semi-trailers and a control trailer.
The incinerator, with emission control and monitoring systems, consists of
a feed module, an incinerator module, a utility module and a control
trailer. The major components of the feed module are a slurry feed tank,
slurry feed pump, recycle pump and associated piping and instrumentation.
The major components of the incinerator module are the incinerator vessel,
dual fuel slurry burner, off-gas quencher, demister, combustion air blower,
venturi scrubber and scrub recycle pump. The utility module includes an
air compressor, an air dryer, an electric steam generator and the
electrical switch gear. The control trailer contains the monitoring/
analytical equipment, the incinerator instrument packs, etc.

The incinerator has been designed to process mixtures of waste components

found in colored smoke, flare and dye compounds. These components are
listed below.

Maior Constituents: Minor Constituents:

Auramine hydrochloride Asphaltum
Barium chlorate Castor oil
Barium nitrate Dextrin
Hexachlorobenzene Diatomaceous earth
Magnesium powder Ethyl alcohol
Potassium chlorate Graphite
Potassium perchlorate Gum Arabic
Sodium oxalate Linseed oil
Strontium nitrate Orange shellac
Sugar Red gum
Xylene-azo-beta-naphthol Sodium bicarbonate
1-methylamino-antraquinone
1,4-di-p-toluidino-anthraquinone
1,9-benz-10-anthrone
3,4,8,9-dibenzpyrene-5,10-benzoquinone

Additional components are added to the above to permit injection of the

waste components as a liquid or slurry. Other additives are used to
enhance transport and combustion properties. Mixture additives can include
the following:

Fuel oil - solvent for smoke/flare components, adjustment of

heating value.
Water - solvent for smoke/flare components.
Surfactant - emulsifying/wetting agent for oil/water
mixtures.
Aluminum stearate/aluminum oleate - gelling agent for
adjustment of suspension properties.
The waste feed system includes the waste feed tank and the waste feed pump.
The waste feed tank is a 379 liter (100 gal) feed mix tank which is a free-
standing, hinged top, stainless steel tank fitted with an electric mixer
and an internal tank mixer. The waste feed pump is a severe-duty chemical
pump developed for transferring slurries which can operate at no-flow
conditions without overheating the captured feed material.

The incinerator is a refractory-lined cylinder, vertically oriented and

supported by adjustable clips. The interior volume of the incinerator
chamber is estimated to be about 1.13 m3 (40 ft3). The operating range of
the incinerator is 782-12050 C (1440 - 2200 0 F). The slurry feedrate to the
incinerator is 38.6 kg/hr (85 lb/hr). The incinerator head and exit
transition are lined with castable refractory secured with metal anchors.

28
SANDIA NATIONAL LABORATORIES, Albuquerque, NM
CONTRIBUTOR: Dr. David Anderson

TRANSIENT BURN STUDIES

SANDIA National Laboratories continues to study the burning behavior of
titanium subhydride/potassium perchlorate (TiH1 6/KClO 4 ). Recent research
is aimed at studying the dynamic compaction of the confined cylindrical
charge as the pyrotechnic burns.
Flash radiography, optical fibers and piezoelectric pressure transducers
were used to study the phenomenon. Lead disks, placed between the
increments of powder, serve as x-ray tracers. Fiber optics are used to
monitor the location of the ignition front. The pressure transducers
monitor the pressure history inside the closed test device. The data
indicate that a significant amount of compaction occurs as the charge
burns. References 50 and 51 provide additional information. To complement
this research, a semi-analytical model was developed 2 to determine the
pressure-time history based on the measured burning front velocity. Razani
et al. 53 also studied the effect of equations of state on the transient
burning analysis of pyrotechnic materials in a closed system. They show
that defining a co-volume for use in transient burning analysis in the
presence of condensed species requires careful considerations. They define
a variable co-volume for use in a simplified transient burning analysis and
show its effect on the pressure-time history of the pyrotechnic materials
burning in a closed system.

The effect of charge mixture ratio of titanium subhydride to potassium

perchlorate and the titanium subhydride particle size on the plume heat
transfer characteristics was also studiedi4 The coarse (8Am) titanium
subhydride produced the best performance when in a 41:59 stoichiometric
ratio with the potassium perchlorate. This material produced the highest
average maximum wall heat transfer rate. This mixture was compared to
those containing 2Am titanium subhydride and a 33:67 oxidizer-rich ratio
with potassium perchlorate.

DIODE LASER IGNITION

Development is continuing toward optically ignited devices using a (GaAl)As
laser diode (820 nm) to replace low energy, hot-wire igniters, detonators
and actuators."5 Optical energy is transmitted from the laser diode to a
pyrotechnic powder such as titanium subhydride/potassium perchlorate by way
of fiber optics. The fiber is coupled to the composition through a
hermetically sealed window, fiber feedthrough or a reimaging lens/window
system. Some advantages are the absence of a bridgewire and electrical
leads. It eliminates powder-bridgewire interface decoupling and corrosion
concerns. The problems of no-fire, conductance after firing, electrostatic
discharge, electromagnetic radiation and infrared concerns are either
eliminated or reduced.
Design parameters of the components needed to assemble the diode laser
ignition system have also been studied. The effects and characterization
of radiative transfer associated with a model of titanium subhydride/
potassium perchlorate laser ignition has been studied from a theoretical
aspect.7 Prototype optical headers containing sealed windows or fiber
segments have been fabricated, loaded with titanium subhydride/potassium
perchlorate, and test fired. The principal findings of this effort are
that a. High optical absorptance at the -800 nm diode laser wavelength is
the most important material factor in obtaining low ignition thresholds.
Titanium subhydride/potassium perchlorate is inherently a good absorber,
b. Powder density and confinement, laser spot size, and the thermal
conductivity of materials at the ignition interface are other parameters
which must be considered when optimizing a diode laser igniter, and

29
c. Ignition of titanium subhydride/potassium perchlorate has been achieved
from commercially available diode lasers at energies below 2 mJ (200 mW for
10 ms).
SRI INTERNATIONAL, Palo Alto, CA
CONTRIBUTOR: Dr. Donald J. Eckstrom

FREE-FLIGHT TEST FACILITY

An important aspect of this program is the need to test the performance of
flares in a turbulence-free windstream. The turbulence-free requirement
precludes the use of wind tunnels or blowdown test facilities like the one
at the Naval Weapons Support Center at Crane, Indiana. Therefore, we
developed a free-flight test facility based on a pneumatically driven
(airgun) launcher. The airgun barrel is 15 cm ID by 6.1 m long and is made
of honed steel. The air tank is of 454 liter capacity and is designed to
ASME specifications and pressure tested for 3.4 x 106 Pa (500 psi). The
tank is fitted with welded flanges that provide O-ring seals to the barrel.
Ten radial ports, each 2.5 x 7.5 cm, provide rapid air passage between the
pressure tank and the barrel.

The flare model is mounted in a sabot consisting of a polyethylene bottle

of approximately 4 liter (1 gallon) capacity that had been filled with
polyurethane foam and allowed to expand into a form of the exact diameter
as the barrel. The top of the bottle was then cut off, and a recess was
formed in the urethane to provide a nest for the flare. The sabot is long
enough to fill the barrel over a length that includes the radial ports and
two O-rings, thus sealing the pressure tank from the barrel before the
shot. A shot is initiated by opening a solenoid valve that connects the
pressure tank with the breech. The resulting buildup of pressure moves the
sabot forward until the radial ports are unsealed, allowing the full tank
pressure to be applied to launch the sabot and flare. A heavy steel ring
is placed on the support beam just beyond the end of the barrel to serve as
a sabot stripper to ensure that there is no interference between the flare
plume and the sabot.

The flare is ignited by an electric match fitted into the hole in the aft
end of standard MJU-8/B flare grains or is taped to the surface of
candidate flare compositions, fabricated locally. The match leads are
brought forward to the front of the sabot and connected to leads soldered
to copper conducting tape that is wrapped on the front 3 cm of the sabot in
such a way that it provides two electrodes. As the sabot exits the barrel,
these electrodes brush against contacts mounted at the end of the barrel.
The contacts, in turn, are connected to a charged capacitor. This
arrangement provides a reliable, fail-safe ignition procedure that
successfully ignites the flare on every launch.

SVERDRUP TECHNOLOGY INC., NSTL, MS

CONTRIBUTOR: Mr. Fred McIntyre
VECTOR MIXER STUDY

The U.S. Army identified the need to study pyrotechnic mixing technology.
Several new and safer mixing concepts were identified 3 '' for potential use
in the manufacturing of pyrotechnics. The MIGRAD mixer manufactured by
APV, was chosen as an alternative to current manufacturing methods
(mix/muller and/or Hobart). A study was conducted on the MIGRAD (Mixer-
Granulator-Dryer) by Pine Bluff Arsenal personnel. The Pine Bluff Arsenal
study showed that the MIGRAD mixing concept, which takes advantage of the
current state-of-the-art technology, was a safe and viable alternative to
current mixing techniques. The VECTOR FLO-COATER was also evaluated in a
similar manner to the MIGRAD mixer. This study was necessary because some

30
of the candidate pyrotechnic mixtures identified by the operating plants
could not be safely blended in the MIGRAD mixer.
The VECTOR FLO-COATER is a multi-purpose fluid bed granulation and/or
coating machine for blending, granulating and drying. The FLO-COATER uses
controlled temperature air flow introduced into the bottom of the mix
container to combine raw materials. A controlled rate binder spray system,
using a pump for delivery and compressed air for atomization, wets the dry
powder and provides for particle growth. The mixing, granulating, drying,
and discharge of the final product are accomplished remotely by either
manual or automatic operation. Timers on either an analog or digital
control panel are used for mixing, binder addition, drying, filter
blowdown, and discharging the finished product.

Typically, once the FLO-COATER power is turned on, dry mixing is

accomplished in approximately one-minute. Mixing is accomplished by
fluidic air flow that lifts and folds the product material over and the
rotor action which moves the mixture in a 3600 movement while it is
fluidized in the product bowl. Binder addition can take place either from
a spray nozzle located in the expansion chamber or in the periphery of the
product bowl. Average binder addition time is approximately 16 minutes.
Once the binder has been added and particle growth has been achieved,
drying is accomplished by adding heated air into the product bowl. Average
drying time is approximately 4 minutes. Remote discharge of the finished
product is accomplished in approximately 3 minutes. A typical mixing,
granulation, drying, and discharging scenario then is approximately
23 minutes for a typical pyrotechnic batch.

A total of 100 live batches of 18 different pyrotechnic mixtures have been

successfully blended in the FLO-COATER without incident. The FLO-COATER
has been certified to mix a total of 58 different pyrotechnic mixtures.

THIOKOL CORPORATION, Marshall, TX

CONTRIBUTOR: Dr. David R. Dillehay
TWIN SCREW EXTRUDER

The initial studies at Thiokol of twin-screw extruder processing used

Werner & Pfleiderer (W&P) twin-screw extruders of a modular barrel design.
This modular design offered flexibility in setup since the barrel modules
could be arranged to give any configuration of feed ports, process sections
and vacuum ports desired. A major problem identified with this design
concerned the problem of jamming of the screws due to feed problems. If
the screws become jammed, the modular barrel design must be disassembled by
disconnecting the screw shaft coupling and pulling the screws through the
barrels with live material on the surfaces, or by unbolting each section of
the barrel and pulling the barrel section over the shafts, again with live
material on the surfaces. To avoid this situation, W&P designed and built
a split barrel extruder that could be remotely opened in case of screw
jamming and also incorporated many other design features specifically
engineered for safety.

The extruder has a nominal screw diameter of 58mm (2.3 inches) and a barrel
length of 1440mm (56.7 inches). The length of the assembled screw elements
on the shaft is 1440mm. This gives an L/D ratio of 24:1. Screw elements
are available in several combinations of length and pitch. The elements
are assembled on splined shafts and end caps are torqued to a minimum of
10.4 kgom (75 ft-lb).

There are three tempered zones in the extruder barrels and a fourth
tempered zone in the die head when using direct extrusion. The tempered
zones are temperature controlled by pumping heated water from hot water

31
heaters through the barrel sections. The heaters are capable of heating
the water to 149 0C (3000 F).

The top barrel section has four openings into the bore of the extruder.
The first opening is near the back of the barrel for feeding polymers or
slurries to the extruder. This port is approximately 6.35mm (0.25 inches)
in diameter. The second port is also near the back of the extruder and is
a large (10.16 x 12.7 cm; 4x5 inches) opening for feeding solids to the
extruder. This is followed closely by another liquid feed port, also
6.35mm (0.25 inches) in diameter. Near the discharge end of the
extruder, there is a large opening (10.16 x 20.32cm; 4x8 inches) used for
removing volatile solvents or gases from the composition. A vacuum vent is
attached to this port and a water-seal vacuum pump is used to draw off
volatiles.

Live infrared decoy flare composition was processed on the twin-screw

extruder in the mixer mode and pressed into test pellets. The pellets were
finished with normal production handling and were tested in the test
tunnel. Performance was excellent. All test parameters were met.
Reproducibility from pellet to pellet was excellent even though the
material is in the mixer for only about 2 minutes. Additional live runs
have been accomplished on the extruder facility with good replication from
mix to mix. Future efforts will include developing criteria and techniques
for processing in the extruder mode. Recharging of feeders and take-away
of processed material are also major areas of interest. One of the main
safety features is the low amount of material in process at any time. The
extruder is run starve-fed with approximately 900g (2 pounds) of
composition in the barrels at any one time. The solvent content of the
flare composition can be reduced through the use of vacuum at the vacuum
port. Test and evaluation of the twin-screw extruder is continuing.

UNIDYNAMICS/PHOENIX, Phoenix, AZ

CONTRIBUTOR: Mr. John W. Fronabarger

USE OF TITANIUM IN BRIDGEWIRE-SENSITIVE PYROTECHNICS

Fine particle size (:l0 gm) titanium is widely used in applications

requiring bridgewire-sensitive pyrotechnics with fast function times.
Unidynamics uses this constituent in compositions for pyrotechnic igniters
and ballistic actuators. Recent Independent Research and Development
studies have shown that the particle morphology of this ingredient is
critical to its performance in hot wire applications. Scanning electron
microscope images of different grades of fine titanium have disclosed that
the type of material which requires the lowest bridgewire firing currents
and yields the shortest function times and fastest pressure rise rates in
actuators is the product exhibiting particles with rough, highly irregular
surfaces resembling cauliflower heads. Materials with smoother, more
rounded particles are less sensitive and slower burning.
HYDROGEN BURNOFF IGNITER

Early in 1980 it was discovered during static firings of liquid

hydrogen/liquid oxygen Space Shuttle Main Engines that excessive
overpressures were encountered below some engine assemblies. These
overpressures were attributed to explosive deflagration of the cloud of
hydrogen gas which formed around the base of the engine just prior to
ignition. Such deflagrations could cause damage in the base heatshield
area and nozzles. The approach taken to resolve this problem was the use
of pyrotechnic compositions to ignite the hydrogen prior to excessive
buildup. Initially, compositions such as magnesium/polytetrafluoroethylene
were used but were not totally satisfactory, e.g., short plume range.
Unidynamics developed an ignition system based on a metalized ammonium
perchlorate/hydroxyterminated polybutadiene polymer composite propellant.

32
The metal used was large particle (- 550 gm) zirconium. This system has
performed successfully and is still in use today for the shuttle
launchings.
WRIGHT LABORATORY
Wright-Patterson Air Force Base, OH
CONTRIBUTOR: Mr. Joe Koesters

INFRARED DECOY FLARES

Recognizing that advanced infrared missile technology is now able to
discriminate decoy flares from aircraft targets and subsequently to reject
the decoy flares, an advanced aerodynamic flare (AAF) program was started.
The decoy flare simulates the infrared radiative power and aerodynamic
characteristics of the aircraft. The decoy contains a pyrotechnic source
to provide the desired infrared radiation and thrust to simulate the
aircraft forward motion. This kinematic property to produce a trajectory
more like that of the target aircraft plus infrared radiative power
distributed as in that of the aircraft makes the decoy flare quite 61.62.63
effective against advanced seekers employing kinematic discrimination.

Another development being evaluated is the special infrared flare (SIRF).

This development is intended to be less susceptible to missile infrared
counter-countermeasures and to simulate aircraft flight and spectral
signature. When dispensed from the aircraft, it flies along for a short
period while it seduces the missile before separating further to create the
needed miss distance. Research efforts are continuing.

Another effort is to optimize decoy flares to be effective at supersonic

speeds where future aircraft are expected to operate. This study will
address the requirement for protection of the aircraft and identify
technologies which should be pursued after wind-tunnel and rocket-sled
testing.

ACKNOWLEDGEMENTS
The author wishes to thank all the contributors of the information and the
visual aids for this paper. The assistance provided by Ms. Janet Hooper in
getting an article translated is appreciated.

REFERENCES
1. Arents, Prosper; Pompa Introitus Ferdinandi, De Nederlandsche
Boekhandle, 1950: This engraving copy from the collection of the printroom
of the city of Antwerp was distributed by the Hendrickx Fireworks Company,
for the occasion of its 150th anniversary; Deurne, 20 September 1984.
2. Isler, J.; Self-Ignition of Single Base Propellants in ProDellants.,
Explosives and Pyrotechnics, i, 40 (1986)
3. Isler, J.; Self-Ignition of Nitrocellulose in Propellants. Ex~losives
and Pyrotechnics, 2, 130 (1984)
4. 1989 members of the Organization for Economic Cooperation and
Development (OECD) were: Australia, Austria, Belgium, Canada, Denmark,
Finland, France, W. Germany, Greece, Iceland, Ireland, Italy, Japan,
Luxembourg, Netherlands, New Zealand, Norway, Portugal, Spain, Sweden,
Switzerland, Turkey, United Kingdom, United States and Yugoslavia. OECD is
located at 2 rue Andre Pascal, F-75775 PARIS 16, and was founded in 1960.
The OECD has established guidelines for testing of chemicals regarding
their environmental impact. These guidelines are internationally used to
check and qualify chemicals and mixtures of chemicals as to their toxicity.
5. Krone, Uwe; Pyrotechnical Mixture for Producing A Smoke Screen, U.S.
Patent 4 968 365, 6 November 1990. This is a potassium nitrate/magnesium
(KM) smoke.

33
6. Krone, Uwe; A Non-Toxic Pyrotechnic Screening Smoke for Training
Purposes in Proceedings of the Fifteenth International rvrotechnics Seminar
at Boulder, CO, 9-13 July 1990; IITRI: Chicago, pp 581-586.
7. Krone, Uwe; Koop, M.; Coupling Agents (Titanates) In Plastic Bonded
Pyrotechnic Smoke Composition in Proceedings of the American Defense
Preparedness Association meeting on Compatibility of Plastics And Other
Materials With Explosives. Propellants and Pyrotechnics, 18-20 April 1988,
New Orleans, LA.
8. Yano, Y.; Condensed Phase Reaction of Boron With Potassium Nitrate in
Propellants. Explosives. Pyrotechnics, Vol 14, No. 5, October 1989,
pp 187-189.
9. Yano, Y.; Kubota, N.; Combustion of Boron/Potassium Nitrate, draft of
unpublished paper, 1990.
10. Kubota, N.; Serizawa, C.; Suzuki, N.; Smokeless Igniters for Solid
Rockets in Proceedings of the 16th International ICT Combined with the 10th
International Pyrotechnics Seminar, ICT, 2-5 July 1985, Karlsruhe, pp 21-1
to 21-13.
11. DING, Jing, The Discovery of Gunpowder and Shock Wave in Chij_ in
Proceedincls of the Fifteenth International Pyrotechnics Seminar at
Boulder CO, 9-13 July 1990; IITRI: Chicago, pp 515-534.
12. HUANG, Haochuan; LI, Fang, Determination of Combustion Response
Function R. for Pyrotechnic Whistlina Composition in Proceedings of
Fifteenth International Pyrotechnics Seminar at Boulder, CO,
9-13 July 1990; IITRI: Chicago, pp 455-467.
13. HUANG, Haochuan; LI, Fang Pyrotechnic Whistle Mechanism in Proceedings
of the Thirteenth Intern-ttonal Pyrotechnics Seminar at Grand Junction, CO,
11-15 July 1988; IITRT: chicago, pp 477-492.
14. LI, Fang; LAO, .. iang, An Estimation of the Maximum Extinction
Coefficient for t -nerical Particle Dispersion in Proceedings of
Fifteenth InternL t. nal Pyrotechnics Seminar at Boulder, CO,
9-13 July 1990" IITRI: Chicago, pp 637-645.
15. HEN, Ruial; DAI, Shizhi, Static Failure Rate Eguation of Ignition
System in PLoceedinqs of Fifteenth International Pyrotechnics Seminar at
Boulder, C2,, 9-13 July 1990; IITRI: Chicago, pp 1017-1029.
16. Loyi, D; Andersson, G.; Nyhlen, H.; Slow Pyrotechnical Compositon -
Heat Transfer Analysis, in Proceedings of 6th International Conference on
Numerical Methods in Thermal Problems, (Eds. Lewis, R. W. and Morgan, K.),
Pine-idge Press, Swansea, Wales, U.K., 1989, pp. 1258-1268.
17. Glarborg, P.; Kee, R. J.; Grear, J. F.; Miller, J. A. PSR: A Fortran
Program for Modeling Well-Stirred Reactors, Sandia National Laboratories,
SAND86-8209, February 1986.
18. Kubota, N.; Serizawa, C. Combustion Process of Ma/TFE Pyrotechnics, in
Propellants. Explosives. Pyrotechnics, Vol 12, No. 5, October 1987,
pp 145-148.
19. Penner, S. S.; Bahadori, M. Y.; Kennedy, E. M. Laminar Diffusion
Flames with Cylindrical Symmetry. Arbitrary Values of Diffusion
Coefficients and Inlet Velocities. and Chemical Reactions in the ADrroach
Streams in Dynamics of Flames and Reactive Systems, pp 261-292, Volume 95,
Progress in Astronautics and Aeronautics, 1984.
20. Burke, S. P.; Schumann, T. E. W. Diffusion Flames in Ind. =q. Q=.
20, 1928, pp 998-1004.
21. Cook, M. D.; Haskins, P. J. Implications of Recent Projectile Impact
Studies for Hazard and Vulnerability Assessment in Proceedings of the
Fourteenth International Pyrotechnics Seminar at Jersey, Channel Islands,
Great Britain, 18-22 September 1989; RARDE NP3: Fort Halstead, UK,
pp 673-681
22. Munger, A. C.; Woods, C. M. The Implications of Using Insensitive
Materials in Hot-Wire Devices in Proceedings of the Fifteenth International
Pyrotechnics Seminar at Boulder, CO, 9-13 July 1990; IITRI: Chicago,
pp 735-742.
23. Short, J. E. Fire Resistant Photoflash Cartridge
U.S. Patent 3 699 890, 24 October 1972.
24. Jane's Defence Weekly, volume 12, number 12, 23 September 1989, p 612.

34
25. Chin, A.; Rankin, M. D.; Hubble, B. R. Insensitive Pyrotechnics-
Improved Binders for Colored Smokes in Proceedings of the Thirteenth
International Pyrotechnics Seminar at Grand Junction, CO, 11-15 July 1988;
IITRI: Chicago, pp 129-139.
26. Chin, A.; Hubble, B. R.; Caldwell, N. J. Thermal Stability and
Mechanistic Investigation of Insensitive Colored Smoke Compositions
Containing 2.4.6-Tribromophenol Under Slow Cook-Off Stimuli in Proceedings
of 1989 Annual Meeting of the Pyrotechnics and Explosives Applications
Section of the American Defense Preparedness Association (In Press).
27. Chin, A.; Caldwell, N. J.; Hubble, B. R. Desensitization of Colored
Smoke Compositions by Caramelization of Sucrose Under Slow Cook-Off
Stimuli, Presented at the 1990 Annual Meeting of the Pyrotechnics and
Explosives Application Section of the American Defense Preparedness
Association, 2-4 October 1990.
28. Kennedy, J. R.; Ringwald, M. G.; Schonberger, J. A.; Lohkamp, C. W.;
Small Craft Combat Survivability Enhancement Through the Use of Smoke in
Naval Engineers Journal, pp 114-126, May 1989.
29. Brown, P. R.; Sanders, T. J.; Huxhold, R. G.; Simulator. Tactical Use
Flare (STUF): A Low Cost Training Round in Proceedings of the 1990 Annual
Meeting of the Pyrotechnics and Explosives Application Section of the
American Defense Preparedness Association at SANDIA, 2-4 October 1990, in
press.
30. Suurkuusk, J.; Wadso, I.; Chemica Scripta (Sweden), 20, 155 (1982)
31. Elmqvist, C. J.; Lagerkvist, P. E.; Svensson, L. G.; J. Hazardous
Materials, 7, 281, (1983)
32. Lagerkvist, P. E.; Svensson, L. G.; Elmquist, C. J.; Ampoule
Microcalorimetry for Stability Testing of Primary Explosives and
Pyrotechnics in Proceedings of the Ninth International Pyrotechnics Seminar
at Colorado Springs, CO, 6-10 August 1984, IITRI: Chicago, pp 323-336
33. Svensson, L. G.; Taylor, D. E.; Forsgren, C. K.; Backman, P. 0.;
Proceedings of 1985 American Defense Preparedness Association Annual
Meeting on the Compatibility of Plastics and Other Materials with
Explosives, Propellants and Pyrotechnics, p. 19 (1985)
34. Svensson, L. G.; Taylor, D. E.; Forsgren, C. K.; Backman, P. 0.;
Proceedings of the 1986 American Defense Preparedness Association Annual
Meeting on the Compatibility of Plastics and Other Materials with
Explosives. Propellants and Pyrotechnics, p. 86 (1986)
35. Short, James E. Jr., Fast Cook-Off Proaram in Proceedings of Second
International Pyrotechnics Seminar at Snowmass-at-Aspen, CO,
20-24 July 1970; IITRI: Chicago, pp 43-54. (AD-913407)
36. Gilliam, Clarence W.; Johnson, Duane M. Pollution Abatement
Reclamation of Red Phosphorus Smoke Compositions in Proceedings of Fourth
International Pyrotechnics Seminar at Steamboat Village, CO, 22-
26 July 1974; IITRI: Chicago, Paper 25, pp 0-10. (AD-A057599)
37. Dinerman, C. E.; Gilliam, C. W. Ecological Disposal/Reclaim of Navy
Colored Smoke Compositions in Proceedinas of Fifth International
Pyrotechnics Seminar at Vail, CO, 12-16 July 1976; IITRI: Chicago, pp 168-
188. (AD-A087513)
38. Shaw, G. A.; Munson, W. 0.; Dinsdale, V. T.; McIntosh, M. J.
Reclamation of Propellant and Flare Ingcredients in Proceedings of Fifth
International Pyrotechnics Seminar at Vail, CO, 12-16 July 1976; IITRI:
Chicago, pp 628-642. (AD-A087513)
39. Short, J. E.; Montgomery, F. E. Environmentally Acceptable Method for
the Demilitarization of the MK 24 and the MK 45 Aircraft Parachute Flares
in Proceedings of Sixth International Pyrotechnics Seminar at Estes Park,
CO, 17-21 July 1978; IITRI: Chicago, pp 537-544. (AD-A063797)
40. Short, J. E.; Montgomery, F. E. Environmentally Acceptable Method for
the Demilitarization of the Red Phosphorus Munitions in Proceedings of
Sixth International Pyrotechnics Seminar at Estes Park, CO, 17-21 July
1978; IITRI: Chicago, pp 545-554. (AD-A063797)
41. Short, J. E.; Montgomery, F. E. A Pilot Plant for the Demilitarization
of Photoflash Munitions in Proceedings of the Seventh International
Pyrotechnics Seminar at Vail, CO, 14-18 July 1980; Volume 2; IITRI:
Chicago, pp 599-610. (AD-A145289)

35
42. Simpson, G.M. Waste Disposal in Proceedings of the Fourteenth
International Pyrotechnics Seminar at Jersey, Channel Islands, Great
Britain, 18-22 September 1989; RARDE NP3: Fort Halstead, UK, pp 417-421
43. Montgomery, F. E.; Short, J. E.; Weaver, W. J. Reclamation of
Materials From Photoflash Cartridges U.S. Patent 4 333 737, 8 June 1983.
44. Colvin, R. E.; Douda, B. E.; Montgomery, F. E.; Short, J. E. Process
for Disposing of Decoy Flare Material U.S. Patent 4 276 100, 30 June 1981.
45. Douda, B. E.; Parrish, C. F.; Short, J. E. Solvent Having High Flash
Point U.S. Patent 4 260 509, 7 April 1981.
46. Montgomery, F. E.; Short, J. E.; Weaver, W. J. Method for Disposing of
Red Phosphorus Composition U.S. Patent 4 163 682, 7 August 1979.
47. Doades, W. E.; Short, J. E.; Whorrall, K. S. Method for Disposal of
Tracer Bullets U.S. Patent 3 982 930, 28 September 1976.
48. Parrish, C. F.; Short, J. E.; Whorrall, K. S. Method for Disposal of
Pyrotechnic Waste U.S. Patent 3 930 844, 6 January 1976.
49. Musselman, K. A.; Short, J. E. Process for Disposing of Pyrotechnic
Flares U.S. Patent 3 897 237, 29 July 1975.
50. Hingorani-Norenberg, Sheryl L.; Razani, A.; Shahinpoor, M. Compaction
of ITilA./KCIO, Pyrotechnic Powder During Confined Burn, SANDIA report
SAND90-0600C, 1990. See also Proceedings of the Fifteenth International
Pyrotechnics Seminar at Boulder, CO, 9-13 July 1990; IITRI: Chicago,
pp 403-419.
51. Hingorani-Norenberg, S. L. An Experimental Study of the Burn Rate of
TiH 1 6,/KCl-0 Pyrotechnic Under Confinement, SANDIA report SAND88-2393, 1988.
52. Razani, A; Shahinpoor, M.; Hingorani-Norenberg, S. L. A Semi-
analytical Model for Pressure-Time History of Granular Pyrotechnic
Materials in a Closed System in Proceedings of the Fifteenth International
Pyrotechnics Seminar at Boulder, CO, 9-13 July 1990; IITRI: Chicago,
pp 799-813.
53. Razani, A; Shahinpoor, M.; Hingorani, S. L. Effect of Eguations of
State on Transient Burning Analysis of Pyrotechnic Materials in a Closed
System, SANDIA report SAND90-1851A, 1990
54. Evans, N. A.; Brezowski, C. F. The Effect of Charae Mixture Ratio and
Particle Size on Igniter Plume Heat Transfer Characteristics in Proceedings
of the Fifteenth International Pyrotechnics Seminar at Boulder, CO,
9-13 July 1990; IITRI: Chicago, pp 261-276.
55. Jungst, R. G.; Salas, F. J. Diode Laser Ignition of Explosive and
Pyrotechnic Components, SANDIA report SAND90-0641A, 1990.
56. Jungst, R. G.; Salas, F. J.; Watkins, R. D.; Kovacic, L. Development
of Diode Laser-Ignited Pyrotechnic and Explosive Components in Proceedings
of the Fifteenth International Pyrotechnics Seminar at Boulder, CO, 9-13
July 1990; IITRI: Chicago, pp 549-579.
57. Skocypec, P. D.; Mahoney, A. R.; Glass, M. W.; Jungst, R. G.; Evans,
N. A.; Erickson, K. L. Modeling Laser Ignition of Explosives and
Pyrotechnics: Effects and Characterization of Radiative Transfer in
Proceedings of the Fifteenth International Pyrotechnics Seminar at Boulder,
CO, 9-13 July 1990; IITRI: Chicago, pp 877-894.
58. Shook, Thomas E.; Aikman, Loy M.; Frauenthal, Max; Garcia, David;
Janski, Joe G.; and McIntyre, F. L.; Remote Mixing and Handling Procedures
for Pyrotechnic Materials in Design Considerations for Toxic Chemicals and
Explosives Facilities, Edited by Ralph A. Scott, Jr. and Laurence J.
Doemeny, ACS Symposium Series 345, American Chemical Society,
Washington, DC 1987.
59. Dillehay, David R.; Processing of Energetic Materials on Twin Screw
Ex r in Proceedings of Fifteenth International Pyrotechnics Seminar at
Boulder, CO, 9-13 July 1990; IITRI: Chicago, p 219.
60. bztap, Selquk; The Pyrotechnic Whistle and Its Applications in
PYROTECHNICA: Occasional Papers in Pyrotechnics, Parts I and II, Issue XI
June 1987, pp 49-54 and Issue XIII August 1990, pp 19-21;
Pyrotechnica Publications, Austin, TX.
61. Womble, M. E., Advanced Offboard Countermeasures in Journal of
Electronic Defense, Vol. 12, No. 11, November, 1989 pp 37-38.
62. Helberg, K. W. Electronic Warfare Technology-Trends and Visions in
Journal of Electronic Defense, Vol. 13, No. 5, May, 1990, pp 47-63.

36
63. Galatowitsch, S. Expendables Cover ThL Spectrum in Defense
Electronics, Vol. 22, No. 9, September, 1990 pp 47-53.
64. Griffiths, T. T., Pyrotechnic Igniters for Use in Extended Carrier
Shells in 4th International Conference of the "Groupe de Travail de
Pyrotechnie" supported by Centre National d'Etudes Spatiales at La Grande-
'6.otte, France, 5-9 June 1989; Association Francaise de Pyrotechnie: Paris,
pp 121-126.
65. Commercial Operators Seek to Counter Growing Heat-Seekina Missile
Threat and More Capable IR-Guided Weapons Prompting Improved Jammers.
Decoys respectively in Aviation Week and Space Technology, Vol. 129,
No. 12, 19 September 1988, page 43-44 and Vol. 131, No. 11,
11 September 1989, pp 50-57.
66. Towning, J. N., Pyrotechnic Flares: Radiant Intensity and Radiance
Calculations in Proceedings of the Fourteenth International Pyrotechnics
Seminar, at Jersey, Channel Islands, Great Britain, 18-22 September 1989;
RARDE NP3: Fort Halstead, UK, pp 537-550.
67. Queay, J.; Barnes, P., Co-chairmen, Proceedings of Workshop on
Sensitivity of Pyrotechnic Compositions Especially Electrostatic Hazards
Relating to Magnesium Teflon Viton Formulations and Processing at Waltham
Abbey, 8-10 September 1987; RARDE NP3: Fort Halstead, UK.
68. linston, S. F.; Arnell, R. D.; Allford, F. G., Multi-Layered
Metal/Metal Oxide Coatings by Ion Plating for Pyrotechnic Applications in
Proceedings of the Fourteenth International Pyrotechnics Seminar at Jersey,
Channel Islands, Great Britain, 18-22 September 1989; RARDE NP3:
Fort Halstead, UK, pp 73-79.
69. Allford, F. G.; Place, M. S., The Development and Production of
Pyrotechnic Systems from the Vapour Phase, Parts One and Two, in
Proceedings of the Fifteenth International Pyrotechnics Seminar at
Boulder, CO, 9-13 July 1990; IITRI: Chicago, pp 1-34.
70. Shimizu, Takeo; A Concept and The Use of Negative Explosives in
Proceedings of the Eleventh International Pyrotechnics Seminar at Vail, CO,
7-11 July 1986; IITRI: Chicago, pp 537-553.
71. Shimizu, Takeo; Techniques for the Manufacture of Fireworks:
(1) Non-illuminating Delay Charaes (2) Use of Metal Powder presented at the
XIth European Pyrotechnics Congress, Tenerife, Spain, 1989.

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