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STP 7C-1977

This document, prepared by the ASTM Committee D-2 on Petroleum Products and Lubricants, serves as a comprehensive reference on the significance of testing for petroleum products. It outlines the quality characteristics, testing methods, and applications for various petroleum materials, including crude oils, gaseous fuels, automotive gasoline, and aviation fuels. The volume is structured into chapters, each focusing on specific products and their respective testing standards, with suggestions for further reading included.

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STP 7C-1977

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SIGNIFICANCE OF TESTS

FOR PETROLEUM PRODUCTS

Prepared by
ASTM Committee
D-2 on Petroleum Products
and Lubricants

ASTM SPECIAL TECHNICAL PUBLICATION 7C

Kenneth Boldt
Union Oil Company of California
editors
B. R. Hall
American Petroleum Institute

List price $11.75

04-007030-12

AMERICAN SOCIETY FOR TESTING AND MATERIALS

1916 Race Street, Philadelphia, Pa. 19103

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9 AMERICAN SOCIETY FOR TESTING AND MATERIALS 1977
Library of Congress Catalog Card Number: 76-29513

NOTE
The Society is not responsible, as a body,
for the statements and opinions
advanced in this publication.

Printed in Ta]lahassce. Fla.

January 1977

This book has been developed through the joint efforts of the American
Society for Testing and Materials (ASTM) and the Institute of Petroleum (IP).
ASTM, particularly its Committee D-2 on Petroleum Products and Lubricants,
and IP are long-established sources of standard testing and evaluation methods
for petroleum and petroleum products. Many of these standard methods are
accepted internationally as yardsticks for the determination of product quality.
The purpose of this volume is to provide an informative reference text on the
significance of ASTM and IP test results that are used in commerical transactions
to definitively describe petroleum raw materials and petroleum products. To
ensure orderly treatment, separate chapters have been prepared for each major
raw material or end product. The general approach in each chapter is as follows:
(a) A definitive description of the raw material or product is presented along
with its known or prospective use applications.
(b) The primary quality characteristics that define the material in those use
applications are outlined.
(c) The particular tests and analytical procedures applicable to the quality
assessment for the material are indicated.
(d) Suggestions for further reading are listed.
Each chapter has been written as an entity. Since many tests are applicable to
several products, this results in a certain amount of repetition. Repetition was
believed to be preferable to elaborate cross referencing.
Although this book will be revised periodically, there will be no assurance that
the test methods or specifications cited are current. Up-to-date standards can be
found in the appropriate volumes of the Annual Book of ASTM Standards and
IP Standards for Petroleum and Its Products.

Viscosity Index Tables for Celsius Temperatures, DS 39B (1975), $30.00,

05-039020-12

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Acknowledgments
This volume has been developed over a number of years through the joint
efforts of the American Society for Testing and Materials and the Institute of
Petroleum. In the process, chapters have been written, revised, and rewritten
until it became difficult to distinguish between author, reviewers, and editors.
Hopefully, the following list of acknowledgments includes all who contributed
to the process.

Editors
Kenneth Boldt Union Oil Company of California
B. R. Hall American Petroleum Institute
Associate Editor
W. D. Dysart Union Oil Company of California
Crude Oils
J. O'Donnell BP Research Centre, U.K.
C. E. Webber Sun Oil Company
Gaseous Fuels and Light Hydrocarbons
R. E. Cannon Gas Processors Association
C. A. Munson Petro-Tex Chemical Corp.
F. W. Selim Phillips Petroleum Co.
Petroleum Solvents
D. M. Fenton Union Oil Company of California
A. J. Goodfellow Carless, Capel and Leonard Ltd., U.K.
J. F. Hickerson Exxon Company, U.S.
S. A. Yuhas Exxon Chemicals
Automotive Gasoline
K. A. Boldt Union Oil Company of California
J. A. English Chevron Research Co.
R. L. Everett General Motors Corp.
S. T. Griffiths The Associated Octel Co., Ltd., U.K.
H. R. Porter Standard Oil Company of California
J. H. Macpherson Chevron Research Co.
Aviation Fuels
W. G. Dukek Exxon Research and Engineering Co.
R. I. GottshaU Gulf Research and Development Co.
D. T. McAllan BP Research Centre, U.K.
A. G. Robertson Shell International Petroleum Co., Ltd., U.K.
Diesel Engine and Nonaviation Gas Turbine Fuels
G. K. Brower International Harvester Co.
W. H. Kite, Jr. Exxon Research and Engineering Co.

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J. A. McLain Caterpillar Tractor Company
R. E. Pegg Esso Research Centre, U.K.
C. C. Ward U.S. Department of the Interior,
Bureau of Mines
Heating and Power Generation Fuels
J. R. CaUaway Texaco, Inc.
W. H. Kite, Jr. Exxon Research and Engineering Co.
N. J. Schlesser Atlantic Richfield Company
G. G. Stephens BP Research Centre, U.K.
Lubricating Oils
J. B. Berkley Mobil Oil Company, Ltd., U.K.
J. W. Gaynor Amoco Oil Co.
Lubricating Greases
R. S. Barnes Amoco Chemicals Corp.
E. A. Goodchild Hoffman Manufacturing Co., Ltd., U.K.
A. T. Polishuk Sun Oil Company
Petroleum Waxes, Including Petrolatums
R. I. GottshaU Gulf Research and Development Co.
C. F. McCue Esso Research Centre, U.K.
G. A. Weisgerber Exxon Research and Engineering Co.
White Mineral Oils
V. Biske Burmah Oil Trading, Ltd., U.K.
C. F. W. Gebelein Pennsylvania Refining Co.
Petroleum Oils for Rubber
J. S. Sweely Sun Oil Company

Special acknowledgment is given to the Refining Department, American

Petroleum Institute for project sponsorship and to T. W. Legatski as the original
project coordinator.

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Editorial Staff
Jane B. Wheeler, Managing Editor
Helen M. Hoersch, Associate Editor
Ellen J. McGlinchey, Assistant Editor
Kathleen P. Turner, Assistant Editor

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Contents
Introduction 1
Chapter 1--Crude Oils 3
Introduction 3
Sampling 3
Preliminary Evaluation or Assay 4
Gravity 4
Sulfur, Hydrogen Sulfide, and Mercaptan Sulfur 4
Salt Content 6
Water and Sediment 6
Viscosity and Pour Point 6
Metallic Contaminants 7
Distillation 7
Light Hydrocarbon Analysis 8
Characterization Factor 8
Full or Comprehensive Evaluation 8
Crude Oil as a Power Generation Fuel 9
Applicable ASTM/IP Standards 12
Bibliography 13
Chapter 2---Gaseous Fuels and Light Hydrocarbons 14
Introduction 14
Natural Gas 14
Natural Gas Liquids (NGL) 14
Liquefied Refinery Gas (LR Gas) 15
Olefins and Diolefins 15
Quality Criteria 16
Natural Gas 17
Ethane 17
Liquefied Petroleum Gases 17
Natural Gasoline 18
Olefins and Diolefins 19
Ethylene 19
Propylene Concentrates 19
Butylene Concentrates 19
Butadiene 19
Applicable ASTM Specification 20
Applicable ASTM/IP Standards 20
Natural Gas and Ethane 20
Liquefied Petroleum Gas 20

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Natural Gasoline 21
Ethylene 21
Propylene Concentrates 22
Butylene Concentrates 22
Bibliography 22
Chapter 3--Petroleum Solvents 23
Introduction 23
General Uses 23
Product Requirements 23
Solvency 23
Volatility 24
Purity 24
Gravity 25
Odor 25
Toxicity 25
Air Pollution Requirements 26
Types of Hydrocarbons 26
Aliphatics 26
Naphthenes (Cycloparaffins) 28
Aromatics 28
Commercial Hydrocarbon Solvents 29
General Solvent Types 29
Specific Types of Solvents 29
Hexane and Heptane 29
Petroleum Ether 29
Textile Spirits 29
Lacquer Diluent 29
VM&P Naphtha 31
Ink Oils 31
Mineral Spirits 31
Benzene 31
Toluene 31
Xylene 31
Hi-Flash Solvent Naphtha 31
Kerosine 31
Test Methods for Solvents 32
Sampling 32
Specific Gravity 32
Distillation 33
Flash Point 33
Evaporation Rate 34
Kauri-Butanol Value 34
Aniline Point and Mixed Aniline. Point 35
Sulfur 35
Dilution Ratio in Nitrocellulose Solutions 35
Viscosity of Nitrocellulose Solutions 36

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Applicable ASTM Specifications 36
Applicable ASTM/IP Standards 36
Bibliography 40
Chapter 4 Automotive Gasoline 41
Introduction 41
Grades of Gasoline 41
Automotive Gasoline Performance and Information System 42
Antiknock Quality 42
Volatility 44
Other Properties 47
Workmanship and Contamination 47
Sulfur Content and Copper Strip Corrosion 47
Existent Gum and Stability 48
Gravity 48
Rust and Corrosion 49
Hydrocarbon Composition 49
Additives 49
Applicable ASTM Specification 5O
Applicable ASTM/IP Standards 51
Bibliography 51
Chapter 5--Aviation Fuels 53
Introduction 53
Historical Development of Aviation Fuels 53
Aviation Gasoline 54
Composition and Manufacture 54
Specifications 54
Content 54
Fuel Grades 54
Characteristics and Requirements 57
Antiknock Properties 57
Volatility 57
Density 60
Heat of Combustion 60
Freezing Point 61
Storage Stability 61
Sulfur Content 62
Water Reaction 62
Aviation Turbine Fuels (Jet Fuels) 62
Background 62
Fuel Development 63
British Jet Fuels 63
American Military Jet Fuels 64
American Civil Jet Fuels 66
Russian Jet Fuels 66
Other Foreign Jet Fuels 66
International Standard Specifications 69

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Specification Requirements 69
Chemical Properties and Composition 69
Physical Properties--Contaminants 71
Density and Heat of Combustion 72
Volatility 72
Low-Temperature Properties 72
Combustion Quality 73
Water Retention and Separating Properties 73
Thermal Stability 74
Miscellaneous Properties 74
Inspection Data on Aviation Turbine Fuels 74
Aviation Fuel Additives 75
General 75
Additive Types 76
Tetraethyllead (TEL) 76
Color Dyes 76
Antioxidant (Gum Inhibitor) 76
Metal Deactivator 76
Corrosion Inhibitors 77
Fuel System Icing Inhibitor 77
Electrical Conductivity Improver (Antistatic Additive) 78
Nonspecification Additives 79
Biobor JF 79
Antismoke Additives 79
Ignition Control Additive 79
Additive Tests 80
Tetraethyllead 80
Color 80
Antioxidant, Metal Deactivator, Corrosion Inhibitor 80
Fuel System Icing Inhibitor 80
Electrical Conductivity Improver 80
Applicable ASTM Specifications 81
Applicable ASTM/IP Standards 81
Bibliography 83
Fuel Specification Guides 83
Appendixes 83
I. Automotive (Motor) Gasoline--Unsuitability for Avia-
tion Use 83
II. Form for Inspection Data on Aviation Turbine Fuels 84
Chapter 6---Diesel Engine and Nonaviation Gas Turbine Fuels 85
Introduction 85
Diesel Engine 85
Nonaviation Gas Turbine 86
Combustion Process 87
Diesel Combustion 87
Nonaviation Gas-Turbine Combustion 90

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General Fuel Characteristics and Classifications 90
Background 90
Diesel Fuels 91
Nonaviation Gas Turbine Fuels 93
Fuel Properties and Tests 93
Cetane Number 96
Cetane Index 97
Diesel Index 99
Gravity 99
Distillation 101
Viscosity 102
Heat of Combustion 103
Cloud Point 103
Pour Point 104
Flash Point 104
Sulfur 105
Diesel Engines 105
Gas Turbines 106
Carbon Residue 106
Ash 107
Neutralization Number 108
Stabilility 108
Water and Sediment 108
Composition 109
Appearance and Odor 109
Vanadium, Sodium, Calcium, Lead 109
Applicable ASTM Specifications 110
Applicable ASTM/IP Standards 110
Bibliography 111
Chapter 7--Heating and Power Generation Fuel 112
Introduction 112
Kerosine 113
Domestic Heating Oils 113
Residual or Heavy Fuel Oils 115
Crude Oil as a Power Generation Fuel 115
Burning Equipment 116
Kerosine Burners 116
Domestic Heating Oil Burners 117
Residual Oil Burning Equipment 119
Fuel Oil Classification and Specifications 120
Fuel Oil Laboratory Tests and Their Significance 121
API and Specific Gravity or Density 121
Flash and Fire Point 124
Viscosity 124
Pour Point 126
Cloud Point 126

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Sediment and Water Content 127
Ash Content 127
Carbon Residue 128
Sulfur Content 129
Distillation 129
Corrosion 130
Additional Tests 130
Heat Content 130
Stability 131
Maximum Fluidity Temperature 132
Thermal Stability of U.S. Navy Special Fuel Oil 132
Spot Tests 132
Domestic Heating Oil Performance Evaluation 133
Kerosine Performance Evaluation 133
Selection of Burner 133
Burning Characteristics 134
Initial Flame Height--Smoke Point 134
Constancy of Feed to Wick 134
Formation of Char on Wick 134
Formation of Lamp-Glass Deposits 135
Standard Burning Tests 135
Burning Test for Long-Time Burning Oils 136
Applicable ASTM Specification 136
Applicable ASTM/IP Standards 136
Bibliography 137
Chapter 8---LubricatingOils 138
Introduction 138
Assessment of Quality 138
Physical Tests 139
Chemical Tests 139
Physico-Chemical Tests 139
Laboratory Bench Tests 139
Engine and Rig Tests 139
Significance of Tests 139
Composition and Manufacture 140
General Properties 140
Viscosity 141
Viscosity Index 142
Cloud and Pour Points 143
Flash and Fire Points 144
Relative Density (Specific Gravity) and API Gravity 144
Color 145
Automotive Engine Oils 145
Properties 145
Engine Test Specifications and Procedures 146
Examination of Used Oils 147

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Marine Diesel Engine Oils 148
Industrial and Railway Engine Oils 150
Gas-Turbine Lubricants 150
Gas Engine Oils 153
Gear Oils 154
Automatic Transmission Fluids 156
Steam-Turbine Oils 157
Hydraulic Oils 158
Other Lubricating Oils 159
Air Compressor Oils 159
Refrigerator Compressor Oils 160
Steam Cylinder Oils 160
Machine Tool Tableway Lubricating Oils 160
Applicable ASTM/IP Standards 161
Bibliography 163
Chapter 9---Lubricating Greases 164
Introduction 164
Composition 164
Properties 165
Calcium Soap Greases 165
Sodium Soap Greases 165
Lithium Soap Greases 165
Complex Soap Greases 165
Clay Greases 166
Evaluation of Properties and Significance 166
Consistency 166
Cone Penetration 166
NLGI Grades 167
Shear Stability 167
Prolonged Work Penetration 167
Roll Stability 167
Apparent Viscosity 168
Dropping Point 168
Oxidation Stability 169
Effect of Copper on Oxidation Rate 169
Effect of Grease on Copper 170
Oil Separation 170
Evaporation Loss 171
Rust Prevention 171
Lead in Greases 171
Water Washout 172
Extreme Pressure Timken Test 172
Extreme Pressure Four-Ball Test 172
Wear Preventive Characteristics of Grease 173
Leakage Tendencies of Wheel Bearing Greases 173
Functional Life of Ball Bearing Greases 174

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Low-Temperature Torque 174
Torque Stability, Wear, and Brine Sensitivity of Ball Joint
Greases 175
Greases in Ball Bearings at Elevated Temperatures 175
Greases in Small Bearings 175
Grease Flow Properties at High Temperatures 176
Deleterious Particles in Lubricating Grease 176
Applicable ASTM/IP Standards 177
Bibliography 177
Chapter lO--Petroleum Waxes, Including Petrolatums 179
Introduction 179
Occurrence and Refining of Waxes 179
Definitions 180
Applications for Wax 181
Quality Criteria 181
Criteria for Judging Physical Properties 182
Melting Point 182
Viscosity 182
Hardness 182
Strength of Wax 183
Criteria for Judging Chemical Properties 183
Color 183
Odor 183
Oil Content 184
Solvent Extractables 184
Boiling Point Distribution 185
Molecular Weight 185
Criteria for Food Grade Wax 185
Ultraviolet Absorptivity 186
Carbonizable Substances 186
Peroxide Content 186
Criteria for Judging Functional Properties 186
Wax Content of Substrates 186
Blocking Properties 187
Gloss 187
Slip Properties 187
Abrasion Resistance 187
Adhesion 188
Moisture Barrier Properties 188
Test Methods 188
Physical Properties of Petroleum Wax 189
Melting Point (Cooling Curve) 189
Drop Melting Point 189
Congealing Point 189
Kinematic Viscosity 189
Apparent Viscosity of Petroleum Waxes with Additives 189

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Apparent Viscosity of Hot Melt Adhesives and Coating
Materials 190
Needle Penetration 190
Cone Penetration of Petrolatums 190
Tensile Strength 190
Modulus of Rupture 190
Chemical Properties of Petroleum Wax 190
Saybolt Color 190
ASTM/IP Color 191
Odor 191
Oil Content 191
Solvent Extractables 191
Distillation at Reduced Pressure 191
Boiling Range Distribution by Gas Chromatography 191
Molecular Weight by Vapor Pressure 192
Regulatory Test for Food Grade Wax 192
Ultraviolet Absorbance and Absorptivity 192
Carbonizable Substances 192
Peroxide Number 193
Functional Properties of Petroleum Wax 193
Weight of Surface Wax on Waxed Paper 193
Total Wax Loading of Corrugated Paperboard 193
Blocking Point 193
Pressure Blocking Point 194
20-Degree Specular Gloss of Waxed Paper 194
Gloss Retention 194
Coefficient of Kinetic Friction 194
Abrasion Resistance 194
Sealing Strength 194
Water Vapor Permeability (Normal Atmosphere) 194
Water Vapor Permeability (High Humidity) 196
Inspections of Typical Petroleum Waxes 196
Applicable ASTM/IP Standards 196
Bibliography 197
Chapter ll--White Mineral Oils 198
Introduction 198
Manufacture 198
Purity Guardianship 199
Assessment of Quality 199
Acid Test 201
Aniline Point 201
Cloud Point 201
Color and Transparency 201
Dielectric Breakdown Voltage 202
Distillation Range 202
Flash and Fire Point 202

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Fluorescence 203
Neutrality 203
Odor and Taste 203
Peroxide Value 203
Pour Point 204
Refractive Index 204
Smoke Point 204
Gravity, Density and API Gravity 204
Specific Gravity 204
Density 204
Sulfur Compounds 205
Unsulfonated Residue 205
Ultraviolet Absorption Tests 205
Wax Precipitation Point 206
Applicable ASTM/IP Standards 206
Bibliography 206
Chapter 12--Petroleum Oils for Rubber 208
Introduction 208
Historical Background 208
Natural Rubber 208
Synthetic Rubber 208
Oil Extended Rubber 209
Composition of Rubber Oils 209
Molecular Type Analysis 210
Carbon Type Analysis 210
Importance of Composition to Compounders 211
Classification of Rubber Oils 212
Physical Properties of Rubber Oils 213
Specific Gravity 213
Viscosity 213
Color 213
Ultraviolet Absorptivity 214
Refractive Index 214
Aniline Point 214
Flash Point 214
Evaporation Loss 214
Pour and Cloud Point 214
Specialty Application of Process Oils 215
Applicable ASTM/IP Standards 215
References 216

Introduction

Preparing a reliable reference guide on the significance of tests for petroleum

and petroleum products is no simple matter. Test methods define product
quality. Quality, in tum, can be defined as the "fitness" of the material for its
intended use. The history of petroleum is a story of a wide array of end products
with continually changing quality criteria.
For those interested in product quality and its assessment, this means the
situation is never static. There are no frozen standards in the petroleum and
natural gas industries. Many well-established test procedures, which at one time
may have afforded an adequate quality assessment of raw materials or end prod-
ucts or both, have become obsolete and produce results of limited significance.
A number of these old time testing procedures have been replaced by radically
different tests and analytical procedures that provide more accurate and
meaningful appraisal of the qualities of materials. Other prospective new
methods are being examined or under development.
The ultimate adoption of any of these new testing or evaluation methods will
not constitute a "final chapter" on the subject of quality criteria and assessment.
The state of the art is in a continual state of flux. The need for still another
chapter is always "just around the comer."

1
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STP7C-EB/Jan. 1977

Chapter 1--Crude Oils

Introduction
While crude oil occurs underground in most of the world, its origin continues
to be the subject of speculation by scientists. Crude oils are organic in nature
and made up of combinations of carbon and hydrogen with lesser amounts of
sulfur, nitrogen, oxygen, and traces of vanadium, nickel, and other metals. The
compounds of carbon and hydrogen are complex but are principally paraffinic,
naphthenic, and aromatic. Any given crude oil consists of thousands of
compounds, its complexity increasing with the boiling range of the oil.
There is no overall or generally accepted method of classifying crude oils.
What is termed an ultimate analysis gives the composition as a percentage of the
principal elements-carbon, hydrogen, nitrogen, oxygen, and sulfur. A chemical
analysis gives the composition in percentages of paraffinic, naphthenic, and
aromatic type compounds. These types of analyses are valuable in formulating a
general idea of the usefulness of the crude in producing various refinery
products, but the analyses give little indication of the quantity of the various
products that can be produced. To obtain this information, additional evaluation
is necessary.

Sampling
Since many of the properties of crude oils change with change in temperature
and pressure or lengthy exposure to atmospheric environment, proper sampling
is very important. If the dissolved light hydrocarbons such as methane, ethane,
propane, and butane are permitted to escape by exposure to the atmosphere,
qualities such as gravity, vapor pressure, octane number, and distillation tests
will change. The basic principle of sampling is to obtain a sample or a composite
of several samples in such a manner and from such locations in the oil field
separator, storage tank, pipeline, or other container that the sample will be truly
representative of the crude oil or product.
Sample containers must be of a material that will not react with any
component of the crude oil; for example, hydrogen sulfide will react with
ordinary steel containers. Sampling may be individual or continuous, and
different sampling procedures are sometimes required for different laboratory
tests.
Problems of sampling and procedural requirements are presented in ASTM
Sampling Petroleum and Petroleum Products (D 270).

3
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4 SIGNIFICANCE OF TESTS

Preliminary Evaluation or Assay

The preliminary crude oil assay provides general data on the oil and is based
upon a number of standard tests. The tests consist primarily of a fractional
distillation of the oil, a hydrocarbon analysis showing the volume percent of
components lighter than hexane, and a series of tests used by the refiner to
determine how the crude will yield the desired products from a given operation.
Some of the more important tests are used to determine gravity, sulfur content,
salt content, water and sediment, viscosity, pour point, and metallic contami-
nants. These tests, and fractional distillation, hydrocarbon analysis, and
characterization factors, will be discussed briefly, and test method references
will be furnished. (Table 1 presents preliminary evaluations on four typical crude
oils from the United States, Venezuela, Nigeria, and Canada.)

Gravity
The American Petroleum Institute (API) gravity of a crude enters into most
pricing structures, and it is used for the correction of temperature and volume in
bulk oil measurement. The test for API gravity is a simple hydrometer method
which is described in ASTM Test for API Gravity of Crude Petroleum and
Petroleum Products (Hydrometer Method) (D 287).

Sulfur, Hydrogen Sulfide, and Mercaptan Sulfur

The sulfur content of crude oil is an important quality because the complexity
and expense of the refining operation increase tremendously as the sulfur
content of the crude increases. Sulfur content varies from practically nothing to
as high as several percent in some crudes.
Hydrogen sulfide is evolved during the distillation process. Generally, the
other sulfur compounds concentrate in the heavier distillation residue. Residual
fuel oils containing more than very small amounts of sulfur are subjected to
severe price penalties at the marketplace. In addition, they are often barred as
fuel by federal, state, or local environmental laws.
Sulfur in crude oils is usually determined by oxidizing a sample in a bomb and
converting the sulfur compounds to barium sulfate which is determined
gravimetrically, as described in ASTM Test for Sulfur in Petroleum Products
(General Bomb Method) (D 129/IP 61).
Hydrogen sulfide and mercaptan sulfur can be estimated by several methods.
Refineries choose the one best suited to their situation. One estimation of
hydrogen sulfide can be made by distilling out the dissolved gas, absorbing it in a
suitable chemical solution, and analyzing the solution. A more frequently used
method for determining hydrogen sulfide and mercaptan sulfur is by a
potentiometric titration in which silver sulfide and silver mercaptides are
determined in a nonaqueous solution.

TABLE 1-Preliminary evaluation of typical crude oils.

Texas Gulf Venezuela Nigerian Canada

Coast Mix (Lagomar) (Bonney) (Redwater)

PROPERTIES
Gravity (API at 60~ 36.5 30.7 38.1 34.9
Paraffin wax, weight % 1.84
Sulfur, weight % 0.16 1.48 0.14 0.56
Salt, lb/1000 bbl 7.0 /---.2.0 <2.0 3.0
Viscosity, SUS at 77OF 41.0 107.0 38.4 47.8
Viscosity, SUS at 100OF 37.3 64.3 35.7 41.7
Characterization factor
(midboiling point) 11.76 11.95 11.90 11.89
Flash point, ~ <40.0 <40.0 <40.0 <40.0
Pour point, OF 5.0 10.0 - 35.0 10.0
Water and sediment, volume % 0.1 trace trace trace
Color 2820 30160 2950 19340
Reid vapor pressure at 100OF 3.2 2.5 6.9 8.4
Total acid number
(Neutral Number) 0.56 0.11 0.24 0.23
Hydrogen sulfide, lb/1000 bbl <0.5 0.8 0.0009 87.2
Mercaptans, lb/1000 bbl <0.5 0.3 <0.0001 16.1
Iron, ppm 8.0 10.0 7.0 5.0
Nickel, ppm 0.9 17.0 5.0 12.0
Vanadium, ppm 0.7 175.0 0.3 3.0
Copper 0 0 0 0
DISTILLATION
Initial boiling point, OF ~50 <50 <5O <50
5% 196 203 178 155
10% 245 269 220 230
20% 322 369 289 299
30% 398 422 375 382
40% 461 566 450 477
50% 513 677 518 573
60% 572 788 592 680
70% 654 907 684 792
80% 759 1047 780 892
90% 884 9 897 1032
95% 1000 994
End point, ~ 1033 1()83 1045 lO5O
Recovery, % 96 84 96 92
Residue, % 4 16 4 8
Loss 0 0 0 0
LIGHT HYDROCARBON ANALYSIS VOLUME %
Ethane 0.04 0.07 0.11 0.16
Propane 0.28 0.38 0.95 1.13
I-butane 0.32 0.24 0.92 0.68
Butane 0.71 0.91 1.96 2.23
I-pentane 0.91 0.74 1.69 1.65
Pentane 0.97 1.29 1.57 1.93
2-methyl pentane 0.82 0.77 1.02 1.18
3-methyl pentane 0.40 0.37 0.53 0.75
Hexane and heavier 95.55 95.23 91.25 90.28

Salt Content
The salt content of crudes varies over a rather wide range, which results
principally from two factors-production practices in the oil fields and the
handling of the crude in tankers bringing it to the refinery. Even a very small salt
content is critical to refinery operations because of the constant accumulation of
salt in key units of the refinery such as stills, heaters, and exchangers. In
addition to caking up this equipment, certain metallic salts break down and
liberate corrosive acids during the processing operation.
A widely employed test for inorganic chlorides is by potentiometric titration
in a nonaqueous solution as described in ASTM Test for Salt in Crude Oil
(Electrometric Method) (D 3230). Refiners normally use adaptations of this
type of test. Settling, heating, chemical treating, and mixing with water all
reduce salt content. In stubborn cases, a high potential electric field across the
settling vessel is helpful.

Water and Sediment

In refining operations, the presence of water and sediment leads to major
difficulties such as corrosion, uneven heating and plugging in heaters and
exchangers, and adverse effects on product quality.
Sediment normally exists in crude oils as extremely fine, well-dispersed solids.
Solids that originate in the reservoir from which the crude came, or in drilling
fluids used to drill the wells, may take the form of sand, clay, shale, or rock
particles. Other sediments such as scale can be picked up from tubing, pipe,
tanks, and other production and transportation equipment. Water may appear in
the crude as droplets or as emulsion and can contain chemical salts and other
harmful substances.
Methods used for the determination of water and sediment in the oil fields
differ from those used in the refinery for a number of practical and economic
reasons. The field operator selects one of three centrifugal test methods best
suited to the crude oil and the particular operating situation. Usually waxy crude
samples are heated. An aromatic solvent such as toluene is used with asphaltic
crudes, and other samples are treated with emulsifiers. In the refinery, the water
is measured by distillation and the sediment by extraction. These procedures are
described in ASTM Tests for Water and Sediment in Crude Oils (D 96), ASTM
Test for Water in Petroleum Products and Bituminous Materials by Distillation
(D 95/IP 74), and ASTM Test for Sediment in Crude and Fuel Oils by
Extraction (D 473/IP 53).

Viscosity and Pour Point

Although the viscosity and viscosity variation with change in temperature are
important for establishing performance standards of lubricating oils, viscosity

determinations on crude oils are used principally in the design of field gathering
systems and the lines and pumps between refinery storage and the processing
facility. In these systems, viscosity and pour-point determinations provide the
keys for solving transportation problems associated with crude oils.
Viscosity is determined at two different temperatures-25~ (77~ 100~
(212~ The procedure for determining kinematic viscosity is preferred today.
However, the results of the test are often converted to Saybolt units for
reporting purposes. The kinematic viscosity is determined by measuring the time
for the liquid to flow under gravity through a glass viscometer, and it is
described in ASTM Determination of Kinematic Viscosity of Transparent and
Opaque Liquids (and the Calculation of Dynamic Viscosity) (D 445/IP 71).
Tables for converting to Saybolt units appear in ASTM Conversion of Kinematic
Viscosity to Saybolt Universal Viscosity or to Saybolt Furol Viscosity (D 2161).

Metallic Contaminants
Metallic trace components such as iron, sodium, nickel, vanadium, lead, and
arsenic have an adverse effect on refining or processing operations. These
materials are catalyst poisons, and some of them do additional harm. For
example, vanadium compounds damage turbine blades and refractory furnaces.
Sodium can cause problems in furnace brickwork.
Since numerous laboratory techniques are available to analyze a crude oil for
metallic contaminants, the one used is a matter of individual preference.
However, one such procedure is described in ASTM Test for Trace Metals in Gas
Turbine Fuels (Atomic Absorption Method) (D 2788).

Distillation
In the preliminary assay of crude oils, a distillation is performed under poor
conditions of fractionation. Temperatures of the distilled vapor are recorded at
initial boiling points and at the following volume percentage fractions of the
charge in the receiver: 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 95, and at the end
point. Crudes will crack at temperatures above 260 to 316~ (500 to 600~ as
evidenced by an increase in the distilling rate while the vapor temperature
stabilizes and the appearances of smokey vapor. For this reason, many assay
laboratories interrupt the distillation at a temperature around 232~ (450~ and
then reduce the pressure to 1 mm Hg. This permits the distillation to continue at
reduced temperatures right up to the end point with no danger of cracking. The
temperature readings are converted from actual temperatures at 1 mm pressure
to the corresponding temperatures at atmospheric pressure.
Apparatus and procedure for this type distillation are described in ASTM Test
for Distillation of Petroleum Products at Reduced Pressure (D 1160). If desired,
this procedure can be easily modified by starting the distillation at atmospheric
pressure and finishing under vacuum.

Light Hydrocarbon Analysis

Most crude oil assays and all comprehensive or full examinations include an
analysis of the light hydrocarbons dissolved in the oil, usually ethane through
pentane or sometimes hexane. The apparatus used is referred to frequently as a
gas liquid partition chromatograph. Any chromatograph having a thermostated
oven and detection system of proper sensitivity is satisfactory. A description of
the test is found in ASTM Determination of C2 through Cs Hydrocarbons in
Gasolines by Gas Chromatography (D 2427).

Characterization Factor
A tool used by refiners to correlate some of the important characteristics of
crude oil is an empirical relationship generally referred to as the Characterization
Factor. There are variations or modifications of the original concept developed
by Watson, Nelson, and Murphy ~ but basically it follows

K= rB
-3--
where
TB = Molal average boiling point in Rankine temperature, and
S = specific gravity at 60*F.

Full or Comprehensive Evaluation

The tests utilized in making a preliminary assay are relatively simple. The
results give a useful and general picture of the quality of the oil, but they do not
provide sufficient data for an economic evaluation or adequate knowledge of the
quality and quantity of the products the crude can yield. A more comprehensive
evaluation is required to supply this information, and each refiner tailors the full
assay to meet his particular needs-good lube stock, maximum motor fuel
production, jet and diesel fuels, etc. The evaluation starts with a true boiling
point distillation. Simply stated, this is a distillation of the crude oil under good
fractionating conditions. The equipment consists of a kettle, heater, packed
fractionating column, condenser, receiver, temperature recorders, and the
necessary vacuum pump and control apparatus to permit the later stages of the
distillation to be conducted under vacuum. Sometimes a secondary condenser,
using a solid carbon dioxide and acetone or other suitable liquid coolant, will be
added for recovering the lighter boiling fractions such as propane and butanes.
This also can include apparatus for recovering and measuring the amount of
vented hydrogen sulfide gas by an agent such as acidified cadmium chloride
solution.

t Watson. Nelson, and Murphy, Industrial Engineering Chemistry, Vol. 27, 1935, p. 1460.

Samples of overhead distillate between desired temperature intervals are

removed from the distillate receiver, measured or weighed, and then analyzed
individually or in blends to appraise their value as motor fuel, fuel oil, reformer
charge, etc. The true boiling point curve is plotted showing volume percent
distilled versus temperature. Figure 1 is such a curve for a typical crude oil.
Looking at Fig. 1, it can be seen that liquefied petroleum gas, constituting 1.6
percent of the sample, distills at temperatures below 15.6~ (60~ gasoline
distills at temperatures up to 232~ (540~ kerosine and jet fuels up to 2880C
(550~ distillate and diesel fuels are in the 232 to 3710C (450 to 700~ range
and so on until residual fuel oil and asphalt comprise the residue at temperatures
above 482~ (9000F). The procedure for conducting a true boiling point
distillation is described in ASTM Distillation of Crude Petroleum (15 Theoretical
Plate Column) (D 2892).
A few of the principal properties taken from a comprehensive evaluation of a
Louisiana-Mississippi crude oil mix are shown in Table 2. Space does not permit
inclusion of all the various test results on individual distillate cuts necessary to
evaluate them for lube stock, reformer chalge, solvent refining potential, motor
fuel, and others.

Crude Oil as a Power Generation Fuel

The use of crude oil as a power generation fuel recently has received
considerable attention. The factors that have promoted this use are fuel
availability, cost, and environmental aspects. The energy shortage has prompted
electric utilities to resort to the burning of crude oil under the boilers of power
stations and to use crude oil as the fuel for gas-turbine operations of standby
generators.
The specifications for crude oils for this purpose have not been established,
but there are known critical factors that must be considered. Since crude oils
normally have relatively low-flash points, their use has associated fire hazards
and explosive aspects. This fact necessitates the use of proper storage and
handling facilities. These facilities must be explosion proof, vapor proof, and
vapor retaining. Furthermore, the crude oil must be fluid or pumpable, and it
must have low ash and sulfur contents to meet emission standards that satisfy
environmental regulations. If these properties are not prevalent in the crude oil,
sulfur dioxide and fly ash scrubbing or removal equipment must be provided to
assure compliance.
Crude oils used as gas-turbine fuel also must have very low-metallic contents to
ensure adequate turbine blade performance and comply with the manufacturer's
requirements.
Standard tests for burner fuels described elsewhere in this book are also
applied to crude oils destined for use as power generation fuels.

1200

1100

1000

900

000
DISTILLATION AT DISTILLATION
ATMOSPHERIC PRESSURE UNDER VACUUM

700 RESIDUALS
-j
I-
<
nq
ud
G.
600

LUBE STOCK
500

400 DISTILLATE AND

DIESEL FUELS

300

200 KEROSENE[
I
GASOLINES AND I
JET FUELSI

100
LIQUEFIED PETROLEUM GAS

0 " " '

0 't0 20 30 40 S0 60 70 00 90 100
VOLUME PERCENT OF CRUDE OIL DISTILLED
FIG. 1 - T r u e boiling point distillation curve Louisiana-Mississippi crude mix.

TABLE 2-Portions of a comprehensive evaluation of crude oil

Louisiana-Mississippi crude oil mix.

PROPERTIES
Gravity, API at 60~ 38.3
Specific gravity, 60OF 0.8333
Paraffin wax, weight % 4.71
Sulfur, weight % 0.10
Salt, lb/1000 bbl 15.0
Viscosity, SUS at 77OF 47.2
Viscosity, SUS at 100OF 40.4
Characterization factor (midboiling point) 12.09
Flash point, OF 39.0
Pour point, ~ 5.0
Water and sediment, volume % 0.04
Color 5220.0
Reid vapor pressure at 100OF 3.2
Total acid number (neutral number) 0.18
Hydrogen sulfide lb] 1000 bbl 0.4
Mercaptans, lb/1000 bbl 0.4

DISTILLATION
Initial boiling point, ~ 49.0
5% 149.0
10% 208.0
20% 298.0
30% 397.0
40% 484.0
50% 562.0
60% 648.0
70% 749.0
80% 860.0
90% 992.0
95%
End point 1070J0
Residue 6.0
Loss 0

LIGHT HYDROCARBON ANALYSIS VOLUME %

Ethane 0.02
Propane 0.34
I-butane 0.42
Butane 0.84
I-pentane 1.21
Pentane 1.15
2-methyl pentane 1.13
3-methyl pentane 0.57
Hexane and heavier 94.32

TABLE 2-Portions o f a comprehensive evaluation of crude oil

Louisiana-Mississippi crude oil mix.
(Continued.)
PRODUCT EVALUATION
Butanes and lighter, volume % 1.6
Debutanized straight run gasoline, volume % 3.2
Octane number clear (BON) 75.3
Motor reformer charge, volume % 11.3
Fresh heavy naphtha, volume % 7.8
Heavy gas oil, volume % 47.7
Vacuum tower distillate, volume % 7.2
Vacuum tower bottoms, volume % 9.5
Potential benzene 0.44
Potential toluene 2.00
Potential xylene 1.24

ApplicableASTM/IPStandards
ASTM IP Title
D 95 74 Water in Petroleum Products and Bituminous
Materials by Distillation
D 96 Water and Sediment in Crude Oils
D 129 61 Sulfur in Petroleum Products by the Bomb Method
D 270 Sampling Petroleum and Petroleum Products
D 287 API Gravity of Crude Petroleum and Petroleum
Products (Hydrometer Method)
D 323 Vapor Pressure of Petroleum Products (Reid Method)
D 445 71 Kinematic Viscosity of Transparent and Opaque
Liquids (and the Calculation of Dynamic
Viscosity)
D 473 53 Sediment in Crude and Fuel Oils by Extraction
D 1160 Distillation of Petroleum Products at Reduced
Pressure
D 2161 Conversion of Kinematic Viscosity to Saybolt
Universal Viscosity or to Saybolt Furol
Viscosity
D 2427 Determination of C2 through Cs Hydrocarbons in
Gasolines by Gas Chromatography
D 2788 Trace Metal in Gas Turbine Fuels (Atomic
Absorption Method)
D 2892 Distillation of Crude Petroleum (15 Theoretical
Plate Column)

Bibfiography
The Bureau o f Mines Routine Method for the Analysis of Petroleum, U.S. Bureau of Mines
Bulletin 490.
Manual on Hydrocarbon Analysis, ASTM STP 332, American Society for Testing and
Materials, first edition 1933.
Moody, G. B., "Origin, Migration, and Occurence of Petroleum," Petroleum Exploration
Handbook, McGraw-Hill, New York, Chapter 5.
Nelson, W. L., Petroleum Refinery Engineering, 4th ed., McGraw-Hill, New York, 1958.
"Properties of Crude Oils and Liquid Condensate," Petroleum Production Handbook, T.
C. Frick, Ed., Vol. II, McGraw-Hill, New York, Chapter 18.
Symposium on Hydrocarbon Analysis, ASTM STP 389, American Society for Testing and
Materials, 1965.

Chapter 2 Gaseous Fuels and Light

Hydrocarbons

Introduction

Natural Gas
The primary use for natural gas is as a fuel for the production of heat. Large
quantities are used also as the source of hydrogen in the production of ammonia.
Natural gas is a mixture of hydrocarbon and nonhydrocarbon gases found in
porous formations beneath the earth's surface, often in association with crude
petroleum. The principal constituent of most natural gases is methane with
minor amounts of heavier hydrocarbons and certain nonhydrocarbon gases such
as nitrogen, carbon dioxide, hydrogen sulfide, and helium. Raw natural gas may
be subclassified as follows:
Nonassociated Gas-Free gas not in contact with significant amounts of crude
oil in the reservoir.
Associated Gas-Free gas in contact with crude oil in the reservoir.
Dissolved Gas-Gas in solution with crude oil in the reservoir.
Following processing and conditioning into a merchantable or t~mished
product, natural gas is composed primarily of methane (CH4) and ethane
(C~H6).

Natural Gas Liquids (NGL )

Natural gas liquids (NGL) are mixtures of hydrocarbons which are extracted in
liquid form from raw natural gas in lease separators, field facilities, or gas
processing plants. A significant component of natural gas liquids is condensate.
Condensate is similar in characteristics and application to a very light crude oil.
Natural gas liquids may be produced as a "raw mix" or unfractionated stream,
fractionated into individual components, or fractionated into various commer-
cial mixtures including liquefied petroleum gas (LP gas) and natural gasoline.
The individual components and commercial products which may be fraction-
ated from natural gas liquids include:
Ethane-A normally gaseous paraffinic compound (C2H6) having a boiling
point of approximately - 88~ (- 127~ Ethane may be handled as a liquid at
very high pressures and at temperatures below 90~
Virtually all ethane produced as a separate liquid product are used as a
feedstock for the production of ethylene-a basic petrochemical whose
applications are covered more fully in the section on olefins and diolefins.

14
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CHAPTER 2 ON GASEOUS FUELS AND LIGHT HYDROCARBONS 15

Propane-A normally gaseous paraffinic hydrocarbon (Ca Hs) having a boiling

point of approximately - 42~ (- 44~ It may be handled as a liquid at ambient
temperatures and moderate pressures. Commercial propanes may include varying
amounts of ethane, butanes, and liquefied refinery gases.
Butane-A normally gaseous paraffinic hydrocarbon (C4HI o) which is handled
usually as a liquid at ambient temperatures and moderate pressures. Butane may
be fractionated further into normal butane, which has a boiling point of
approximately 0~ (32"F), and isobutane, which has a boiling point of
approximately 1 I*F.
Liquefied Petroleum Gas (LP Gas)-A mixture of hydrocarbons, principally
propane and butanes obtained from either natural gas liquids or refinery gases,
which can be stored and handled as liquids at ambient temperatures and
moderate pressures. Commercial LP gas also may contain small quantifies of
ethane and varying quantities of propylene or butylene or both from refinery
gases.
The original use for liquefied petroleum gas was as a fuel gas in areas where
pipeline utility gas was not available. Later, these materials were fractionated
into their separate components, principally propane and butane, as preferred
feedstocks for the petrochemical industry.
Natural Gasoline-A mixture of hydrocarbons (extracted from natural gas)
that consists mostly of pentanes and hydrocarbons which are heavier than
pentane.
In the beginning of the natural gasoline industry, the only use for natural
gasoline was as motor fuel or as a blending agent in the production of motor
fuel. Later, the individual components of natural gasoline, namely isobutanes,
butanes, pentanes, and isopentanes, were separated as base stocks for reforming,
alkylation, synthetic rubber, and other petrochemicals.

Liquefied Refinery Gas (LR Gas]

Liquefied refinery gases are mixtures of hydrocarbons which are recovered
during the refining of crude oil. These materials are composed principally of
propane, butanes, propylene, and butylenes, and they can be stored and handled
at ambient temperatures and at moderate pressures.

Olefins and Diolefins

Many light olefins and diolefins which are produced in the refinery are isolated
for petrochemical use. The individual products are:
Ethylene-A normally gaseous olefinic compound (C2H4) having a boiling
point of approximately - 104"(3 (- 155"F). It may be handled as a liquid at very
high pressures and low temperatures. Ethylene is made normally by cracking an
ethane or naptha feedstock in a high-temperature furnace and subsequent
isolation from other components by distillation.
The major uses of ethylene are in the production of ethylene oxide, ethylene

dichloride, and the polyethylenes. Other uses include the coloring of fruit, EP
rubbers, ethyl alcohol, and medicine (anesthetic).
Propylene Concentrates-A mixture of propylene and other hydrocarbons,
principally propane and trace quantities of ethylene, butylenes, and butanes.
Propylene concentrates may vary in propylene content from 70 percent tool up
to over 95 percent mol and may be handled as a liquid at normal temperatures
and moderate pressures. Propylene concentrates are isolated from the furnace
products mentioned in the preceding paragraph on ethylene. Higher purity
propylene streams are further purified by distillation and extractive techniques.
Propylene concentrates are used in the production of propylene oxide, isopropyl
alcohol, polypropylene, and the synthesis of isoprene.
Butylene Concentrates-These are mixtures of butene-1, cis- and trans-
butene-2, and, sometimes, isobutene (2-methyl propene) (C4Ha). These prod-
ucts are stored as liquids at ambient temperatures and moderate pressures.
Various impurities such as butane, butadiene, and Cs's generally are found in
butylene concentrates.
Virtually all of the butylene concentrates are used as a feedstock for either:
(1) an alkylation plant, where isobutane and butylenes are reacted in the
presence of either sulfuric acid or hydrofluoric acid to form a mixture of CT to
C9 paraffins used in gasoline, or (2) butylene dehydrogenation reactors at
butadiene production facilities.
Butadiene-A normally gaseous hydrocarbon (C, H~) having a boiling point of
24.1~ It may be handled as a liquid at moderate pressure. Ambient
temperatures are generally used for long-term storage due to the easy formation
of butadiene dimer (4-vinyl cyclohexene-1). Butadiene is produced by two major
methods: the catalytic dehydrogenation of butane or butylenes or both, and as a
by-product from the production of ethylene. In either case, the butadiene must
be isolated from other components by extractive distillation techniques and
subsequent purification to polymerization-grade specifications by fractional
distillation.
The largest end use of butadiene is as a monomer for production of GR-S
synthetic rubber. Butadiene is also chlorinated to form 2-chioro butadiene
(chloroprene) used to produce the polychloroprene rubber known as neoprene.

Quality Criteria
Quality of a product may be defined as its fitness for a purpose. Once the
required quality is determined, it is controlled by appropriate testing and
analysis. This section will outline quality criteria for significant gaseous fuels and
light hydrocarbons. Appropriate American Society for Testing and Materials and
Institute of Petroleum (ASTM/IP) methods for testing and analysis will be listed
in parenthesis. The full titles of the methods can be found at the end of the
chapter under the heading, "Applicable ASTM/IP Standards."

Natural Gas
The principal quality criterion of natural gas is its heating value (ASTM D 900
or ASTM D 1826). In addition, the gas must be readily transportable through
high-pressure pipelines. Therefore, the water content, as defined by the water
dew point (ASTM D i 142), must be considered to prevent the formation of ice
or hydrates in the pipeline. Likewise, the amount of entrained hydrocarbons
heavier than ethane, as defined by the hydrocarbon dew point, should be
considered to prevent accumulation of condensible liquids that may block the
pipeline.
Natural gas and its products of combustion must not be unduly corrosive to
the materials with which they come in contact. Thus, the detection and
measurement of hydrogen sulfide (ASTM D 2385 or ASTM D 2725) and total
sulfur (ASTM D 1072 or ASTM D 3031) are important. The odor of gas must
not be objectionable; so, in some cases, mercaptan content (ASTM D 2385) is
significant.
If the gas is to be liquefied by cryogenic processing and stored in liquid form,
carbon dioxide will separate out of the cold liquid as a solid and interfere with
the refrigeration system. Carbon dioxide can be determined by ASTM D 1137 or
ASTM D 1945. If the gas is to be used as a feedstock for the production of
hydrogen or petrochemicals, a complete analysis (ASTM D 1137 or ASTM D
1945) must be made, because some gases contain materials that are deleterious
to these processes.

Ethane
Quality criteria for ethane as a petrochemical feedstock are specific to the
particular process used for petrochemical manufacture. In general, however, such
feedstocks must be very low in moisture content (ASTM D 1142), oxygen
(ASTM D 1136, ASTM D 1137 or ASTM D 1945), carbon dioxide (ASTM D
1137 or ASTM D 1945), sulfur compounds (ASTM D 1072), and other elements
that will interfere with the process or the catalysts used in petrochemical
manufacture.

Liquefied Petroleum (LP) Gases

For most purposes, liquefied petroleum gas will be stored, handled, and
transported as a liquid and used as a gas. In order to handle, store, and transport
it safely, the vapor pressure must be known (ASTM D 1267). To be sure that LP
gas will convert from liquid to vapor under the intended conditions of use, it is
necessary to know something about its volatility (ASTM D 1837). Vapor
pressure is an indicator of volatility, but it gives little or no indication of the
least Volatile components. For this purpose, the results of a weathering test
(ASTM D 2158) are needed. The combination of vapor pressure and the results
of a weathering test is a good measure of volatility and, therefore, a good
indicator of the suitability of LP gas for its intended use.

Copper tubing is used extensively in LP gas systems. As a result, a copper strip

corrosion test (ASTM D 1838) is important. Propane vaporizes at temperatures
far below the freezing point of water. Therefore, it is important to know that
the moisture content of propane (ASTM D 2713) is low enough so that it will
not cause freeze-up problems.
Since regulations covering proper fdling of LP gas containers are based upon
the specific gravity of the liquid, the exact specific gravity of each batch of LP
gas must be known (ASTM D 1657).
As with other fuel gases, the products of combustion should not be
unnecessarily corrosive. The common source of corrosive combustion products
from LP gas is the sulfur compounds contained in it. Total sulfur content
(ASTM D 2784) is a measure of the corrosivity of the combustion product.
When LP gas is vaporized, it is undesirable to leave behind nonvolatile
materials that can plug up equipment or cause controls to operate improperly.
The residue test (ASTM D 2158) is an indicator of the nonvolatile materials
present in LP gas.
When LP gas is intended for use as a petrochemical feedstock, a component
analysis is essential. The best and quickest way to analyze such a material is by
means of a gas chromatograph (ASTM D 2888 or ASTM D 2163/IP 264). This
instrument is such a quick, reliable, and accurate tool that it is being used more
and more to replace many of the older physical tests, when the composition of
an LP gas is known, it is possible to calculate many of its other properties
(ASTM D 2598).
Octane number is an important characteristic of LP gas used as engine fuel
(ASTM D 1835). Octane number can be determined by the test for knock
characteristics (ASTM D 2623[IP 238), or it can be calculated after a
chromatographic analysis has been made (ASTM D 2598).

Natural Gasoline
For use as motor fuel or as a component of motor fuel, the primary criteria
for the quality of natural gasoline are its volatility and knock performance. The
basic measures of volatility are vapor pressure (ASTM D 323) and distillation
(ASTM D 216/IP 191). Knock performance is measured by rating in knock test
engines by both the motor (ASTM D 2700/IP 236) and research (ASTM D
2699/IP 237) methods.
Other considerations for natural gasoline used in motor fuels are copper
corrosion (ASTM D 130/IP 154) and gravity (ASTM D 1298/IP 160). Although
gravity has a minor direct relationship with quality, it is necessary to determine
gravity for measurement and shipping.
When natural gasoline is used as a feedstock for further processing or
petrochemicals, the list of quality criteria is almost endless. For nearly all
petrochemical uses composition by hydrocarbon types is needed, and, fre-
quently, a complete analysis of specific components is made (ASTM D 2427). If

a catalytic process is involved, total sulfur (ASTM D 1266/IP 191) is very

important, because sulfur tends to destroy catalyst activity.

Olefins and Diolefins

Ethylene-Since ethylene is a high-purity product (normally supplied at 99.5
percent mol or higher), the quality criteria of interest are trace components.
Those components of greatest concentrations are hydrogen, carbon monoxide,
carbon dioxide, oxygen, and acetylene. Generally, moisture and sulfur contents
also are quite critical to ethylene-based processes. All of the above impurities are
generally catalyst poisons to polymerization processes even in the low mols per
million concentration ranges. Therefore, the analytical problems are magnified
greatly. To date, ASTM does not have a standard method for moisture at these
low levels, but a new trace sulfur method, based on microcoulometry, has been
adopted (ASTM D 3246). Ethylene purity is determined by quantitative analysis
of the trace impurities and subtracting the sum of their concentrations from 100
percent (ASTM D 2504 and ASTM D 2505).
Propylene Concentrates-Propylene concentrate streams generally require a
component analysis, depending upon their final use. The best method is by gas
chromatography (ASTM D 2427). Another gas chromatography method is used
to identify major impurities (ASTM D 2163/IP 264). Sulfur may be determined
by the oxidative microcoulometric technique (ASTM D 3246) just mentioned
or, more commonly, by the Wickbold combustion method (ASTM D 2784). As
is the case for ethylene, moisture in propylene is critical. Several field tests and
a few laboratory tests are in use by individual firms, but no standard method for
moisture has been adopted to date. The problems in sampling for moisture
content, especially in the less than 10 ppm range, are hard to overcome, but
efforts are underway in ASTM to standardize a method.
The trace impurities in 90 percent or better propylene, which is used in
polymerization processes, become quite critical. Hydrogen, oxygen, and carbon
monoxide are determined by one technique (ASTM D 2504), and acetylene,
ethylene, butenes, butadiene, methyl acetylene, and propadiene are determined
by using a very sensitive analytical method (ASTM D 2712).
Butylene Concentrates-The major quality criterion for butylene concentrates
is the distribution of butylenes which is measured, along with other components,
by gas chromatography (ASTM D 1717). Trace impurities generally checked are
sulfur (ASTM D 2784), chlorides (ASTM D 2384), and acetylenes (ASTM D
1020). These impurities are sometimes catalyst poisons or become unwanted
impurities or both in the final product. When butylene concentrates are used as
an alkylation unit feedstock, the diolefm content becomes important.
Butadiene-The major quality criteria for butadiene are the various impurities
that may affect the polymerization reactions for which butadiene is used. The
gas chromatographic examination (ASTM D 2593/IP 194) of butadiene
determines the gross purity as well as Ca, C4, and C5 impurities. Most of these

hydrocarbons are innocuous to polymerizations, but, some, such as butadiene

- 1,2 and pentadiene - 1,4, are capable of polymer cross-linking.
Acetylenes are determined by using a chemical test method (ASTM D 1020),
but a new gas chromatographic method for acetylenes is under investigation in
ASTM. Butadiene dimer is identified by gas chromatography (ASTM D 2426),
while carbonyls are determined by the classical hydroxylamine hydrochloride
reaction with carbonyls (ASTM D 1089). Total residue is determined to check
for nonvolatile matter (ASTM D 1025). Peroxide level is measured by using
ASTM Method D 1022.
ASTM D 1550, ASTM Butadiene Measurement Tables, provides the data
necessary for proper calculation of commercial quantities of butadiene.

Applicable ASTM Specification

D 1835 Specifications for Liquefied Petroleum (LP)Gases

Applicable ASTM/IP Standards

ASTM IP Title
NATURAL GAS AND ETHANE
D 900 Calorific Value of Gaseous Fuels by the
Water-flow Calorimeter
D 1070 Specific Gravity of Gaseous Fuels
D 1072 Total Sulfur in Fuel Gases
D 1136 Analysis of Natural Gases by the Volumetric-
Chemical Method
D 1137 Analysis of Natural Gases and Related Types of
Gaseous Mixtures by the Mass Spectrometer
D 1142 Water Vapor Content of Gaseous Fuels by
Measurement of Dew-Point Temperature
D 1145 Sampling Natural Gas
D 1826 Calorific Value of Gases in Natural Gas Range
by Continuous Recording Colorimeter
D 1945 Analysis of Natural Gas by Gas Chromatography
D 2385 Hydrogen Sulfide and Mercaptan Sulfur
in Natural Gas (Cadmium-Sulfate
Iodometric Titration Method)
D 2725 Hydrogen Sulfide in Natural Gas (Methylene
Blue Method)
D 3031 Total Sulfur in Natural Gas by Hydrogenation
LIQUEFIED PETROLEUM GAS
D 1265 Sampling Liquefied Petroleum (LP) Gases

D 1267 Vapor Pressure of Liquefied Petroleum

(LP) Gases (LP-Gas Method)
D 1657 Specific Gravity of Light Hydrocarbons by
Pressure Hydrometer
D 1837 Volatility of Liquefied (LP) Gases
D 1838 Copper Strip Corrosion by Liquefied Petroleum
(LP Gases)
D 2158 Residues in Liquefied Petroleum (LP) Gases
D 2163 264 Analysis of Liquefied Petroleum (LP) Gases
and Propylene Concentrate by Gas
Chromatography
D 2598 Calculation of Certain Physical PrOperties of
Liquefied Petroleum (LP) Gases from
Compositional Analysis
D 2623 238 Knock Characteristics of Liquefied Petroleum Gases
by the Motor (LP) Method
D 2713 Dryness of Propane (Valve Freeze Method)
D 2784 Sulfur in Liquefied Petroleum Gases
(Oxy-Hydrogen Burner or Lamp)
D 2888 Analysis of Liquefied Petroleum Gases (LPG)
by Process Gas Chromotography
NATURAL GASOLINE
D 130 154 Copper Corrosion from Petroleum Products
by the Copper Strip Tarnish Test
D 216 191 Distillation of Natural Gasoline
D 323 Vapor Pressure of Petroleum Products (Reid Method)
D 1266 101 Sulfur in Petroleum Products (Lamp Method)
D 1298 160 Density, Specific Gravity, or API Gravity of
Crude Petroleum and Liquid Petroleum Products
by Hydrometer Method
D 2427 Determination of C2 through C5 Hydrocarbons
in Gasolines by Gas Chromatography
D 2699 237 Knock Characteristics of Motor Fuels by the
Research Method
D 2700 236 Knock Characteristics of Motor and Aviation
Type Fuels by the Motor Method
ETHYLENE
D 2504 Noncondensible Gases in Ca and Lighter
Hydrocarbon Products by Gas Chromatography
D 2505 Ethylene, Other Hydrocarbons, and Carbon Dioxide
in High-Purity Ethylene
D 3246 Sulfur in Petroleum Gases by Oxidative
Microcoulometry

Applicable ASTM/IP Standards (Continued.)

ASTM IP Title
PROPYLENE CONCENTRATES
D 1265 Sampling Liquefied Petroleum (LP) Gases
D 2163 264 Analysis of Liquefied Petroleum (LP) Gases and
Propylene Concentrates by GC
D 2504 Noncondensible Gases in C3 and Lighter
Hydrocarbons by Gas Chromatography
D 2712 Hydrocarbon Traces in Propylene Concentrates
by Gas Chromatography
BUTYLENE CONCENTRATES
D 1020 Alpha Acetylenes in Butadiene, Butadiene
Concentrates, and Butane-Butene Mixtures
(Silver Nitrate Method)
D 1265 Sampling Liquefied Petroleum (LP) Gases
D 1717 Analysis of Commercial Butane-Butylene Mixture
by Gas Chromatography
D 2384 Traces of Volatile Chlorides in Butane-Butene
Mixtures
D 2784 Sulfur in Liquefied Petroleum Gases
(Oxy-Hydrogen Burner or Lamp)
BUTADIENE
D 1020 Alpha Acetylenes in Butadiene, Butadiene
Concentrates, and Butane-Butene Mixtures
(Silver Nitrate Method)
D 1022 Peroxide Content of Light Hydrocarbons
D 1023 Separation of Residue from Butadiene
D 1025 Nonvolatile Residue of Polymerization Grade
Butadiene
D 1088 Boiling Point Range of Polymerization Grade
Butadiene
D 1089 Carbonyl Content of Butadiene
D 2426 Butadiene Dimer and Styrene in Butadiene
Concentrates by Gas Chromatography
D 2593 194 Butadiene Purity and Hydrocarbon Impurities
by Gas Chromatography

Bibliography
Gasmaking and Natural Gas, British Petroleum, 1972.
Katz, D. L., Handbook of Natural Gas Engineering, McGraw-Hill,New York, 1969.

Chapter 3 Petroleum Solvents

Introduction
The term "petroleum solvents" describes the special liquid hydrocarbon
fractions obtained from petroleum for use in industrial processes and commer-
cial formulations to dissolve, suspend, or transport the other ingredients of the
process or formulation. In recent years, the variety of petroleum solvents has
been increased considerably due to the development of refinery processes
designed primarily for the transformation of low-octane feedstocks to
high-octane fuels. These new developments led to the production of certain
important solvents and intermediates which were obtained previously only from
the coal carbonizing industry. By definition, the solvents obtained from the
petrochemical industry-the alcohols, ethers, etc.-are outside the scope of this
chapter.
Petroleum solvents are available for a variety of applications. Modern refining
techniques produce solvents with a high degree of purity and stability in a wide
range of grades and boiling points. Petroleum solvents are particularly attractive,
because they are readily available in large-volumes at low costs compared to
solvents from other sources.

General Uses
Solvents are used extensively by industry in manufacturing processes for such
diverse products as paint, printing ink, polish, adhesives, perfumes, glues, fats,
etc. Further uses are found in the dry cleaning, leather, and fur industries and
the pesticide field. Solvents, in highly purified condition, also are becoming
increasingly important for use as reaction media in certain catalytic processes.

Product Requirements
The variety of applications emphasizes the versatility of petroleum solvents.
The main characteristics which determine the suitability of a petroleum fraction
for a particular use are its solvent properties, volatility, purity, gravity, odor,
toxicity, and air pollution control/limitations.

Solvency
In many applications, petroleum solvents are used as a vehicle to dissolve
resins, oils, gums, or waxes. In other cases, the solvent merely suspends such
items as pigments, Idlers, and water. Examples of this are their use in the
printing ink, rubber coating and dipping, paint, lacquer, and polish industries.

23
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24 SIGNIFICANCE OF TESTS

Solvent properties are determined by the hydrocarbon types present. In

general, aromatic hydrocarbons have the highest solvent power and straight-
chain aliphatics the lowest.
A primary characteristic of solvency is the ability of the solvent to dissolve a
resin or other film formers. In general, the more polar resins require the more
polar solvents, that is, alcohols, esters, and ketones.
The amount of film former that the solvent will dissolve determines the solids
content (or nonvolatile content) of the system and ultimately the viscosity and
flow characteristics of the finished product. This is the most common basis for
rating solvents as to solvency for a particular resin.
As a solvent is added to a resin in increasing amounts, there is a point at which
the resin precipitates or "kicks out." This "dilution limit" is expressed as the
percent nonvolatile when precipitation occurs. The dilution limit is used
frequently as an indication of the relative solvency between solvents.

Volatility
Next to solvency, volatility may be the most important property of a solvent
since volatility largely governs evaporation rate or drying time. Volatility is
determined by the distillation temperature or range of temperatures for the
solvent. Pure hydrocarbons such as pentane, hexane, heptane, benzene, toluene,
and xylene are characterized by a narrow boiling range of 2 to 3~ Other
petroleum solvents that are mixtures of many,hydrocarbons have wide boiling
range widths that vary with their composition.
An excellent example of the importance of evaporation rate can be found in
the factors considered in the selection of a solvent for coatings. In coatings,
evaporation rate influences levelling, flowing, sagging, wet-edge time, and gloss.
The optimum evaporation rate varies with the method of application, from
fastest for spraying to intermediate for brushing to slowest for flow coating and
conveyor.
The choice of a solvent for a given application is dictated also by temperature
of use. A high-boiling sample will be required for a heat-set ink where the
operating temperature may be as high as 600~ (316~ but a low-boiling
solvent would be selected for fast drying in a foil printing press. Fortunately,
solvents are available to satisfy the wide range of requirements for evapoTation
rates and temperatures.

Pur#y
The purity of the various hydrocarbon solvents pertains not only to the minor
concentrations of nonhydrocarbon contaminants but, in some cases, particularly
with the highly purified lower boiling aromatics, to the presence of other
undesirable hydrocarbons.
Petroleum solvents, other than hydrocarbons such as toluene, are mixtures of
straight, branched-chain, and cyclic paraffins and aromatic hydrocarbons with a

possible trace of olefinic material. With this composition, they are, in the refined
state, inert substances. As inert materials, solvents may be used in the
preparation of surface coatings and adhesives and in a multitude of applications
without risk of side effects due to reaction with other substances in the
formulation or with the application surface.
The importance of any particular impurity will be a function of the solvent's
application. As a result, purchasers generally set solvent specifications. Normally,
part of these specifications will contain limits on the maximum level of specific
contaminants germane to their processes.

Gravity
Gravity, as defined later, is proportional to density. Since costs calculations
are based on density, this solvent property becomes very important in the
marketplace.

Odor
The odor of a solvent generally refers to the odor of the vapor during and
shortly following application. Occasionally, there may be a persistent residual
odor contributed by trace contaminants.
Ordinarily, the odor of industrial product finishes is not critical because
finishers become accustomed to strong smelling solvents, and most of the vapors
are removed by exhaust systems. However, finishers are likely to object if the
paint from one supplier has a different odor than that obtained from another.
Odor is most critical for interior trade sales products such as paints used in
homes. Even the mild odor of the typical aliphatic hydrocarbon solvents
frequently is considered unpleasant. This has contributed to the widespread
acceptance of latex paints which, by comparison, have subdued odors.
In the case of paints, chemists have little leeway regarding odor, since the
solvents must be chosen primarily for solvency and evaporation rate. To date,
the numerous "deodorants" promoted for use in paint have been of limited
value. A partial solution is the use of mineral spirits which are almost odor free.

Toxicity
The toxicological properties of the various hydrocarbon solvents are quite
important. The threshold limit values (TLVs) adopted by the American
Conference of Governmental Industrial Hygienists (ACGIH) limit the use of
solvents in high concentration in workroom air. In some cases, the choice
between different solvent systems is based solely on TLVs. (Threshold limit
values for individual solvents are available from ACGIH.)
Toxicity of solvents pertains to the potential injury to health that could occur
if the solvent gets into the bloodstream through inhalation. As an example,
benzene is sufficiently toxic to prohibit its use in federal paint specifications.

For this reason, paint manufacturers discourage the use of benzene in paint and
paint remover formulations.
As another example, toluene and xylene are more toxic than the aliphatic
hydrocarbons in the same boiling range. Therefore, aliphatic systems are
preferred to toluene and xylene if the loss of solvency can be made up by the
use of oxygen containing compounds.
Solvents used in paints for home use are relatively nontoxic. However,
prolonged breathing of concentrated solvent vapors should be avoided.

Air Pollution Requirements

The ability of a solvent to meet air pollution requirements has become an
increasingly important consideration. Most air pollution regulations prescribe the
quantity of a given solvent that may be discharged into the air over a given time
interval and the composition of allowable solvent blends.
Los Angeles Rule 66, which emphasizes the use of non- or low-aromatic
hydrocarbons, has served as a guide for other regions and municipalities.
Limitations under Rule 66 are not based on toxicity but on the susceptibility of
the solvents to undergo photochemical reactions which cause smog and eye
irritation. Rule 66 limits the use of toluene to 20 percent of the solvent and
xylenes to 8 percent (by volume).

Types of Hydrocarbons
The hydrocarbons may be divided into subgroups in different ways based on
chemical composition. The division that promotes the easiest understanding is:
1. Aliphatics.
(a) Normal paraffins, CnH2 n * 2.
(b) Isoparaffins, CnH2n + 2.
2. Naphthenes (cycloparaffins), CnH2n"
3. Aromatics, CnH2n _ 6.
4. Olefins, CnH2n"
Each of these divisions will be discussed in subsequent paragraphs. Corre-
sponding structural formulas, based on compounds having six carbon atoms, are
shown in Fig. 1.

Aliphatics
There are two types of open chain or aliphatic hydrocarbon solvents: normal
paraffins and isoparaffins. The normal paraffins have a straight chain of carbon
atoms, while the isoparaffins have side chains. Commercial solvents are in the
range of compounds with 6 to 15 carbons with the most widely used solvents
being compounds with 7 to 12 carbons.
Both types of paraffins conform to the principle that increasing molecular
weight results in lower solvency and lower volatility. The normal paraffins are

HHHHHH H
I

H--C-C-C-C-C-C--H H--C--H
H ! HHH
, : I!l
H--C--C--C-C-C--H
n-Hexane

Isohexane

H ~I H
I
~c\
H ! H H-C C-H

H-C
i II
C-H

H H L
Cyc lohexane Benzene
(Naphthene) (Aromatic )

HHH

C-C-C--H

3 -Hexene
(Olefin)
FIG. 1-Chemical structures o f some C 6 hydrocarbons.

characterized by low solvency and mild odor. As implied by the name, the
isoparraffins are isomers of the normal paraffins which they resemble in
solvency. Their only distinctive and significant property is extremely low odor.
They are almost odorless in the C9 and higher range.

Naphthenes ( Cycloparaf~ns )
The only naphthenes that are present in paint solvents in significant quantity
are cyclopentane, cyclohexane, and their alkyl substituted homologues. The
amount of naphthenes in nonaromatic hydrocarbon solvents varies greatly-from
0 to 90 percent by volume. Because of their cyclic structure, the naphthenes are
less volatile than paraffins with the same number of carbons and have stronger
solvency. They possess an odor similar to that of the terpenes which eliminates
them from low-odor solvents.

Aromatics
All of the aromatics are based on the unsaturated, six carbon ring structure of
benezene as shown in Fig. 2. The compounds of higher molecular weight are
called alkyl benzenes because they are benzene with one or more hydrogens
replaced by alkyl groups, such as methyl, ethyl, or butyl. This is shown in Fig. 2
for toluene and ortho-xylene, one of the three xylene isomers.

H H H

It I I --%

H H H

Benzene Toluene O-Xylene

FIG. 2-Structure o[ lower aromatic hydrocarbons.

The more important products that are higher than xylene in molecular weight
are n-propylbenzene, iso-propylbenzene (cumene), n-butylbenzene, and iso-
butylbenzene. Mixtures of these higher molecular weight compounds are sold as
a solvent under the name Hi-flash Solvent Naphtha.
Outstanding properties of the aromatic solvents, in comparison with aliphatic
hydrocarbons, are much higher solvency and stronger odor. Although naph-
thenes are a minor factor, it is not too strong to say that the solvent power of
commercial hydrocarbon solvents is roughly in proportion to their aromatic
c,ontent.

The almost pure aromatic hydrocarbons are correctly designated benzene,

toluene, and xylene. Commercial grades with distillation ranges up to 10*C are
equally satisfactory for use in coatings. These materials are known as benzol,
toluol, and xylol.

Commercial Hydrocarbon Solvents

General Solvent Types

The foregoing discussion of hydrocarbon solvents by chemical types provides a
background for the commercial products and their usage. While a paint chemist
should have some interest in the chemical constituents of solvents, his primary
concern must be with the commercial solvents as purchased. Of necessity, his
selection and use of solvents is based solely on the properties of commercial
products as determined by tests. Solvent users are guided mainly by the
following commercial classification of hydrocarbon solvents:
1. Narrow cut aliphatics.
2. Special boiling range solvents.
3. Mineral spirit types.
4. Aromatics.
5. Kerosine.
The approximate properties of these typical hydrocarbon solvents are shown
in Table 1.

Specific Types of Solvents

Although industrial users of solvents are guided by the commercial classifica-
tion just outlined, there are specific types of commercial solvents that merit a
thumbnail description.
Hexane and Heptane-Hexane and heptane are used frequently in multistage
processes where the solvent must be still present in one step, but be gone
completely before a subsequent step. They are also used as solvents and
suspending agents in the petrochemical industry where they are recovered and
reused. Heptane is used in place of hexane when a higher flash point or higher
boiling range solvent is needed.
Petroleum Ether-Petroleum ether is the fastest evaporating of the commonly
used solvents and therefore has obvious advantages, but its flash point is
correspondingly low. It is used as a solvent for oils, fats, waxes, in paints and
vamishes, and as a fuel.
"Textile" Spirits-This close cut solvent is predominantly hexane. It is used
only when very fast setting is desired, but since it has a broader boiling range
than hexane, evaporation occurs over a longer time interval.
Lacquer Diluent-Lacquer diluent is designed primarily for use in nitrocellu-
lose lacquer as a replacement, or partial replacement, for toluene. Lacquer
diluent is used in place of toluene because it is cheaper. The quality of lacquer

Distillation Evaporation Flash Kauri- G3

Range, ~ Rate Point, Butanol Aniline Aromatics Sp Gr Z
I
Initial Dry Point N = BuAc = 100 Tag Closed Cup, *F Value Point, *F Volume % 60/60
3,
NARROW-CUT ALIPHATICS Z
O
Hexane 151 157 >1000 ~ 31 146 <1 0.680 m
Heptane 201 209 600 23 38 127 3 0.728 O
SPECIAL BOILING POINT SOLVENTS
m
Petroleum ether 95 140 >1000 -60 26 150 0 0.645
Textile spirits 145 175 850 -20 34 134 5 0.690
Rubber solvent 144 248 700 ~0 36 131 5 0.712
Lacquer diluent 200 220 400 20 40 120 15 0.728
VM&P naptha 210 300 150 45 38 130 10 0.752
Ink oil 495 560 ~1 240 26 176 <5 0.820
MINERAL SPIRITS
Regular (Stoddard) 320 380 10 108 39 130 15 0.789
140-flash point 360 400 5 140 35 143 15 0.792
Odorless 350 380 7 125 27 184 <1 0.759
High solvency 320 380 8 110 44 105 30 0.808
AROMATICS
Benzene 175 177 500 '(10 115 57 a 99+ 0.885
Toluene 230 232 200 40 105 46 a 99+ 0.870
Xylene 282 285 60 83 98 52 a 99+ 0.869
High-flash aromatic naphtha 310 350 19 107 92 56 a 98+ 0.874
High-flash aromatic naphtha 360 410 4 151 90 64a 97+ 0.891
Heavy aromatic naphtha 360 540 1 152 105 76 a 86+ 0.933
KEROSINE
Regular 350 515 1 140 30 160 <25 0.804
Odorless 400 480 1 170 27 190 <1 0.782

aMixed aniline point, ~

diluent is proportional directly to aromatic content. The more aromatics, the

better the quality. Lacquer diluents are used also as solvents in gravure inks for
printing.
VM&P Naphtha-Large quantities of VMSff' naphtha are used. It resembles
regular mineral spirits in hydrocarbon type composition and has about the same
solvency. However, it is lower boiling, has a lower flash point, and evaporates
much faster. The fast evaporation and low-flash point make it generally
unsuitable for interior architectural finishes, but it is well adapted for
application by spraying and, in some cases, by dipping. The grades with an initial
boiling point of about 235~ or higher are differentiated frequently as high-flash
VM&P naphtha.
Ink Oils-Ink oils are used in place of kerosines where narrow-cut ink solvents
are desired. The narrow cut provides better drying control of the ink.
Mineral Spirits-Mineral spirits constitute about three fourths of all hydro-
carbon solvents used in the paint industry and 90 percent of the solvents in
architectural finishes. It comprises four general types: (1) regular, (2) odorless,
(3) high flash, and (4) high solvency. Within each of these types, there are
products that offer a choice in boiling range and volatility, and thus permit some
control of "setting" rate, brushability, and wet-edge time.
Benzene fBenzol)-The use of benzene in coatings is considered bad practice
because the vapors are toxic. Its only common use by the paint industry is in
solvent type paint and varnish removers where it is more effective than the
higher-boiling aromatics.
Toluene (Toluol)-Toluene is used widely when maximum solvency and rather
fast evaporation are desired. It is the best fast diluent for nitrocellulose lacquers
and also is used in synthetic enamels of several types. The industrial pure grades
with distillation ranges of a few degrees centigrade give the same results as the
I*C nitration grade.
Xylene (Xylol)-Xylene is essentially a mixture of the ortho, meta, and para.
isomers of xylene with ethylbenzene. It is used instead of toluene where slower
evaporation is sought. In both lacquers and synthetic enamels, xylene is used
frequently in admixture with toluene. It is the sole or main hydrocarbon solvent
in many synthetic industrial enamels that are applied by spraying. Unlike
toluene, xylene does not require a red label for interstate shipments.
Hi-Flash Solvent Naphtha-Formerly this term referred only to a high-boiling
fraction obtained from coal tar. Today, it also covers an equivalent product that
is derived from petroleum. Many industrial paints require at least a portion of a
strong hydrocarbon solvent that evalSorates slower than xylene. Hi-flash Solvent
Naphtha fills this need.
Kerosine-Kerosine is the only hydrocarbon solvent that is rated as having a
wide distillation range. It is used when extremely slow setting and rather low
solvency are desired, and the kerosine odor is permissible. Two such purposes are
wood fillers and putties. In most applications, kerosine is combined with a larger
amount of mineral spirits.

Test Methods for Solvents

The most important tests conducted on solvents are shown in Table 2. These
tests are of two general types. Control tests are those used to test shipments for
uniformity and compliance with specifications, and evaluation tests are those
conducted on new materials to determine their properties and suitability for use.
As a rule, the control tests are more simple. Some tests may be used for both
purposes.
The following paragraphs address sampling techniques for petroleum solvents
and discuss the purposes and principles of the tests listed in Table 2. Specific
details on the various tests can be found in the Annual Book o f A S T M
Standards, Volumes 23, 24, and 25.
TABLE 2-ASTM tests commonly conducted on solvents.

Specific gravity D 891

AorB
Distillation
(a) petroleum type solvents D 86
(b) Other solvents D 1078
Flash point
(a) tag closed tester D 56
(b) tag open tester D 1310
Evaporation rate pending
Kauri-butanol value of hydrocarbon solvents D 1133
Aniline point of hydrocarbon solvents D 1012
Mixed aniline point of hydrocarbon solvents D 1012
Copper corrosion, aliphatic hydrocarbons D 1616
Copper corrosion, aromatic hydrocarbons D 849
Dilution ratio in nitrocellulose solutions D 1720
Viscosity of nitrocellulose solutions D 1343

Sampling
Because of the high standards set for petroleum solvents, it is essential to
employ the correct techniques when taking samples for tests. Mishandling, or the
slightest trace of contaminant, can give rise to misleading results. Sampling
methods are described in ASTM Sampling Petroleum and Petroleum Products (D
270). Special care is necessary to ensure that containers are scrupulously clean
and free from odor. Samples should be taken with the minimum of disturbance
so as to avoid loss of volatile components. In the case of the lightest solvents, it
may be necessary to chill the sample.
While awaiting examination, samples should be kept in a cool, dark place to
ensure that they do not discolor or develop odors.

Specific Gravity
The determination of specific gravity serves two purposes: it provides a check
on the uniformity of shipments, and it permits calculation of the weight per
gallon.

SpeciFic gravity is defined as the ratio of a weight of a given volume of

material to the weight of an equal volume of water under specified conditions.
Specific gravity for petroleum solvents is usually determined by ASTM Tests for
Specific Gravity of Industrial Aromatic Hydrocarbons and Related Materials (D
891). A gravity balance or a glass hydrometer is used with this procedure.
Producers of petroleum solvents frequently use American Petroleum Institute
(API) gravity instead of specific gravity. API gravity was developed to permit the
use of whole numbers.
To avoid dealing with two kinds of gravity, paint laboratories usually convert
the API values to specific gravity by use of conversion tables or by the formula

API gravity, deg = 141.5 - 131.5

sp gr at 60/60~
For figuring formula yields and important composition relationships, paint
laboratories must have a list of raw materials that includes the weight per gallon
of all liquid materials at normal operating temperature. When the specific gravity
of solvents is determined at the customary 60/60"F, a temperature conversion
factor must be used to obtain the specific gravity at 70*F, and this factor differs
with the solvent. This corrected specific gravity must then be converted to
pounds per gallon.

Distillation
The significance of distillation results is based on the close relationship to
volatility which, in turn, largely governs evaporation rate. ASTM Test for
Distillation of Petroleum Products (D 86[IP 123) is used for solvents with a wide
distillation range (this includes the common aliphatic and aromatic naphtha
solvents). ASTM Test for Distillation Range of Volatile Organic Liquids (D
1078) is the procedure used for solvents with a narrow range of distillation
(aromatic hydrocarbons, alcohols, esters, and ketones). Regardless of solvent
type, a very narrow distillation range has no direct advantage in coatings.
However, it may have significance as an indication of the degree of purity of
oxygenated solvents.

Flash Point
The flash point of a liquid is the lowest temperature at which application of a
flame causes the vapor above the sample to ignite. Flash point is indicative of
potential fire hazard. The most common method of determing flash point is with
the ASTM Flash Point by Tag Closed Tester (D 56) which confines the vapor
until the instant the flame is applied. However, Interstate Commerce Commis-
sion regulations on the shipping of flammable solvents are based on the ASTM
Flash Point of Liquids by Tag Open-Cup Apparatus (D 1310) which gives
slightly higher values.
Copyright by ASTM Int'l (all rights reserved); Tue Dec 29 16:07:05 EST 2015
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34 SIGNIFICANCE OF TESTS

In mixtures of solvents and in coatings, the flash point is substantially that of

the lowest flash portion that is present in an appreciable amount.

Evaporation Rate
Although there is a significant relation between distillation range and
evaporation rate, the relationship is not direct. Because of its importance, several
methods of measuring evaporation rates of straight solvents (not the solvent in a
film coating) have been developed by various commercial and governmental
organizations. Efforts are underway in ASTM to standardize a procedure.
A simple procedure for evaporation rate that can be conducted in any
laboratory with sufficient precision for practical purposes is as follows:
Use tared 1-ounce shallow salve cans with covers and do weighing on
an analytical balance. Weigh 1 gram of test solvent in one can and 1
gram of n-butyl acetate in another can. Place the containers in a
draft-free area, preferably with controlled temperature and humidity.
Remove the covers and reweigh at intervals until the samples have
completely evaporated. The time in minutes for n-butyl acetate divided
by the time for the test solvent is the evaporation rate. It may be
advisable to change the size of the samples for solvents that are quite
fast or quite slow. A very slow tail of a few percent may be disregarded.
Evaporation rates are usually expressed relative to n-butyl acetate, which is
assigned a value of one. A value of 0.4 means that the solvent evaporates 0.4
times as fast as butyl acetate and a value of 2.5 means 2.5 times as fast. Since the
last 5 percent of a solvent may show a definite lag in evaporation but has small
influence on performance, it is sometimes disregarded in assigning the rate.
There is a formula for calculating approximate evaporation rates from
distillation temperatures. However, solvent producers supply information on the
individual solvents, so the only possible need for such calculations is for solvent
mixtures. In view of the complexity of the calculations, direct determination
probably would take no longer and be no less reliable.

Kauri-Butanol Value
ASTM Test for Kauri-Butanol Value of Hydrocarbon Solvents (D 1133) is
used to determine relative solvent power. The kauri-butanol (K-B) value is the
number of milliliters of the solvent, at 77"F (25~ required to produce a
defined degree of turbidity when added to 20 g of a standard solution of gum
kauri resin in normal butyl alcohol. For K-B values of 60 and over, the standard
is toluene which has an assigned value of 105. For K-B values under 60, the
standard is a blend of 75 percent n-heptane and 25 percent toluene which has an
assigned value of 40. Higher values indicate greater solvent power. The K-B value
of products that are classified as regular mineral spirits normally varies between
34 and 44; xylene is 93, and the aromatic naphtha solvents range all the way
from 55 to 108.

Aniline Point and Mixed Aniline Point

ASTM Test for Aniline Point and Mixed Aniline Point of Hydrocarbon
Solvents (D 1012) is another method for determining the solvent power of
hydrocarbon solvents. It is a more precise technique than the method for K-B
value, and the results have better correlation with performance in coatings. The
two methods may indicate a reversal of solvent power when applied to solvents
that are in the same range. Therefore, in evaluation testing it is best to employ
both methods. For control purposes, one method should be adequate, since
there is no significant difference in repeatability.

Su~r
Copper strip corrosion tests are used to detect the presence and determine the
relative amounts of sulfur compounds in solvents. Sulfur compounds are
objectionable because they impart odor and may cause darkening of cooked
varnishes and resins.
ASTM Test for-Copper Corrosion of Industrial Aromatic Hydrocarbons (D
849) is used for the determination of sulfur compounds in aromatic hydro-
carbons while ASTM Test for Copper Corrosion by Mineral Spirits (Copper Strip
Test) (D 1616) is applicable for sulfur compounds in aliphatic hydrocarbons.
With modem refining methods, copper corrosion tests have assumed less
importance. They are now considered optional even for control testing.

Dilution Ratio in Nitrocellulose Solutions

Solvent mixtures for nitrocellulose lacquers contain three classes of volatile
liquids: active solvents, latent solvents (alcohols), and diluents. The active and
latent solvents may be grouped together under the term "oxygenated solvents."
The diluents are hydrocarbon solvents which have no solvency for nitrocellulose
and employed mainly to reduce cost without sacrifice of quality. The proportion
of hydrocarbon solvents that can be used without precipitation of the
nitrocellulose differs with the kind of hydrocarbon. The dilution ratio test
determines this proportion for particular hydrocarbon solvents. The dilution
ratio is
volume of hydrocarbon solvent at the end point
volume of butyl acetate
This ratio is roughly proportional to the aromatic content of the hydrocarbon.
The dilution ratio test also is usefully applied to the oxygenated solvents.
Oxygenated solvents differ in the amount of diluent that they will tolerate. This
affects the cost of formulating with a particular oxygenated solvent. For this
purpose, a single diluent, toluene, is employed, and the amount is varied with
each oxygenated solvent being tested.

Viscosity of Nitrocellulose Solutions

One of the disadvantages of nitrocellulose in coatings is that the more durable
grades produce solutions that have high viscosity and, therefore, low solids at a
viscosity suitable for application. The viscosity of a solution is affected by the
kind of solvent or mixture of solvents. ASTM Test for Viscosity of Cellulose
Derivatives by Ball-Drop Method (D 1343) is designed to determine the inherent
viscosity characteristic of various grades of nitrocellulose. The test is equally
suitable for comparing the viscosity effect of solvents by varying the solvent
while holding the kind and amount of nitrocellulose constant.

Applicable ASTM Specifications

Aliphatic Hydrocarbons
D 235 Petroleum Spirits (Mineral Spirits)
D 484 Hydrocarbon Dry Cleaning Solvents
D 838 Naphtha, Refined Solvent
D 839 Solvent Naphthas, Crude Light
D 840 Solvent Naphthas, Crude Heavy
D 1836 Commercial Hexanes

Aromatic Hydrocarbons
D 362 Toluene, Industrial Grade
D 364 Xylene, Industrial Grade
D835 Benzene, -485, Refined (Nitration Grade)
D836 Benzene, Industrial Grade
D 841 Toluene, Nitration Grade
D 843 Xylene, Nitration Grade
D 845 Xylene, Five Degree
D 846 Xylene, Ten Degree
D 2359 Benzene, - 535, Refined

ApplicableASTM/IPStandards
PhysicalProperties
ASTM IP Title
VOLATILITY
Distillation
ASTM D 86 IP 123 Distillation of Petroleum Products
(Wide Range)
ASTM D 850 Distillation of Aromatic Hydrocarbons
ASTM D 1078 Distillation of Petroleum Products
(Narrow Range)

ASTM D 1160 Distillation of Petroleum Products at

Reduced Pressure
ASTM D 2887 Boiling Range Distribution of Petroleum
Fractions by GC

Flash Point
ASTM D 56 Flash Point by Tag Closed Tester
ASTM D 92 IP 36 Flash and Fire Points by Cleveland Open Cup
ASTM D 93 IP 34 Flash Point by Pensky-Martin Closed Tester
ASTM D 1310 Flash Point of Liquids by Tag Open-Cup
Apparatus

Autoignition Temperature
ASTM D 2155 Autoignition Temperature of Liquid
Petroleum Products

Residue
ASTM D 1353 Nonvolatile Matter in Volatile Solvents

DENSITY AND SPECIFIC GRAVITY

ASTM D 287 API Gravity of Petroleum and Petroleum
Products (Hydrometer)
ASTM D 891 Specific Gravity of Industrial Aromatic
Hydrocarbons
ASTM D 941 Density and Specific Gravity of Liquids
by Lipkin Bicapillary Pycnometer
ASTM D 1217 Density and Specific Gravity of Liquids
by Bingham Pycnometer
ASTM D 1298 IP 160 Density, Specific Gravity, or API Gravity of
Crude Petroleum and Liquid Petroleum Prod-
ucts by Hydrometer Method
ASTM D 1555 Volume and Weight of Industrial Aromatic
Hydrocarbons
ASTM D 2935 Apparent Density of Industrial Aromatic
Hydrocarbons

FREEZING POINT
ASTM D 250 Cloud Point
ASTM D 852 Solidification Point of Benzene
ASTM D 1015 Freezing Points of High-Putity Hydrocarbons
ASTM D 1493 Solidification Point of Industrial
Organic Chemicals

Applicable ASTM/IP Standards

Physical Properties (Continued.)

ASTM IP Title

VISCOSITY
ASTM D 88 Saybolt Viscosity
ASTM D 445 IP 71 Kinematic Viscosity of Transparent and
Opaque Liquids
ASTM D 2161 Conversion of Kinematic Viscosity to
Saybolt Universal Viscosity or to
Saybolt Furol Viscosity

COLOR
ASTM D 156 Saybolt Color of Petroleum Products
ASTM D 848 Acid Wash Color of Industrial Aromatic
Hydrocarbons
ASTMD 1209 Color of Clear Liquids (Platinum-Cobalt Scale)

REFRACTIVE INDEX
ASTM D 1218 Refractive Index and Refractive Dispersion
of Hydrocarbon Liquids

SOLVENCY
ASTM D 611 Aniline Point and Mixed Aniline Point of
Petroleum Products and Hydrocarbon Solvents
ASTM D 1012 Aniline Point and Mixed Aniline Point of
Hydrocarbon Solvents
ASTM D 1133 Karui-Butanol Value of Hydrocarbon Solvents
ASTM D 1343 Viscosity of Cellulose Derivatives by
Ball-Drop Method
ASTM D 1720 Dilution Ratio in Cellulose Nitrate Solutions
for Active Solvents, Hydrocarbon Diluents,
and Cellulose Nitrates

ODOR
ASTM D 1296 Odor of Volatile Solvents and Diluents

DEFINITIONS AND HANDLING

ASTM D 268 Volatile Solvehts for Use in Paint, Lacquer
and Related Products, Sampling and Testing

ASTM D 270 Sampling Petroleum and Petroleum Products

ASTM D 288 Definitions of Terms Relating to Petroleum
ASTM D 1086 Measuring Temperature of Petroleum and
Petroleum Products
ASTM D 1250 IP 200 Petroleum Measurement Tables

Chemical Properties
ASTM IP Title

BULK COMPOSITION

ASTM D 1016 Purity of Hydrocarbons from Freezing Point

ASTMD 1319 " IP 156 Hydrocarbon Types in Liquid Petroleum
Productsby FIA
ASTMD 2008 Ultraviolet Absorption of Petroleum Products
ASTM D 2268 Analysis of High Purity n-Heptane and
lsooctane by Capillary GC
ASTM D 2306 Xylene Isomer Analysis by GC

IMPURITY DETERMINATIONS
Hydrocarbon Types
ASTM D 851 Paraffins in Industrial Aromatic Hydrocarbons
ASTM D 875 Calculation of Olefins and Aromatics in
Petroleum Distillates from Bromine Number
and Acid Absorption
ASTM D 1017 Benzene and Toluene by Ultraviolet
Spectrophotometry
ASTM D 1019 IP 145 Olefinic plus Aromatic Hydrocarbons in
Petroleum Distillates
ASTM D 1159 IP 130 Bromine Number of Petroleum Distillates
and Commercial Aliphatic Olefins by
Electrometric Titration
ASTM D 1491 Bromine Index of Aromatic Hydrocarbons
by Potentiometric Titration
ASTM D 1658 Carbon Number Distribution of Aromatic
Compounds in Naphthas by Mass Spectrometry
ASTM D 2267 Aromatics in Light Naphthas by GC
ASTM D 2360 Nonaromatic Hydrocarbons in Monocyclic
Aromatic Hydrocarbons by GC
ASTM D 2600 IP 262 Aromatic Traces in Light Saturated
Hydrocarbons by GC
ASTM D 2710 Bromine Index of Petroleum Hydrocarbons
by Electrometric Titration

Chemical Properties (Continued.)

ASTM IP Title
Sulfur
ASTM D 130 IP 154 Detection of Copper Corrosion from Petroleum
Products by Copper Strip Tarnish Test
ASTM D 849 Copper Corrosion of Industrial Aromatic
Hydrocarbons
ASTM D 853 Hydrogen Sulfide and Sulfur Dioxide Content of
Industrial Aromatic Hydrocarbons
ASTM D 1266 IP 107 Sulfur in Petroleum Products (Lamp Method)
ASTM D 1616 Copper Corrosion by Mineral Spirits
ASTM D 2324 Carbon Disulfide in Benzene
ASTM D 3120 Trace Quantities of Sulfur in Light Liquid
Petroleum Hydrocarbons by Oxidative
Microcoulometry
Oxygen
ASTM D 1021 Oxygen in Light Hydrocarbon Vapors
ASTM D 1022 Peroxide Content of Light Hydrocarbons

Acidity
ASTM D 847 Acidity of Benzene, Toluene, Xylenes,
Solvent Naphthas and Similar Industrial
Aromatic Hydrocarbons
ASTM D 1093 Acidity of Distillation Residues of
Hydrocarbon Liquids
ASTM D 2896 Total Base Number of Petroleum Products by
Potentiometric Perchloric Acid Titration
Water
ASTM E 203 Water Using Karl Fischer Reagent
ASTM D 1364 Water in Volatile Solvents
(Fischer Reagent Titration Method)
ASTM D 1744 Water in Liquid Petroleum Products by
Karl Fischer Reagent

Bibliography
Durrans, T. H., Solvents, Chapman & Hall, London, 1957.
Marsden, L., Solvents Guide, Cleaver-Hume,London, 2nd edition, 1963.
Mellan, I., Handbook of Solvents, Vol. 1, Reinhold,New York, 1957.
Mellan, I., Industrial Solvents, Reinhold, New York, 2nd edition, 1950.
Mellan, I., Industrial Solvents Handbook, Noyes Data Corporation, Newark, New Jersey,
1970.
Modern Petroleum Technology, Institute of Petroleum,London, 3rd edition, 1962.
Petroleum Products Handbook, V. B. Guthrie, Ed., McGraw-Hill,New York, 1960.
Reynolds, W. W., Physical Chemistry of Petroleum Solvents, Reinhold, New York, 1963.

Chapter 4 Automotive Gasoline

Introduction

Automotive gasolines are used to fuel internal combustion spark-ignition

engines. While gasolines discussed in this chapter are used primarily in passenger
car and highway truck service, they also are used extensively in off-highway
utility vehicles, farm machinery, two- and four-stroke cycle marine engines, and
other spark-ignition engines employed in a variety of different service applica-
tions.
Automotive gasolines essentially are blends of hydrocarbons derived from
petroleum. In addition, they may contain selected additives that impart specific
features to the finished gasoline. The hydrocarbons are derived from fractional
distillation of crude oil as well as from complex processes that increase either
the amount or quality of the gasoline obtained. These components vary from
individual compounds such as normal butane to wide-boiling range products that
contain hundreds of different hydrocarbons. The properties of commercial
gasolines are influenced by the refinery practices employed and the nature of the
crude oils from which they are produced. Finished gasolines encompass a boiling
range of about 85 to 437~ (30 to 225~
Gasolines are blended to satisfy diverse automobile requirements. Antiknock
quality, distiUation characteristics, vapor pressure, sulfur content, oxidation
stability, and anticorrosion behavior are balanced to provide satisfactory vehicle
performance. Additives may be used to provide or enhance specific performance
features.
This chapter summarizes the significance of the more important physical and
chemical characteristics of automotive gasolines and describes pertinent test
methods for defining or evaluating these properties.

Grades of Gasoline
Historically, automotive gasolines have been classified into two grades-
"premium" and "regular"-on the basis of octane number. In recent years, the
research octane number of premium gasoline has been about 100 while that of
regular gasoline has been about 94. (The significance of octane numbers will be
discussed in the following section.) In high-altitude areas of the country, both
premium and regular octane levels have been somewhat lower than at sea level
because car octane requirements decrease with altitude. "Super premium,"
"intermediate," and "subregular" grades of gasoline also have been marketed as
well as blends of high- and low-octane grades.
With the exception of one premium gasoline marketed on the east coast of the

41
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42 SIGNIFICANCE OF TESTS

United States, all automotive gasolines until 1970 contained lead alkyl
antiknock compounds to increase octane quality. Because lead antiknock
compounds are detrimental to the performance of catalytic emission control
systems, U.S. passenger car manufacturers, in 1971, began to build engines
designed to operate satisfactorily on gasolines of nominal 91 research octane
number. Some of these engines were designed to operate on unleaded fuel while
others required low-lead fuel. The 91 octane level was chosen in the belief that
low-lead and unleaded gasolines could be made available in the quantities
required using current refinery processing equipment. Accordingly, during 1970,
unleaded and low-lead gasolines were introduced to supplement the conventional
gasolines already available.
Unleaded fuels are generally defined as those to which no lead antiknock
compound has been added deliberately. However, a small amount of lead pickup
can occur in gasoline distribution. Since most vehicles in the United States were
equipped with catalytic converters beginning with the 1975 model year, the U.S.
government (Environmental Protection Agency) required most service stations,
beginning in July 1974, to offer for sale at least one grade of unleaded gasoline.
This gasoline must have a research octane number of at least 91 and contain no
more than 0.05-g lead/gal and no more than 0.005-g phosphorus/gal. Low-lead
fuels, as opposed to unleaded fuels, are those to which lead antiknock
compound has been added with a maximum concentration of 0.5-g lead/gal.
"Conventionally leaded" gasolines are those having lead contents above 0.5 but
no more than 4.23-g lead/gal.

Automotive Gasoline Performance and Information System

In 1972, the American Society for Testing and Materials (ASTM) and the
Society of Automotive Engineers (SAE) published an Automotive Gasoline
Performance and Information System (ASTM STP 510,4, SAE J 282). The
purpose of the system is to provide a set of consumer-oriented performance
standards for motor gasolines with understandable symbols that indicate to the
consumer the characteristics of the product and the level of its performance
regardless of season or location. The four performance factors incorporated into
the symbol (gasoline pump label) are antiknock performance, exhaust emission
control system compatibility, induction system cleanliness, and driveability
performance. Initially, the symbol system deals with only the first two factors,
since there are no standardized performance tests to evaluate engine induction
system cleanliness and vehicle driveability. However, space has been provided to
include this information in the symbol when suitable performance tests are
developed.

Antiknock Quality
The definitions and test methods for antiknock performance for automotive
gasolines are set forth in ASTM Specifications for Automotive Gasoline (D 439).

The antiknock quality of gasoline is of prime importance. If antiknock quality is

too low, knock occurs. Knock is a high pitch, metallic rapping noise. In addition
to being audibly annoying, in severe cases, knock may lead to uncontrolled
preignition which can cause burning of piston crowns and other engine damage.
There is also evidence that knock increases the rate of engine wear. The potential
durability, power, and fuel economy of a given engine is realized only when the
gasoline antiknock quality is adequate. However, there is no advantage in using a
gasoline having antiknock quality higher than the engine requires.
Knock depends on complex physical and chemical phenomena highly
interrelated with engine design and operating conditions. It has not been possible
to completely characterize the antiknock performance of gasoline with any
single measurement. The antiknock performance of a gasoline is related
intimately to the engine in which it is used and the engine operating conditions.
Furthermore, this relationship varies from one engine design to another and may
even be different among engines of the same design due to normal production
variations.
The antiknock quality of a gasoline is measured by several methods. These
procedures employ single-cylinder laboratory engines and more realistic, but
much less precise, mnlticylinder engines in cars. Two single-cylinder methods
have been standardized to measure antiknock quality: ASTM Test for Knock
Characteristics of Motor Fuels by the Research Method (D 2699[IP 237) and
ASTM Test for Knock Characteristics of Motor and Aviation-Type Fuels by the
Motor Method (D 2700/IP 236).
Both of these tests procedures employ a variable-compression-ratio engine.
The motor method operates at a higher speed and inlet mixture temperature
than the research method. The procedures relate the knocking characteristics of
a test gasoline to standard fuels which are blends of two pure hydrocarbons-
isooctane (2,2,4-trimethylpentane) and n-heptane. These blends are called
primary reference fuels. By definition, the octane number of isooctane is 100,
and the octane number of n-heptane is zero. At octane levels below 100, the
octane number of a given gasoline is the percentage by volume of isooctane in a
blend with n-heptane that knocks with the same intensity at the same
compression ratio as the gasoline when compared by one of the standardized
engine test methods. The octane number of a gasoline greater than 100 is based
upon the required milliliters of tetraethyllead to be added to isooctane to
produce knock with the same intensity as the gasoline. The number of milliliters
of tetraethyUead in isooctane is converted to octane numbers greater than 100
by use of tables included in the research and motor methods referred to
previously.
The octane number of a given blend of either isooctane and n-heptane or
tetraethyllead in isooctane is, by definition, the same for the research and motor
methods. However, the research and motor octane numbers will be rarely the
same for commercial gasolines. Therefore, when considering the octane number
of a given gasoline, it is necessary to know the engine test method. Commercial

gasoline typically will have an octane number approximately eight units lower
by the motor method than by the research method, illustrating the important
effect of engine operating conditions on antiknock performance. The numerical
difference between the research and motor octane numbers can be used to
estimate the antiknock quality of gasolines in multicylinder engines and under
different operating conditions. Research octane number is, in general, the better
indicator of antiknock quality for engines operating at full throttle and
low-engine speed. Motor octane number is the better indicator at full throttle,
high-engine speed and part throttle, low- and high-engine speed.
The antiknock performance of gasolines in cars, or road octane number, may
be determined directly by using primary reference fuels and manually controlled
ignition timing to vary the knocking tendency of the engine. The most
commonly used test methods are the Coordinating Research Council, Inc. (CRC)
Modified Borderline (F-27) and Modified Uniontown (F-28) research techniques.
When using these procedures, the knocking tendencies of test gasolines and
reference fuels usually are compared at the lowest audible level of knock. Road
octane number of a gasoline is defined as being equal to the octane number of
the primary reference fuel blend that produces the same knock intensity while
operating under the specified test conditions.
For most automotive engines and operating conditions, the road octane
number of a gasoline will be between its research and motor octane numbers.
The relationship between research and motor octane numbers used to predict
the road antiknock quality of gasolines is dependent upon the vehicles and
operating conditions. Antiknock Index is a currently accepted method of
relating research octane number (RON) and motor octane number (MON) to
actual road antiknock performance of cars. It is obtained by summing one half
the RON and MON of a gasoline; that is, (RON + MON)/2.
The Automotive Gasoline Performance and Information System (ASTM STP
510A, SAE J 282) referred to earlier describes six levels of antiknock
performance to include all engine antiknock requirements. The six designated
antiknock levels are shown in Table 1.
The tendency of gasolines to knock can be decreased markedly by the
addition of very small quantities of chemical additives known as antiknock
compounds. The lead aikyls (tetraethyllead, tetramethyllead, and physical and
chemically reacted mixtures of these two materials) are the most commonly
used antiknock compounds. These compounds are added to gasoline in the form
of fluids that also contain an identifying dye and organic halides. The organic
halides aid in scavenging the combustion products of the lead alkyls from the
combustion chamber during the exhaust cycle.

Volatility
The volatility characteristics of a gasoline are also of prime importance.
Gasoline is used in a great variety of engines with large variations in operating
conditions and under a wide range of atmospheric temperatures. These variations
Copyright by ASTM Int'l (all rights reserved); Tue Dec 29 16:07:05 EST 2015
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CHAPTER 4 ON AUTOMOTIVE GASOLINE 45

TABLE I-Antiknock requirements for gasolines.

Antiknock Indexa
Number Minimum
Designation Application (RON + MON)/2

1 for cars with low antiknock needs ~87

2 meets antiknock needs of most 1974 and later 87 b

model cars.

3 for most 1970 and prior model cars designed to 89c

operate on "regular" gasoline, and for 1971 and
later model cars that requke higher antiknock
performance than provided for in designation 2

4 a "mid-premium" or "intermediate" designation 91.5

which meets the lower antiknock needs of some
cars designed to run on "premium" gasolines and
the higher antiknock needs of some cars designed
to run on "regular"

5 for most 1970 and prior model cars with high 95 c

compression ratio engines designed to run on
"premium" gasolines, and for later model cars
with high-compression-ratio engines

6 for cars with high-compression-ratio engines de- 97.5

signed to run on "premium" gasoline, but requir-
ing higher antiknock performance than designa-
tion 5

aOne half the sum of the research octane number (RON) and motor octane number
(MON): The antiknock index of gasoline for use in areas where altitude is greater than 2000
ft (600 m) may be reduced one-half (0.5) number for each succeeding 500 ft (150 m) but
not to exceed a total of three (3) numbers.
bin addition, the minimum motor octane number must be 82.
Cln the following states, this minimum may be reduced by one-half (0.5) number:
Arkansas, Iowa, Kansas, Minnesota, Missouri, Montana, Nebraska, North Dakota, Oklahoma,
South Dakota, Wisconsin, and Texas west of 99 deg longitude.

impose many limitations on the volatility of gasoline if it is to give satisfactory

performance. Gasoline that vaporizes too readily in pumps, fuel lines, and
carburetors will cause decreased fuel flow to the engine resulting in rough engine
operation or stoppage (vapor lock). Conversely, gasolines that do not vaporize
readily enough may cause hard starting and poor warm-up and acceleration, as
well as unequal distribution of fuel to the individual cylinders, which may cause
knock. Fuels that vaporize too readily also may cause, if certain atmospheric
conditions exist, ice formation in the carburetor throat resulting in rough idle
and stalling.
The volatility of automotive gasoline must be carefully "balanced" to provide
the optimum compromise among performance features that depend upon the

vaporization behavior. Superior performance in one respect may give serious

trouble in another. Therefore, volatility characteristics of automotive gasolines
must be adjusted for seasonal variations in atmospheric temperatures and
geographical variations in altitude.
Since gasoline is a mixture of many hydrocarbons, it does not have a single
boiling point. Its tendency to vaporize is characterized by determining a series
of temperatures at which various percentages of the gasoline have evaporated as
described in ASTM Test for Distillation of Petroleum Products (D 86/IP 123).
The temperatures at which 10, 50, and 90 percent evaporation occurs are used
to characterize the volatility of automotive gasolines.
Vapor pressure is the force per unit area exerted on the walls of a closed
container by the vaporized portion of the liquid contained therein. For
hydrocarbon mixtures such as gasoline, the vapor pressure depends on the ratio
of vapor to liquid in the container and the temperature. Vapor pressure of
gasoline, when measured at 100*F (38~ in a bomb having a 4[1 ratio of air to
liquid, is known as Reid vapor pressure (Rvp). It is described in ASTM Test for
Vapor Pressure of Petroleum Products (Reid Method) (D 323).
Gasoline vaporization tendency may also be expressed in terms of vapor/liquid
ratio (V/L) at temperatures and pressures approximating those found in critical
parts of the fuel system as presented in ASTM Test for Vapor-Liquid Ratio of
Gasoline (D 2533).
In general terms, the following relationships between volatility and perfor-
mance apply:
(a) High.vapor pressures and low temperatures for 10 percent evaporated are
both conducive to ease of cold starting. However, under hot-operating
conditions, they are also conducive to vapor lock and increased vapor formation
in fuel tanks and carburetors. The amount of vapors formed in fuel tanks and
carburetors, which must be contained by the evaporative loss control system, are
related to the Rvp and distillation temperatures, respectively. Thus, a proper
balance must be maintained and seasonally adjusted for good overall per-
formance.
(b) Although vapor pressure is a factor in the amount of vapor formation
under vapor-locking conditions, vapor pressure alone is not a good index. A
better index for measuring the reactive vapor-locking performance of gasolines in
current model cars is the temperature for 20 vapor/liquid ratio. The lower the
temperature at V/L = 20, the greater the tendency to cause vapor lock.
(c) The temperature for 50 percent evaporated is a broad indicator of
warm-up and acceleration performance under cold-starting conditions. The lower
the 50 percent evaporated temperature, the better the performance. However,
carburetor icing tendency and consequent engine stalling are increased by low 50
percent evaporated temperatures.
(d) The temperature for 90 percent evaporated and the final boiling point
(FBP) indicate the amount of relatively high-boiling components in gasoline. A
high 90 percent evaporated temperature, because it usually is associated with

higher density and high-octane number components, may contribute to

improved fuel economy and resistance to knock. If the 90 percent evaporated
temperature and the FBP are too high, they can cause poor mixture distribution
in the intake manifold and combustion chambers, excessive combustion chamber
deposits, and excessive varnish and sludge deposits in the engine.
Volatility characteristics of automotive gasolines are defined by ASTM
Specifications for Automotive Gasoline (D 439). The ASTM specification
provides five volatility grades with varying limits of maximum or minimum
vaporization tendency to adjust for seasonal and geographical changes in
temperature and the altitude in which the gasoline is to be used. These volatility
characteristics have been established on the basis of broad experience and
cooperation between gasoline suppliers and manufacturers of automotive
vehicles and equipment. Gasolines meeting this specification usually have
provided satisfactory performance in typical passenger car service. Obviously,
certain equipment or operating conditions may require or permit variations from
these limits. Also, inasmuch as each volatility grade covers a relatively broad
range of use temperatures, it is evident that these grade limits may be used to
formulate alternate intermediate limits for specific temperature levels or to
adjust for alternate gasoline distribution practices.

Other Properties
In addition to providing acceptable antiknock quality and volatility character-
istics, automotive gasolines must also provide for satisfactory engine cleanliness,
both physical and chemical. The following properties have a direct beating on
the overall performance of a gasoline.

Workmanship and Contamination

A finished gasoline is essentially a blend of petroleum fractions visually free of
undissolved water, sediment, and suspended matter. It is clear and bright when
observed at 70~ (2 I~ Physical contamination may occur during distribution
of the fuel. Control of such contamination is a matter requiring constant
vigilance. Solid and liquid contamination can lead to restriction of fuel metering
points, improper seating of inlet valves, corrosion, fuel line freezing, gel
formation, and filter plugging. ASTM Test for Water and Sediment in Distillate
Fuel by Centrifuge (D 2709), or ASTM Tests for Particulate Contaminant in
Aviation Turbine Fuels (D 2276/IP 216) may be used to determine the presence
of contaminants.

Sulfur Content and Copper Strip Corrosion

Crude petroleum contains sulfur compounds, most of which are removed
during refining. Currently, the average sulfur content of gasolines distributed in
the United States is about 0.03 percent by weight, with the maximum reported
values generally being less than 0.15 percent by weight.

Sulfur oxides formed during combustion may be converted to acids that

promote rusting and corrosion of engine parts and piston ring and cylinder wall
wear. Sulfur oxides formed in the exhaust are undesirable atmospheric
pollutants; however, the contribution of automotive exhaust to total sulfur
oxide emissions is negligible. Sulfur content is usually determined by ASTM Test
for Sulfur in Petroleum Products (Lamp Method) (D 1266/IP 107). Presence of
corrosive sulfur compounds can be detected by ASTM Test for Detection of
Copper Corrosion from Petroleum Products, by the Copper Strip Tamish Test
(D 130/IP 154).

Existent Gum and Stability

During storage, gasolines may oxidize slowly in the presence of air and form
undesirable oxidation products called gum. The gum is usually soluble in the
gasoline but may appear as a sticky residue on evaporation. These residues may
deposit on carburetor surfaces, intake valves, stems, and guides. ASTM
Specification for Automotive Gasoline (D 439) limits gasoline to a maximum of
5 mg of gum/100 ml of gasoline. ASTM Test for Existent Gum in Fuels by Jet
Evaporation (D 381/IP 131) is a test to determine the amount of existing gum.
(Many motor gasolines are deliberately blended with nonvolatile oils or additives
or both which remain as residues in the evaporation step of the existent gum
test. A heptane washing step is therefore necessary to remove these so that the
deleterious material or existent gum may be determined.)
Automotive gasolines have a negligible gum content when manufactured, but
may form gum during extended storage. ASTM Test for Oxidation Stability of
Gasoline (Induction Period Method) (D 525/IP 40) is a test to indicate the
tendency of a gasoline to form gum in storage. It should be recognized, however,
that the method's correlation may vary markedly under different storage
conditions and with different gasoline blends. Most automotive gasolines contain
special chemicals (antioxidants) to prevent oxidation and gum formation. Some
gasolines also contain metal deactivators for this purpose. Commercial gasoline is
not designed for abnormally severe conditions of storage. Gasoline purchased for
severe bulk storage conditions or for prolonged storage in vehicle fuel systems
generally has additional amounts of antioxidant and metal deactivator added.

Gravity
"Gravity" is a term used to denote the density of gasolines and is useful as a
means of identification. Two methods of expressing gravity commonly are used.
Specific gravity is the ratio of the mass of a given volume of gasoline at a
temperature of 60~ (15.6~ to the mass of an equal volume of water at the
same temperature. Typically, automotive gasolines have specific gravities
between 0.72 and 0.75 and American Petroleum Institute (API) gravities
between 65 and 57. API gravity is based on an arbitrary hydrometer scale and
related to specific gravity as follows

API gravity, deg = 141.5 - 131.5

sp gr (60/60"F)
Gravity of gasoline is determined using ASTM Test for Density, Specific
Gravity, or API Gravity of Crude Petroleum and Liquid Petroleum Products by
Hydrometer Method (D 1298/IP 160).

Rust and Corrosion

Filter plugging and engine wear problems are reduced by minimizing rust and
corrosion in fuel distribution and vehicle fuel systems when engines are idle.
Modifications of ASTM Test for Rust-Preventing Characteristics of Steam-
Turbine Oil in the Presence of Water (D 665/IP 135) are used to measure rust
protection of gasolines.

Hydrocarbon Composition
The major hydrocarbon-type constituents of gasoline are paraffins, olefins,
and aromatics, and they are identified by using ASTM Test for Hydrocarbon
Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption (D
1319112 156). Nonstandardized analytical procedures are available which permit
much more detailed analyses.

Additives
Gasoline additives are used to enhance or provide various performance features
related to the satisfactory operation of engines as well as to minimize gasoline
handling and storage problems. These compounds complement refinery pro-
cessing in attaining the desired level of product quality.
The amount and variety of additives used in gasolines have grown rapidly. For
many years, antiknocks were almost the only additives used; however, now the
list also includes combustion chamber deposit modifiers, antioxidants, metal
deactivators, corrosion or rust inhibitors, carburetor anti-icing additives, fuel line
antifreeze agents, gasoline detergents, gasoline dispersants, and identifying dyes.
Gasoline additives currently available are shown by class and function in Table
2.
TABLE 2-Commercial gasoline additives.

Class or Function Common Additive Type

1. Antiknock compounds-to improve re- lead alkyls, such as tetraethyllead, tetra-

search, motor and road octane quality. methyllead, and physical or reacted mix-
tures: organo-manganesecompounds, such
as methyl cyclopentadienyl manganese
tricarbonyl
2. Combustion deposit modifiers-to mini- organic or organo-metallic compounds
mize surface ignition, rumble, preigni- usually containing phosphorus
tion, and spark plug fouling

TABLE 2-Commercial gasoline additives.

(Continued.)

Class or Function Common Additive Type

3. Antioxidants-to minimize oxidation and phenylene diamine, pheno, and amino-

gum formation in gasoline and improve phenol compounds
handling and storage characteristics

4. Metal deactivators-to deactivate small diamine and aminophenol compounds

traces of copper and other metal ions
that are powerful oxidation catalysts.

5. Corrosion or rust inhibitors-to minimize derivatives of carboxylic, sulfonic, or phos-

corrosion and rusting of fuel system phoric acids, many of which have surface-
and storage and handling facilities active properties

6. Carburetor anti-icing additives-to mini- derivatives of carboxylic, sulfonic, or phos-

mize engine stalling due to ice accumu- phoric acid that have surface-active prop-
lation on the throttle erties: freeze point depressants such as
alcohols and glycols

7. Gasoline detergents-to remove or mini- amines and derivatives of carboxylic, sul-

mize or both the accumulation of fonic, or phosphoric acid having surface-
deposits in the throttle section of the active properties, some of which are
carburetor, which adversely affect the polymeric
metering characteristics

8. Gasoline dispersants-to extend PCV amines and low-molecular-weight synthetic

valve life, reduce engine sludge, and polymers: specific fractions of special oils
remove or minimize or both the accu-
mulation of deposits in the carburetor,
intake manifold, intake parts, and
underside of the intake valves

9. Deposit control additives-to combine derivatives, usually a m i n o - o r aminoimido-

the functions of classes 7 and 8 with of polymeric hydrocarbons of molecular
the additional effects of minimizing the weight in the 500 to 2000 range: used in
accumulation of varnish and sludge combination with special oils
deposits on piston rings and skirts,
rocker arms, and covers as well as
removing and minimizing gumming
deposits in the PCV system

I0. D y e s - to identify gasoline blends oil soluble and liquid dyes

NOTE-Some materials may also be marketed as multifunctional or multipurpose

additives performing more than one of the functions described in items 5, 6, 7, 8,
and 9.

Applicable ASTM Specification

D 439 Specification for Automotive Gasoline

Applicable ASTM/IP Standards

ASTM IP Title
D 86 123 Distillation of Petroleum Products
D 130 154 Detection of Copper Corrosion from Petroleum
Products by the Copper Strip Tarnish Test
D 323 Vapor Pressure of Petroleum Products (Reid Method)
D 381 131 Existent Gum in Fuels by Jet Evaporation
D 525 40 Oxidation Stability of Gasoline (Induction
Period Method)
D 665 135 Rust-Preventing Characteristics of Steam-Turbine Oil
in the Presence of Water
D 1266 107 Sulfur in Petroleum Products (Lamp Method)
D 1298 160 Density, Specific Gravity, or API Gravity of Crude
Petroleum and Liquid Petroleum Products
by Hydrometer Method
D 1319 156 Hydrocarbon Types in Liquid Petroleum Products
by Fluorescent Indicator Adsorption
D 2276 216 Particulate Contaminant in Aviation Turbine Fuels
D 2533 Vapor-Liquid Ratio of Gasoline
D 2699 237 Knock Characteristics of Motor Fuels by the
Research Method
D 2700 236 Knock Characteristics of Motor and Aviation-Type
Fuels by the Motor Method
D 2709 Water and Sediment in Distillate Fuels by Centrifuge

Bibliography

ASTM Manual for Rating Motor, Diesel, and Aviation Fuels, American Society for Testing
and Materials, 1974-1975.
Benson, J. D., Bigley, H. A., Jr., and Keller, J. L., "Passenger Car Driveability in Cool
Weather," SAE 710138, Society of Automotive Engineers, 1971.
Bettoney, W. E., Burt, J. G., and Scheule, H. J., "Factors Affecting the Performance of
Additives in Gasoline," Sixth World Petroleum Conference Proceedings, Section VI,
Paper 22, June 1963, pp. 111-130.
"CRC Revised Road Rating Techniques," Report No. 436, Coordinating Research
Council, Inc., July 1970.
Dimitriades, B., Eccleston, B. H., and Hum, R. W., "An Evaluation of the Fuel Through
Direct Measurement of Photochemical Reactivity of Emissions," Paper presented at the
62nd Annual Air Pollution Control Association Meeting, New York, June 1969.
Everett, R. L., "Measuring Vehicle Driveability," SAE 710137, Society of Automotive
Engineers, 1971.
Felt, A. E. and Kerley, R. V., "Engines and Effects of Lead-Free Gasoline," SAE 710367,
Society of Automotive Engineers, 1971.
Fuchs, E. J., "Unleaded Versus Leaded Fuel Results in Laboratory Engine Tests," SAE
710676, Society of Automotive Engineers, 1971.

Kerley, R. V. and Thurston, K. W., "Knocking Behavior of Fuels and Engines," SAE
Transactions, Vol. 64, 1956, p. 554.
Manual on Hydrocarbon Analysis, ASTM STP 332A, American Society for Testing and
Materials, 1968.
Pahnke, A. J. and Bettoney, W. E., "Role of Lead Antiknocks in Modem Gasolines," SAE
710842, Society of Automotive Engineers, 1971.
Sheahan, T. J., Doter, C. J., Jr., and Miller, C. O., "Detergent-Dispersant Fuel Performance
and Handling," SAE Paper 690516, Society of Automotive Engineers Mid-Year Meeting,
Chicago, May 1969.

Chapter 5 Aviation Fuels

Introduction
It is difficult to discuss aviation fuels without reviewing the development
history of the various types of aviation fuels and describing quality requirements
in terms of official specifications produced by the cooperative efforts of engine
manufacturers, airline operators, fuel suppliers, and appropriate government
departments. These documents define the required fuel properties and specify
the standard test methods to be used. The international validity of these
specifications and rigid enforcement ensures that fuels of uniform quality are
available on a worldwide basis for all types of aircraft engines.
It is not feasible to include full details of all major international specifications
in this chapter. Even summaries of the main requirements would be of little
permanent value, since these specifications are revised and updated frequently to
meet new aircraft needs or reflect changing supply situations. However, the basic
content of the various specifications covering similar grades of fuel do not differ
greatly, and, with few exceptions, the same fuel properties are controlled in
each. Typical examples of the physical and chemical property requirements
contained in current specifications are included for each of the main aviation
gasoline and jet fuel grades. Comprehensive and more up-to-date details of the
main internationally used specifications can be found in the Specification
Guides, issued and updated regularly by several major oil companies (see the
section on Fuel Specifications Guides).

Historical Development of Aviation Fuels

Aviation gasolines for spark-ignition engines reached their development peak
in the 1939 to 1945 war years. The advent of the gas turbine inhibited further
piston engine development, and, although large quantities of aviation gasoline
will be required for many years, quality test requirements are unlikely to change
significantly.
The first aviation gas-turbine engines were regarded as having noncritical fuel
requirements. Since ordinary illuminating kerosine was the original development
fuel, the first turbine fuel specifications were written largely around the
properties and test methods associated with this weU-established product. With
increased complexity in design of the engine and its control, fuel specification
tests have become inevitably more complicated and numerous. Current demands
for improved performance, economy, and overhaul life will indirectly continue
the trend towards additional tests; nevertheless, the optimum compromise
between fuel quality and availability is achieved largely by the current fuel
specifications.

53
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54 SIGNIFICANCE OF TESTS

Aviation Gasoline

Composition and Manufacture

Aviation gasoline is the most complex fuel produced in a refinery. Strict
process control is required to ensure that the stringent (and sometimes
conflicting) specifications are met for volatility, calorific value, and antiknock
ratings. In addition, careful handling is required during storage and distribution
to guard against various forms of contamination which can affect such properties
as volatility, gum values, and the copper strip corrosion test.
Aviation gasoline consists substantially of hydrocarbons. Sulfur-containing and
oxygen-containing impurities are limited strictly by specification and only
certain additives are permitted (refer to the section on Aviation Fuel Additives).
The main component of high-grade aviation gasolines is isooctane produced in
the alkylation process by reaction of refinery butenes with isobutane over the
acid catalysts. To meet volatility requirements for the final blend, a small
proportion of isopentane (obtained by superfractionation of light straight-run
gasoline) is added. The aromatic component required to improve rich mixture
rating is usually a catalytic reformate. The amount of aromatic components
added is limited indirectly by the gravimetric calorific value requirement.
Only grade 80 fuel can include a proportion of straight-run gasoline because
straight-run gasolines, which contain varying amounts of paraffins, naphthenes,
and aromatics invariably lack the necessary branch-chain paraffins (isoparaffins)
required to produce the higher grade fuels.

Specifications
Content-Aviation fuel specifications generally contain three main sections
covering suitability, composition, and chemical and physical requirements.
The suitability section is included as a safeguard against the possible failure in
service of a fuel which meets all the published physical and chemical tests in the
specification. It throws the onus on the fuel producer to obey the spirit as well
as the letter of the law. This philosophy is inherent in all aviation fuel
specifications.
The composition section stipulates that the fuel must consist entirely of
hydrocarbons except for trace amounts of approved additives, such as alkyl lead
antiknock additive, dyes, and oxidation inhibitors. Its main importance is in
listing the approved additives and, indirectly, in excluding any nonhydrocarbon
material which might be used to improve a critical property of the fuel at the
ultimate expense of other fuel properties.
The chemical and physical requirements section is the one most familiar to
users since it carefully defines the allowable limits for many chemical and
physical properties of the fuel and the standard test methods to be employed.
Fuel Grades-About six basic fuel grades have been in use since the 1939 to

1945 war period. In recent years, the diminishing demand for aviation gasoline
has led to a reduction in the number of grades available. With fewer fuel grades,
manufacturing, storage, and handling costs were reduced with subsequent
benefits to consumers. At present, three grades-80, 100, and 100 lowlead-are
specified in ASTM Specifications for Aviation Gasoline (D 910).
Specifications covering the various grades have been drawn up by a number of
bodies, and these have been revised as engine requirements changed. The most
commonly quoted aviation gasoline specifications are those issued by the U.S.
Department of Defense (military specifications), the British Ministry of Defense
(D Eng RD specifications), and the American Society for Testing and Materials
(ASTM D 910). Table 1 lists the main aviation gasoline specifications in current
use and indicates the various grades together with their identifying dye colors.
Due to the international nature of aviation activities, the technical require-
ments of all the Western specifications are virtually identical, and only
differences of a minor nature exist between the specifications issued in the
various major countries. The Russian GOST specifications (and their East
European equivalents) differ in the grades covered and also in respect to some of
the limits applied, but, in general, the same fuel properties are controlled, and
most test methods basically are similar to their Western equivalents (American
Society for Testing and Materials (ASTM) and Institute of Petroleum (IP)
standards). Russian aviation gasoline grades are summarized in Table 2.
Table 3 provides detailed requirements for aviation gasoline as contained in
ASTM Specification for Aviation Gasoline (D 910). In general, the main
technical requirements of all other Western specifications are virtually identical
to those in Table 3, although differences occur in the number of grades covered
and, in some cases, the amount of tetraethyllead (TEL) permitted. The various
grades within the specification differ fundamentally in only a few vital respects
such as color, antiknock ratings, and TEL content. This is true of all the Western
aviation gasoline specifications. The Russian GOST specification exhibits
additional grade-to-grade variations in properties such as distillation range and
vapor pressure.
The limits specified for Western grades of aviation gasoline were, in most cases,
dictated originally by military aircraft engine requirements. Since then, the
performance requirements for civil and military aircraft engines have changed
very little. However, improved fuel manufacturing techniques and the reduced
demand for certain grades has allowed fuel suppliers to produce modified fuel
grades more suited to market requirements. In some cases, the objective has been
to offer a technically superior fuel; in other cases, the aim has been the
reduction of production, storage, and handling costs by providing a fuel suitable
for use in a wider range of engine types than was possible with the standard
grades.
Motor gasoline is unsuitable for use in aircraft for both technical and safety
reasons. These reasons are discussed in Appendix I.

if)
z

z
TABLE 1-Aviation gasolines-main international specification grades. t~
ITI

O
"n

NATO D. ENG. RD. 2485 MIL-G-5572

m
Identifying Code British Ministry U.S. Department ASTM Pratt &
Color Number of Defense of Defense D 910 Whitney Use --t

Colorless F-13 73 9 blending, etc.

Colorless 9 ~ . 80 nonleaded 9 ~ . 80/87 ~ minor civil

and
Red F-12 80/87 80 9 ~ military

Blue F-15 91/96 100 iowlead 91/98 obsolete, except

100 lowlead
Green F-18 100/130 100/130 100 100/130 main civil

Brown . ~ 9 9 . 9 108/135 limited civil

Purple F-22 115/145 115/145 115/145 main military

TABLE 2-Russian aviation gasoline grades.

Specification Grade Color Use

GOST-1012 B. 70 colorless current

GOST-1012 B. 91/115 green obsolete (?)
GOST-1012 B. 95/130 yellow obsolete (?)
GOST-1012 B. 100/130 bright orange current
GOST-5761 BA (115[ 160) varies obsolete (?)

Characteristics and Requirements

Antiknock Properties-The various fuel grades are classified by their "anti-
knock" quality characteristics as determined in single-cylinder laboratory
engines. Knock, or detonation, in an engine is a form of abnormal combustion
where the air/fuel charge in the cylinder ignites spontaneously in a localized area
instead of being consumed progressively by the spark-initiated flame front.
Knocking combustion can damage the engine and give serious power loss if
allowed to persist. The various grades are designed to guarantee knock-free
operation for a range of engines from those used in light aircraft up to
high-powered transport and military types.
The antiknock ratings of aviation gasolines are determined in standard ASTM
and Cooperative Fuel Research Committee (CFR) laboratory engines by
matching their performance against reference blends of pure isooctane and
n-heptane. Fuel rating is expressed as an octane number (ON) which is defined as
the percentage of isooctane in the matching reference blend. Fuels of higher
performance than isooctane (100 ON) are tested against blends of isooctane with
various amounts of antiknock additive. The rating of such fuel is expressed as a
performance number (PN) which is defined as the maximum knock-free power
output obtained from the fuel expressed as a percentage of the power obtainable
on isooctane.
The antiknock rating of fuel varies according to the air/fuel mixture strength
employed. This fact is used in defining the performance requirements of the
higher grade aviation fuels. As mixture strength is increased (richened), the
additional fuel acts as an internal coolant and suppresses knocking combustion
which, in turn, permits a higher power rating to be obtained. Since maximum
power output is the prime requirement of an engine under rich takeoff
conditions, the "rich mixture performance" of a fuel is determined in a special
supercharged single-cylinder engine using ASTM Test for Knock Characteristics
of Aviation Fuels by the Supercharge Method (D 909/IP 119). Similarly,
economic cruising operation of an engine is obtainable with weak (lean) mixture
strengths. "Weak mixture performance" is determined by ASTM Test for Knock
Characteristics of Motor and Aviation-Type Fuels by the Motor Method (D
2700/IP 236).
Until 1975, ASTM Specification for Aviation Gasoline (D 910) designated

Grade 80 Grade 100 Grade 100 LL o~

63
Knock value, min octane number, lean rating 80 100 100 Z
"11
Knock value, rain octane number, rich rating 87 isooctane plus 1.28ml of isooctane plus 1.28ml of
tetraethyllead per gallon tetraethyllead per gallon
Z
0
Color red green blue rrl
0
Dye content -i'1
Permissible blue dye, max mg]gal 0.5 4.7 5.7 .-I
Permissible yellow dye, max mg/gal none 5.9 none m
Permissible red dye, max mg/gal 8.65 none none -.I
t..r
Tetraethyllead, max ml/gal 0.5 4.0 2.0

Net heat of combustion min Btu/lb 18 720 18 720 18 270

REQUIREMENTS FOR ALL GRADES
Distillation temperature, ~ (*C)
10 percent evaporated, max temperature 167 (75)
40 percent evaporated, rain temperature 167 (75)
50 percent evaporated, max temperature 221 (105)
90 percent evaporated, max temperature 275 (135)
Final boiling point, max "12(~ 338 (170)
Sum of 10 and 50 percent evaporated temperatures rain OF (*C) 307 (135)
Distillation recovery, rain percent 97
Distillation residue, max percent 1.5
Distillation loss, max percent 1.5
Acidity of distillation residue shall not be acid
Vapor pressure, max lb 7.0
Copper strip corrosion, max No. 1
Potential gum (5 h aging gum), max mg/100 ml 6
Visible lead precipitate, max, rag/100 ml 3
Sulfur, weight max, percent 0.05
Freezing point, max ~F (*C) -72 (-58)
Water reaction volume change not to exceed F2 ml
Permissible an tioxidants, max lb/1000 bbl 4.2

aASTM Specification for Aviation Gasolines (D 910).

aviation gasoline grades with two numbers, for example, "grade 100/130." The
lower number denoted an antiknock of 100 minimum by the weak mixture test
procedure, and the higher number 130 minimum by the rich mixture procedure.
Although the ASTM specification now uses only one number to designate grade
(the number from the weak mixture procedure), other specifications still use
both.
Volatility-All internal combustion engine fuels must be easily convertible
from storage in the liquid form to the vapor phase in the engine to allow
formation of the combustible air/fuel vapor mixture. If gasoline fuel volatility is
too low, liquid fuel enters the cylinders and washes lubricating oil from the walls
and pistons. This would increase engine wear and cause dilution of the crankcase
oil. Poor volatility can also give rise to critical maldistribution of mixture
strength between cylinders. If volatility is too high, fuel can vaporize in the fuel
tank and supply lines giving undue venting losses and the possibility of fuel
starvation through "vapor lock" in the fuel lines. The cooling effect due to rapid
vaporization of excessive amounts of highly volatile material also can cause ice
formation in the carburetor under certain conditions of humidity and air
temperature. Many modern aircraft have anti-icing devices on the engines
including the provision of carburetor heating, but not all light aircraft are so
equipped, and carburetor icing can be a serious problem.
Distillation (or volatility) characteristics are determined with a procedure
(ASTM D 86/IP 123) in which a sample of the fuel is distilled and the vapor
temperature recorded for the percentages of evaporation or distillation through-
out the range. Distillation points are selected to control volatility in the
following ways:
1. The 10 percent maximum and 40 percent minimum boiling points at 75~
(167~ control front-end volatility. The minimum value ensures that volatility is
adequate for normal cold starting. The maximum value is a safeguard against
vapor lock, fuel system vent losses, and carburetor icing.
2. The 50 percent minimum boiling to 105~ (221~ ensures that the fuel has
even distillation properties and does not consist of low-boiling and high-boiling
components only. This provides control over the rate of engine warm-up and
stabilization of slow-running conditions.
3. The minimum of 135~ (307~ for the sum of 10 percent and 50 percent
evaporated temperatures also controls the overall volatility and indirectly places
a lower limit on the 50 percent point. The clause is an additional safeguard
against excessive fuel volatility.
4. The 90 percent minimum to 135~ (275~ controls the proportion of less
volatile fuel components and, therefore, the amount of unvaporized fuel passing
through the engine manifold into the cylinders. The limit represents a
compromise between ideal fuel distribution characteristics and commerical
considerations of fuel availability which could be affected adversely by further
restriction of this limit.
5. The final boiling point of 170~ (3380F) excludes any undesirable heavy

material which could cause fuel maldistribution and also dilution of the
crankcase oil.
All spark-ignition engine fuels have a vapor pressure which is a measure of the
tendency of the more volatile fuel components to escape from the fuel tank in
the form of vapor. When an aircraft climbs rapidly to a high altitude, the
atmospheric pressure over the fuel is reduced and may become less than the
vapor pressure of the fuel at its prevailing temperature. If this occurs, the fuel
will "boil," and considerable quantities of the more volatile components will
escape as vapor through the tank vents.
Vapor pressure for aviation gasolines is controlled and determined by the
ASTM Test for Vapor Pressure of Petroleum Products (Reid Method) (D 323/IP
69). Limits are between 5.5 and 7.0 psi. The lower limit is an additional check
on adequate volatility for engine starting. The upper limit guards against
excessive vapor formation during high-altitude flight and "weathering" losses in
storage.
Density-The density of a fuel is a measure of the mass per unit volume. It is
used in fuel load calculations since weight or volume fuel limitations (or both)
may be necessary according to the type of aircraft and flight pattern involved. In
most cases, the volume of fuel which can be carried is limited by tank capacity.
To achieve maximum range, a high-density fuel is preferred because it provides
the greatest heating value per gallon (litre) of fuel. The heating value per pound
(kilogram) of fuel, however, falls slightly with increasing density so that on
occasions where the weight of fuel which can be carried is limited (for example,
to achieve maximum pay load), it can be advantageous to use a lower density
fuel provided adequate tank volume capacity is available.
In the United States, it is common to specify fuel density in terms of
American Petroleum Institute (API) gravity. API gravity may be determined
directly by use of ASTM Test for API Gravity of Crude Petroleum and
Petroleum Products (Hydrometer Method) t~D 287) or calculated from specific
gravity by the following formula

API gravity, deg = 141.5 - 131.5

sp gr 60/60"F
No reference temperature is needed since 60~ is specified in the formula.
Most British and other European specifications define the fuel density in terms
of the relative density under standard conditions. Relative density is the ratio of
the mass of a given volume of fuel to the same volume of water under specified
conditions. ASTM Test for Density, Specific Gravity, or API Gravity of Crude
Petroleum and Liquid Petroleum Products by Hydrometer Method (D 1298[IP
160) may be used to determine relative density.
Heat of Combustion -Heat of combustion is the quantity of heat liberated by
the combustion of a unit quantity of fuel with oxygen. Heat of combustion
affects the economics of engine performance. The specified minimum value is
normally a compromise between the conflicting requirements of maximum fuel

availability and good fuel consumption characteristics. ASTM Test for Heat of
Combustion of Liquid Hydrocarbon Fuels (General Bomb Method) (D 240/IP
12) or ASTM Test for Heat of Combustion of Hydrocarbon Fuels by Bomb
Calorimeter (High-Precision Method) (D 2382) provide a means for direct
measurement of fuel energy content.
An alternative criterion for energy content is the "Aniline Gravity Product"
(AGP) which is related to calorific value and more easily determined. AGP is the
product of the gravity (expressed in degrees API) and the aniline point of the
fuel as determined by ASTM Test for Aniline Point and Mixed Aniline Point of
Petroleum Products and Hydrocarbon Solvents (D 611/IP 2). Aniline point is the
lowest temperature at which the fuel is miscible with an equal volume of aniline
and is inversely proportional to the aromatic content. The relationship between
AGP and calorific value is given in ASTM Test for Estimation of Net Heat of
Combustion of Aviation Fuels (D 1405[IP 193).
No great variation in either density or heat of combustion occurs in modern
aviation gasolines since they depend on hydrocarbon composition which is
already closely controlled by other specification properties. Both factors have
relatively greater importance with jet fuels as discussed later.
Freezing Point-Maximum freezing point values are set for all types of aviation
fuel as a guide to the lowest temperature at which the fuel can be used without
risk of separation of solidified hydrocarbons. Such separation could lead to fuel
starvation through clogging of fuel lines or filters and loss in available fuel load
due to retention of solidified fuel in the tanks. The standard freezing-point test
involves cooling the fuel slowly until a slurry of crystals form throughout the
fuel and noting the temperature at which all crystals disappear on rewarming the
fuel. Freezing points are determined by ASTM Test for Freezing Point of
Aviation Fuels (D 2386/IP 16).
Storage Stability-Aviation fuel must retain its required properties for long
periods of storage in all kinds of climates. Unstable fuels oxidize and form
polymeric oxidation products which remain as a resinous solid or "gum" on
induction manifolds, carburetors, valves, etc. as the gasoline is evaporated.
Formation of this undesirable gum must be limited strictly, and it is assessed by
the existent and accelerated (or potential) gum tests.
The existent gum value is the amount of gum actually present in the fuel at
the time of the test. It is determined by ASTM Test for Existent Gum in Fuels
by Jet Evaporation (D 381/IP 131). The accelerated gum test, ASTM Test for
Oxidation Stability of Aviation Fuels (Potential Residue Method) (D 873/IP
138), predicts the possibility of gum forming during protracted storage and
decomposition of the antiknock additive.
To ensure that the strict limits of the stability specification clauses are met,
aviation gasoline components are given special refining treatments to remove the
trace impurities responsible for instability. In addition, limited quantities of
approved oxidation inhibitors are added. Currently, little trouble is experienced
with gum formation or degradation of antiknock additive.

Sulfur Content-Total sulfur content of aviation gasoline is limited to 0.05

percent weight maximum because most sulfur compounds have a deleterious
effect on the antiknock efficiency of alkyl lead compounds. If sulfur content
were not limited, specified antiknock values would not be reached for highly
leaded grades of aviation fuel. Sulfur content is estimated by ASTM Test for
Sulfur in Petroleum Products (Lamp Method) (D 1266/IP 107).
Some sulfur compounds can have a corroding action on the various metals of
the engine system. Effects vary according to the chemical type of sulfur
compound present. Fuel corrosivity is assessed by its action on a copper strip
used in ASTM Test for Detection of Copper Corrosion from Petroleum Products
by the Copper Strip Tarnish Test (D 103/IP 154).
Water Reaction-Federal Method D 3251 and ASTM Test for Water Reaction
of Aviation Fuels (D 1094) are the historical tests for water reaction. The
original intent of the tests was to prevent the addition of high octane and water
soluble components such as ethyl alcohol to aviation gasoline. The test methods
involved shaking 80 ml of fuel with 20 ml of water under standard conditions
and observing phase volume changes and interface condition. Many specifica-
tions for aviation gasoline now have phase separation requirements in addition to
those for volume changes and interface condition. Water Reaction of Aviation
Fuels (IP 289) rates all three of these criteria.

Aviation Turbine Fuels (Jet Fuels)

Background
Aircraft gas-turbine engines require a fuel with quite different properties from
those for aviation gasoline. Probably the greatest difference is that antiknock
value is of no importance and is replaced by the need for a heating fuel of good
combustion characteristics and high-energy content. Illuminating kerosine was
chosen as the fuel for the first generation of engines largely because of its ready
availability, low-fire hazard, good combustion properties, and, not least, the
war-time need to conserve gasoline supplies. As engine and fuel system designs
have become more complicated, so have the fuel specifications become more
varied and restrictive. Jet fuel quality worldwide is dictated on the commercial
side largely by the British Ministry of Defence (D Eng RD) specifications and
those of the airlines, engine manufacturers, and industry groups such as ASTM
and the International Air Transport Association (IATA). Military jet fuel is
dictated largely by the U.S. Department of Defense (U.S. MIL) specifications
and corresponding D Eng RD specifications. Grades of commercial and military
fuels are identical virtually in basic properties and differ mainly in the types of
additives permitted. The only significant exception is the fuel type used in
Russia and most East European countries. These grades are based on USSR state
standards (GOST specifications) and differ in several major respects from their
nearest "Western" equivalents.
Only two basic types of jet fuel are in general use worldwide: the kerosine

type and the wide-cut gasoline type. The former is a modified development of
the illuminating kerosine originally used in gas-turbine engines. The latter is a
wider boiling-range material which includes some gasoline fractions developed
primarily in the United States to improve on availability from crude oil. In
addition, a number of specialized fuel grades are required for limited military use
and as referee fuels.

Fuel Developments
Jet fuel development has differed somewhat in Europe and America, but, in
recent years, the British and U.S. specification requirements have been brought
gradually into line in the interests of military (North Atlantic Treaty
Organization) (NATO) standardization. Because of the differences in early
development philosophy, a brief historical review of the way the quality
requirements have developed in different countries is a necessary preamble to a
discussion of the test requirements and their significance.
British Jet Fuels-The British jet fuel specification D Eng RD 2482, issued
shortly after World War II, was based on the experience gained from operations
with illuminating kerosine. It was rather restrictive on aromatics (12 percent
max), sulfur content (0.1 percent max), and calorific value (18 500 Btu/lb rain)
but contained no burning quality requirements. Although further experience
permitted relaxation of some of the early requirements, it became necessary to
introduce additional tests as new service problems were encountered and amend
some existing test limits. For example, the progressive development of more
powerful turbine engined aircraft with greater range and altitude performance
made the -40"C (-40~ freezing point limit of the D Eng RD 2482 type fuel
inadequate to ensure that hydrocarbon wax would not separate from fuel during
prolonged cold soaking at altitude. A new D Eng RD 2494 specification was
then issued with a maximum freezing point of - 50~ (- 58~ This fuel quality
still remains the optimum compromise between engine development require-
ments, fuel cost, and strategic availability.
While D Eng RD 2494 (Avtur) is now the standard British civil jet fuel, a new
D Eng RD 2453 specification (Avtur/FSH) was issued in 1967 incorporating
anti-icing and corrosion inhibitor additives in line with the latest U.S. military
and NATO requirements.
A less volatile kerosine fuel for use in naval carrierborne aircraft with a
flashpoint of 140~ min was defined originally by the D Eng RD 2488
specification. In answer to the need for improved low-temperature performance,
a later specification, D Eng RD 2498 (Avcat), introduced a modified
freezing-point requirement of - 48*C (- 55~ max, as compared with the 40~
(- 40~ for the former D Eng RD 2488 specification.
Because crude oils giving high-gasoline yields are not in abundant supply,
wide-range turbine fuel was never used in the United Kingdom to the extent it is
in the United States. However, the D Eng RD 2486 (Avtag) specification was
introduced in 1951 to cover a fuel grade basically identical to the American

wide-cut JP-4 grade (MIL-T-5624). This fuel grade has been used widely,
particularly under NATO arrangements. More recently, the grade has been
brought completely into line with the American equivalent with the issue in
1967 of the D Eng RD 2454 specification (Avtag/FS 11) which incorporates
anti-icing and corrosion inhibitor additives.
A feature of all the above D Eng RD specifications not at present included in
their U.S. military equivalents is that electrical conductivity improver additive is
permitted by user agreement.
Table 4 lists the British D Eng RD specifications for aviation fuels and related
products.
American Military Jet Fuels-In the United States, jet fuel development
followed a different pattern. The early U.S. specification for JP-1 called for a
paraffinic kerosine with a freeze point of -60~ (76T). These restrictive
requirements limited the availability of the fuel, and the grade soon became
obsolete. JP-1 has been superseded by a series of military wide-cut fuels.
The wide-range distillate type of turbine fuel originated in the United States
where it was realized that in rimes of military emergency the fuel supply could
be increased considerably if more of the readily available gasoline fractions were
incorporated into jet fuel to supplement the basic kerosine component. This
philosophy is the converse of the World War II choice of kerosine for the early
jet engines which was chosen in order to conserve gasoline stocks for the then
predominate piston-type aircraft engines.
The first wide-cut grade (JP-2) allowed a Reid Vapor Pressure of 2 lb max to
increase availability through the inclusion of heavy gasoline fractions. Experi-
ence suggested that a further increase in volatility might be tolerated to give an
advantage in engine starting, and the specification of JP-3, therefore, was
introduced with vapor pressure limits of 5.0 to 7.0 lb. However, operational
problems due to high-venting losses at altitude led finally to the formulation of
the JP-4 specification in 1950. With slight modifications to the specific gravity
and distillation requirements, plus the inclusion of certain additives, JP-4
remains the main fuel for military jet aircraft in the United States and many
other countries.
Kerosine type jet fuels have not achieved any significant military use in the
United States with the exception of JP-5, a low-volarility kerosine fuel used by
naval aircraft during shipboard operations. JP-6 was a light kerosine type fuel of
improved thermal stability intended for a supersonic bomber but has been
declared obsolete. JP-7 is another low-volatility, high-flash point kerosine with
enhanced combustion and thermal stability properties that was developed as a
fuel for very high-performance (Mach 3) aircraft.
Concern over combat hazards when using wide-cut fuels has led the
Department of Defense to reconsider the use of standard kerosine type fuel.
Service trials on a proposed new JP-8 grade fuel have been completed. Although
the trials were successful, the advantages to be gained from switching from JP-4
to JP-8 may be outweighed by the undesirable impact on world jet fuel supplies

British
Joint NATO
D ENG RD Services Code
Specification Designation Number Type Use

2451 AL-31 S-748 ethylene glycol monmethyl ether fuel system icing inhibitor
2453 Avtur/FS 11 F-34 kerosine, with FSII military
2454 Avtag/FS 11 F-40 widecut, with FSII military
2482 Avtur/40 F-30 kerosine, -40~ freeze point obsolete
2485 Avgas ...a aviation gasoline (several grades) general t')
-r
2486 Avtag F-45 wide cut civil >
2488 Avcat/40 F-42 high-flash kerosine, -40"C freeze point obsolete -4
2491 AL-9/24/28 methanol and water/methanol mixtures thrust augmentation fluids m
2492 Avpin S'-746 isopropyl nitrate turbine engine starter fuel ol
2494 Avtur (50) F-35 kerosine, -50~ freeze point civil o
2495 kerosine rocket fuel obsolete z
2496 Avcos cold-starting fuel for piston engine obsolete <
2498 Avcat (4S) F~4 high-flash kerosine, -48~ freeze point naval carrier aircraft
-4
aSee table 5
z
-11
c
m
I-"
t,o

O~
O'1

that might occur if a major international user should change from a wide-cut fuel
to a kerosine type.
Table 5 lists the U.S. military specifications for jet fuels and related products.
American Civil Jet Fuels-The basic civil jet fuel specification used in the
United States is ASTM Specification for Aviation Turbine Fuels (D 1655) which
outlines requirements for three types of fuel: Jet A, a nominal -40~
freeze-point kerosine; Jet A-I, a nominal - 50~ freeze-point kerosine; and Jet B,
a wide-cut gasoline grade (similar to JP-4 but without certain additives).
Jet A is used internally within the United States by all domestic operators,
while Jet A-1 is the standard grade used for international flights. To differentiate
from the military fuel grades (which often contain special additives not used
commonly in civil fuels), the terms Jet A-1 and Jet B are now used worldwide to
describe the basic kerosine and wide-cut gasoline types of civil jet fuel although
the latter is only in fairly limited civil usage at present.
A number of jet fuel specifications also are issued by the major U.S. aircraft
engine manufacturers and certain airlines. These are either similar to the
equivalent ASTM grades or are less restrictive versions of one or more ASTM
grades.
Russian Jet Fuels-A wide range of jet fuels covered by various Russian GOST
specifications are manufactured for both civil and military use. The main grades
are covered also by similar specifications issued by a number of other East
European countries. While Russian jet fuel characteristics in some cases differ
considerably from those of jet fuels used elsewhere, the main properties are
controlled by test methods very similar to their ASTM/IP equivalents. A few
additional test methods, for example, iodine number (related to the olefin
content), hydrogen sulfide content, free sulfur content, and filtration rate are
sometimes included. Thermal stability is usually specified also by a completely
different test procedure.
Limited information is available on some Russian fuel grades, and only a few
of these grades are in regular civil use. Brief details are shown in Table 6. T-I,
TS-1, and more recently T-7 (plus their East European equivalents) are the only
grades normally offered to international airlines at civil airports. In practice,
these grades usually are found to meet the equivalent "Western" kerosine
specifications with the exception of having a lower-flash point (often about
85/95~ and sometimes a poor odor because of high-mercaptan-sulfur content.
Other Foreign Jet Fuels-A number of other countries also issue jet fuel
specifications. The most important of these are indicated in Table 7. In most
cases, these specifications virtually are identical with their American or British
equivalents, particularly in the case of countries committed to multinational
military agreements (for example, NATO or Southeast Asia Treaty Organization)
(SEATO). However, some countries incorporate special national requirements
(for example, the Canadian specifications formally require the mandatory
addition of an electrical conductivity improver additive and some Australian
specifications include a microbiological test requirement). Since France with-

First
Specification Issued Grade Type Use

AN-F-32 1944 JP-1 very low-freeze kerosine obsolete

MIL-F-5616 1950
AN-F-34 1945 JP-2 wide cut (RVP m a x 2 lb) obsolete
AN-F-58 1947 JP-3 wide c u t (RVP 3 to 7 lb) obsolete
MIL-F-5624 1950
MIL-T-5624 1950 JP-4 wide cut (RVP 2 to 3 lb) air force standard
MIL-T-5624 1950 JP-5 high-flash kerosine naval carrier aircraft
MIL-F-25656 1956 JP-6 light kerosine (thermally stable) supersonic b o m b e r s (obsolete)
MIL-T-38219 1965 JP-7 low-volatility kerosine (special properties) very high p e r f o r m a n c e aircraft
r
MIL-T-83133 1968 JP-8 kerosine proposed " s a f e t y " fuel -r
"v
R E L A T E D SPECIFICATIONS -I
i'n
MIL-F-5161 ... referee JP-4 and JP-5 g r o u n d test fuels
ol
MIL-F-5572 Avgas aviation gasoline (several grades) military standard
0
MIL-I-25017 . . . chemical materials fuel soluble corrosion inhibitor z
MIL-F-26524 9 9 thermally stable kerosine flight test fuel
MIL-F-25558 R J-1 high-density kerosine air force ramjet fuel
--4
MIL~-25576 RP-1 narrow-cut kerosine rocket fuel
MIL-J-27275 9. 9 referee JP-6 g r o u n d test fuel Z
"11
MIL-I-27686 FS11 ethylene glycol m o n o m e t h y l ether fuel s y s t e m icing inhibitors
i'n
MIL-F-82522 R J-4 T-H dimer navy ramjet fuel I"-

TABLE 6-Russian/et fuel specifications.

Specification Grade Type Use

GOST-10227 T-1 kerosine from low-sulfur crude (SR) general

GOST-10227 TS-1 kerosine from high-sulfur crude (SR) most common civil
GOST-10227 T-2 wide-cut fuel (SR) a military (?)
T-4 wide cut, high in aromatics unknown
GOST'9"145 T-5 heavy kerosine unknown
T-6 heavy paraffinic kerosine ~HT)b unknown
GOST'l'2308 T-7 very low sulfur TS-1 (HT)-- replacing TS-1
9 T-8 low-volatility kerosine (HT) b supersonic civil

NOTE-TS-1 appears as TC-1 in Russian alphabet.

T-8 is close equivalent to western jet A-1 in all respects.
aSR = straight run.
bHT = hydro treated.

TABLE 7-Minor national aviation fuel specification.

Count/f Jet Fuels Av~tion Gasolines

Kerosine Wide-cut High-Flash

Grade (Avtur) (JP-4) Kerosine 80/87 100/130 115/145

Australia
DEF (AUST) 208 ... 207 215 215 215

Belgium
BA-PF 3 2 ... 5 5 5

Brazil
CNP-08 QAV-1 QAV-4 ...

Canada
3-GP 23 22 24 25 25 25

France
AIR 3405 3407 3404 3401 3401 3401
(TRO) (TR4) (TR5)

Germany
VTL-9130 ... 006 010 001 003 004

Italy
AM-C ... 142 143 102 104 105

Sweden
FSD-MO-754 375 277 ... 236 255 259

drew f r o m N A T O , the F r e n c h specifications have b e e n m o d i f i e d in some

respects f r o m their earlier c o n t e n t .

International Standard Specifications-Modern civil aviation recognizes few

frontiers. Therefore, there is a need for aviation fuels with similar characteristics
to be available in all parts of the world. This is important especially to
international carriers.
Recognizing the potential problems that might arise, the IATA issued two
specifications-one for a kerosine type jet fuel and the other for a wide-cut
gasoline type jet fuel. Although less restrictive, the IATA specifications are
identical in fundamental requirements to those in the main British and American
military specifications. A number of major airlines have adopted the IATA
guidance.
Despite efforts to standardize jet fuels, there are still a number of differences
in minimum quality standards even among the major internationally used
specifications. These differences are of little significance to military organiza-
tions, because they normally purchase jet fuel against their own national
specifications or American or British specifications. Similarly, domestic airlines
are not affected since their fuel supplies are relatively uniform within the
country in which they fly. International air carriers do experience problems
because they often purchase more fuel offshore than they use domestically.
When purchasing jet fuel in other countries, international airlines are faced
with a confusing array of names, definitions, and specifications for jet fuels. As a
partial solution, airlines quote their Jet A-1 requirements against either the D
Eng RD 2494, ASTM D 1655, or IATA specifications. Jet B requirements are
stated against D Eng RD 2486, U.S. Mil-T-5624, ASTM D 1655, or IATA
specifications. Even with these specifications as guidelines, allowable additive
contents frequently are defined poorly.
To alleviate the international air carriers' problems, a workilag group
representative of all major international oil companies that supply fuels outside
North America has drawn up some specifications for jet fuels which are
published under the title: Aviation Fuel Quality Requirement for Jointly
Operated System. The specifications provide precise quality requirements that
incorporate the most stringent requirements of each of the many international
specifications.

Specification Requirements
The requirements for jet fuels stress a different combination of properties and
tests than those required for aviation gasoline. The same basic controls are
needed for such properties as storage stability and corrosivity, but the gasoline
antiknock tests are replaced by tests directly and indirectly controlling energy
content and combustion characteristics. Therefore, it is convenient to deal with
the chemical properties (and composition) separately from the physical
properties of jet fuel.
Chemical Properties and Composition-Jet fuels consist entirely of hydro-
carbons except for trace quantities of sulfur compounds and approved additives.
Since jet fuels are produced normally by blending straight-run distillate

components, they contain virtually no olefins. Olefins are limited by specifica-

tions and usually determined by ASTM Test for Hydrocarbon Types in Liquid
Petroleum Products by Fluorescent Indicator Adsorption (D 1319/IP 156)
although olefins in some specifications are controlled by the ASTM Test for
Bromine Number of Petroleum Distillates and Commerical Aliphatic Olefins by
Electrometric Titration (D 1159[IP 130).
The amounts of aromatics also are limited directly because they do not bum
as clean as other hydrocarbon types. High aromatics can cause smokiness and
carbon deposition in the engines. They also degrade elastomers in the fuel
system and increase the luminosity of the combustion flame, which can
adversely affect the life of certain designs of combustion chamber. Aromatic
content also is determined by ASTM Method D 1319/IP 156.
The principal nonhydrocarbon components permitted in jet fuels are sulfur
compounds. The amount and type of sulfur compound varies with crude source,
but normally there is no difficulty in meeting the specified total sulfur content
which ranges in level between 0.2 and 0.4 percent by weight maximum. ASTM
Method D 1266/IP 107 is used for total sulfur.
Experimental evidence indicates high-sulfur levels may adversely affect the
carbon-forming tendency in combustion chambers, and the presence of large
amounts of sulfur oxides in the combustion gases may lead to corrosion
problems. Direct corrosivity of sulfur compounds is controlled by the copper
strip test (ASTM D 130/IP 154), although this particular procedure is not always
capable of reflecting fuel corrosivity towards all metals used in fuel systems.
Mercaptan sulfur content of jet fuels is limited to a maximum in the range of
0.001 to 0.005 percent by weight because of objectionable odor, adverse effect
on certain fuel system elastomers, and corrosiveness toward fuel system metals.
Mercaptan sulfur is determined by ASTM Test for Mercaptan Sulfur in Aviation
Turbine Fuels (Color-Indicator Method) (D 1219/1P 104) or by the IP Doctor
Test (ASTM D 484/IP 30).
Mercaptan removal from fuel blends can be affected by sweetening processes
which convert them to less objectionable, involatile disulfides. Most sweetening
processes use a chemical reagent which does not affect any reduction in total
sulfur content. The more common hydro fining procedure, however, catalytically
converts all sulfur compounds to gaseous hydrogen sulfide which is then stripped
from the refined fuel. Improper control of any sweetening process can produce
trace materials which will subsequently cause service trouble even though the
fuel meets all the specified physical and chemical tests.
No direct limits are placed on the presence of oxygenated materials. However,
acidic compounds such as phenols and naphthenic acids are controlled by a
variety of acidity tests. Acidity limits specified normally vary with the test
method required. ASTM Test for Neutralization Number by Color-Indicator
Titration (D 974/IP 139) is used widely for total acidity, but it is not
sufficiently sensitive to detect trace acidic materials that adversely affect the
water separating properties of fuel. Therefore, a modified version of ASTM D

974/IP 139 is used in some U.S. military specifications. ASTM Specification for
Aviation Turbine Fuels (D 1655) permits the use of either of two methods for
determining total acidity-D 974/IP 139 or ASTM Test for Total Acidity in
Aviation Turbine Fuel (D 3242).
Oxygen-containing impurities in the form of gum are limited by ASTM Test
for Existent Gum in Fuels by Jet Evaporation (D 381/IP 131) and ASTM Test
for Oxidation Stability of Aviation Fuels (Potential Residue Method) (D 873[IP
138). In practice, the current refined, straight-run fuels have gum values much
lower than specification limits.
The various approved additives for jet fuels include oxidation inhibitors to
improve storage stability, copper deactivators to neutralize the adverse effect of
copper on fuel stability, and corrosion inhibitors intended for the protection of
storage tanks and pipelines. An anti-icing additive (fuel system icing inhibitor) is
called for in many military fuels, and an electrical conductivity improver
(antistatic additive) may be required to minimize fire and explosion risks due to
electrostatic discharges in installations and equipment during pumping opera-
tions. Details of the various approved additives (mandatory or optional) are
included in every specification and discussed in later paragraphs.
Physical Properties-Contaminants-Since jet fuels are subjected to wide
variances in temperatures and pressures, their physical properties must be
controlled closely. In addition, modem fuel systems demand a fuel free from
water, dirt, and other foreign contaminants. To deliver fuel in the desired
condition requires stringent storage and handling procedures. Fine particle
filtration and water separation facilities generally are provided to ensure that dirt
and free water contents are well below maximum levels of 1.0-mg/litre dirt and
30-ppm free water called for by IATA or the more stringent U.S. military
specifications of 1.0-mg/gal dirt and 15 to 20-ppm free water.
ASTM Tests for Particulate Contaminant in Aviation Turbine Fuels (D
2276/IP 216) provide field quality control of dirt content. It can be supple-
mented by a visual assessment of membrane appearance after test against ASTM
color standards.
Another contamination problem is that of microbiological growth activity
which can give rise to service troubles of various types. This problem generally
can be avoided by the adoption of good housekeeping techniques, but major
incidents in recent years have led to the development of several microbiological
monitoring tests for aviation fuel. In one of these, fuel is filtered through a
sterile membrane which is cultured subsequently for microbiological growths.
Other tests employ various techniques to detect the presence of viable
microbiological matter, but none of the tests have yet been standardized.
Free water in jet fuels can be detected with a variety of field test kits
developed over the years by major oil companies. These tests generally rely on
color changes produced when chemicals go into aqueous solution. ASTM Test
for Undissolved Water in Aviation Turbine Fuels (D 3240) has been standardized
recently. It employs a device called the Aqua-Glo II which is capable of more

precise quantitative results than chemical tests although simplicity is sacrificed.

The total water content of aviation fuels (free and dissolved water) can be
determined by the ASTM Test for Water in Liquid Petroleum Products by Karl
Fischer Reagent (D 1744). However, the basic procedure has inadequate
precision, and improvements are needed.
Density and Heat of Combustion-Density and heat of combustion are
important properties of jet fuel since they control the total energy content of
the fuel on a weight or volume basis or both. Specific gravity and calorific values
vary somewhat according to crude source. Paraffinic fuels have a slightly lower
specific gravity but higher gravimetric calorific value than those from naphthenic
crudes. Naphthenic fuels have superior calorific values on a volume basis
(Btu/gal). The relative importance of energy content on a weight or volume basis
depends on the design and flight pattem of an aircraft which could be either
weight or volume limited in its fuel load.
Volatility-Volatility is one of the more obvious differences between kerosine
and wide-cut jet fuels. The low-volatility requirements for kerosine are
controlled by flash point and a small number of distillation points determined
by ASTM Test for Distillation of Petroleum Products (D 86/IP 123). Distillation
tests and the ASTM Test for Vapor Pressure of Petroleum Products (Reid
Method) (D 323/IP 123) control the higher volatility of wide-cut jet fuels. The
overall effect of the volatility tests is to give a reasonable compromise between
safety, combustion efficiency, and fuel availability.
Distillation points of 10, 20, 50, and 90 percent are specified in various ways
to ensure that a properly balanced fuel is produced with no undue proportion of
light or heavy fractions. The distillation end point excludes any heavy material
which would give poor fuel vaporization and ultimately affect engine combus-
tion performance.
Flash point is a guide to the fire hazard associated with the fuel. Flash point
can be determined by several test methods which are not always directly
comparable. The minimum flash point in British military specifications is usually
defined by the Abel Method (iP 170), except for high-flash kerosine where the
ASTM Test for Flash Point by Pensky-Martens Closed Tester (D 93/IP 34) is
specified. The ASTM specification for aviation turbine fuels calls for Test for
Flash Point by Tag Closed Tester (D 56), or ASTM Test for Flash Point of
Aviation Turbine Fuels by Setaflash Closed Tester (D 3243).
Low-Temperature Properties-Jet fuels must have acceptable freezing points
and low-temperature pumpability characteristics so that adequate fuel flow to
the engine is maintained during long cruise periods at high altitude. ASTM Test
for Freezing-Point of Aviation Fuels (D 2386/IP 16) and its associated
specification limits guard against the possibility of solidified hydrocarbons (wax)
separating from chilled fuel and blocking fuel lines, filters, nozzles, etc.
The viscosity of fuels at low temperature is limited to ensure that adequate
fuel flow and pressure are maintained under all operating conditions and that
fuel injection nozzles and system controls will operate down to design

temperature conditions. Viscosity can affect significantly the lubricating prop-

erty of the fuel which has an influence on fuel pump service life. Viscosity is
determined by ASTM Determination of Kinematic Viscosity of Transparent and
Opaque Liquids (and the Calculation of Dynamic Viscosity) (D 445/IP 71).
Combustion Quality-Combustion quality is largely a function of the
hydrocarbon composition of the fuel. Paraffins have excellent burning properties
in contrast to those of aromatics (particularly the heavy polynuclear types).
Naphthenes have intermediate combustion characteristics that are nearer to
those of paraffins. Because of compositional differences, jet fuels of the same
class can vary widely in burning quality as measured by smoke formation,
carbon deposition, and flame radiation.
Smoke point is determined by ASTM Test for Smoke Point of Aviation
Turbine Fuels (D 1322/IP 57). The combustion performance of wide-cut fuels
correlates well with smoke point when a fuel volatility factor is included because
carbon formation tends to increase with boiling point.
The smoke-point test alone is not universally accepted as a reliable criterion
for combustion performance. An alternative test generally accepted is the ASTM
Test for Luminometer Numbers of Aviation Turbine Fuels (D 1740). This test
was developed because combustion chamber life is shortened in certain jet
engines if a fuel produces luminous flames that result in high-liner temperatures.
The luminometer number test apparatus is essentially a smoke-point lamp
modified to include a photoelectric cell for flame radiation measurement and a
thermocouple arrangement to measure temperature rise across the flame.
Water. Retention and Separating Properties-Because of their higher density
and viscosity, jet fuels tend to retain fine particulate matter and water droplets
in suspension for a much longer time than aviation gasoline.
Jet fuels also can vary considerably in their tendency to pick up and retain
water droplets or to hold fine water hazes in suspension depending on the
presence of trace surface active impurities (surfactants). Some of these materials
(such as sulphonic and naphthenic acids and their sodium salts) may originate
from the crude source or from certain refinery treating processes. Others may be
picked up by contact with other products during transportation to the airfield,
particularly in multiproduct pipelines. These latter materials may be natural
contaminants from other less highly refined products (for example, heating oils)
or may consist of additives from motor gasolines (such as glycol-type anti-icing
agents). In addition, some of the additives specified for jet fuels also have surface
active properties. Examples of these are corrosion inhibitors and electrical
conductivity improvers.
The presence of surfactants can also impair the performance of the water
separating equipment (filter/separators) used in fuel handling systems to remove
traces of free (undissolved) water. Very small traces of free water can affect
adversely jet engine and aircraft operations in several ways. The water retention
and separating properties of jet fuels have become a critical quality consideration
in recent years.

The standard water reaction test (ASTM D 1094/IP 289) for jet fuels is the
same as for aviation gasolines, but the interface and separation ratings are
defined more critically. Test assessment is by subjective visual observation.
Although sufficiently precise when made by an experienced operator, the test
can cause rating difficulties under borderline conditions. As a consequence, a
more objective test now is included in many specificiations. It is ASTM Test for
Water Separation Characteristics of Aviation Turbine Fuels (D 2550).
Thermal Stability-Although the conventional (storage) stability of aviation
fuel has long been defined and controlled by the existent and accelerated gum
tests, another test is required to measure the stability of a fuel to the thermal
stresses which can arise during sustained supersonic flight and in some
high-subsonic applications. In high-speed flight, the fuel is subjected to
considerable heat input due to kinetic heating of the airframe and also to the use
of the bulk fuel as a coolant for engine oil, hydraulic and air conditioning
equipment, etc. Consequently, fuel for supersonic flight must perform satisfac-
torily at temperatures up to about 250~ (480~ without formation of lacquer
and deposits which can adversely affect the efficiency of heat exchangers,
metering devices, fuel filters, and injector nozzles.
Research on the problem led to the development of the ASTM-CRC Fuel
Coker (ASTM D 1660) which is a laboratory test apparatus for assessing the
tendency of jet fuels to deposit thermal decomposition products in fuel systems.
Although the fuel coker test provides valuable data, it requires a large fuel
sample and has relatively poor precision. A new ASTM Test for Thermal
Oxidation Stability of Aviation Turbine Fuels (JFTOT Procedure) (D 3241) has
been developed that partially overcomes these disadvantages. It is accepted now
as an alternate to the fuel coker test in the ASTM and military specifications for
aviation turbine fuels.
Miscellaneous Properties-A few specifications for some of the lesser used fuel
grades call for special tests not generally applied to aviation fuels. Examples of
these seldom required tests are: the explosiveness test for JP-5 fuel (Federal Test
Method 1151); color limits as determined by the Saybolt Method (ASTM D
156); and tests for electrical conductivity (ASTM D 2624/IP 274).

Inspection Data on Aviation Turbine Fuels

Many airlines, government agencies, and petroleum companies make detailed
studies of inspection data provided on production aviation turbine fuels. Because
a large number of inspections generally are involved, these studies are made
frequently with the aid of a computer. Without a standardized form for
reporting data from different sources, transcribing the reported data for
computer programming is laborious.
To facilitate the reporting of inspection data on aviation turbine fuels, a
standardized report form has been established by ASTM. It appears as Appendix

II to ASTM Specification for Aviation Turbine Fuels (D 1655) and is shown as

Appendix II to this chapter. The report form has found broad acceptance by
suppliers of both U.S. military and civil fuels.

Aviation Fuel Additives

General
Only a limited number of additives are permitted in aviation fuels, and for
each fuel grade the type and concentration are controlled closely by the
appropriate fuel specifications. Additives may be included for a variety of
reasons, but, in every case, the specifications define the requirements as follows:
Manadatory-Must be present between given minimum and maximum limits.
Permitted-May be added by fuel manufacturer's choice up to a maximum
limit.
Optional-May be added only with agreement of user/purchaser, within
specified limits.
Not allowed-Additives not listed in specifications are not permitted.
In the case of aviation gasolines, there is little significant variation in the types
and concentrations of additives normally present in each standard grade, but
considerable variations occur in the additive content of jet fuels depending on
whether they are for civil or military use and the country of origin. Table 8
summarizes the most usual additive content of aviation fuels on a worldwide
basis (except for Russian grades). Many exceptions occur and reference to the
appropriate specifications should be made to establish the precise requirements.

TABLE 8-Summary of usual additive requirements

for British and U.S. aviation fuels

Aviation Civil Military

Additive Gasoline Jet Fuels Jet Fuels

Color dyes mandatory no no

Tetraethyllead permitted no no
Anti-oxidant mandatory permitted a permitted a
Metal-deactivator no permitted permitted
Corrosion inhibitor normally no b no mandatory
Fuel system icing inhibitor no by special request only mandatory
Electrical conductivity noc optional (by user)d optional (by user)d
improver

aMandatory in British jet fuels produced by hydrogen treating processes.

bNot allowed by British gasoline specification. Permitted at user option in U.S. military
gasoline specification, not by civil gasoline specifications.
Cpermitted in Canadian aviation gasoline.
dUsually included in civil jet fuels outside of United States and in British military jet fuels.
Not permitted in U.S. military jet fuels.

Additive Types

The following paragraphs describe the aviation fuel additives in current use.
No attempt is made to fully list the various chemical and trade names of the
approved materials since these are detailed in the appropriate specifications.
Tetraethyllead (TEL)-TetraethyUead is used widely to improve the antiknock
characteristics of gasoline. An adverse side effect of this additive is the
deposition in the engine of solid lead compounds formed in the combustion
process wlfich promotes spark plug fouling and corrosion of cylinders, valves,
etc. To alleviate this potential problem, a scavenging chemical-ethylene
dibromide-is mixed with the compound. Ethylene dibromide largely converts
the lead oxides into volatile lead bromide which is expelled with the exhaust
gases. As a compromise between economic considerations and the avoidance of
side effects, the maximum addition of TEL is controlled carefully by
specifications using ASTM Test for Lead in Gasoline, Gravimetric Method (D
526/IP 96). TEL is not permitted in jet fuels.
Color Dyes-Dyes are used to identify the different grades of aviation gasoline.
The required colors are achieved by the addition of various combinations of up
to three special anthraquinone-based and azo dyes (blue, yellow, and red). The
amounts permitted are controlled between closely specified limits to obtain the
desired fuel colors. ASTM Test for Color of Dyed Aviation Gasolines (D 2392) is
used to determine color. Dyes are not permitted in jet fuels.
Antioxidant (Gum Inhibitor}-Antioxidant additive is mandatory in aviation
gasolines to prevent the formation of gum and precipitation of lead compounds.
The additive concentration is controlled closely by specifications.
Jet fuels are inherently more stable than gasolines. The use of antioxidants is
permitted but not mandatory in most cases. However, it was established some
years ago that jet fuels which are hydrogen treated (or produced by a "hydrogen
process") tend to generate a high-peroxide content which can cause rapid
deterioration of nitrile rubber fuel system components. This is due to the
removal of most of the naturally occurring inhibiting materials (trace sulfur
compounds) by the hydrogen-desulfurizing treatment. To combat this problem,
the British military specifications make the use of antioxidant mandatory in the
case of hydrogen-treated jet fuels. A maximum permitted limit of 24.0 mg/litre
usually applies for all jet fuels, with a minimum of 8.6 mg/litre when the
additive is made mandatory.
A wide range of antioxidants or gum inhibitors are approved, although the
chemical types permitted vary under different specifications. These additives are
generally phenolic or nitrogen-containing materials.
Metal Deactivator-The use of one approved metal deactivator is permitted in
jet fuels but not in aviation gasoline. Deactivators are used to pacify metallic
materials in jet fuels that might degrade the storage or thermal stability of the
fuel. Metallic copper, which is sometimes introduced into the fuels during a
copper sweetening process to remove mercaptans, is the worst offender. Metallic

deactivators are not needed normally unless the fuel has undergone this copper
sweetening process.
Trace iron compounds also are believed to degrade the thermal stability of jet
fuels to a minor degree. The use of a metal deactivator is under consideration to
combat potentially adverse effects from trace iron that enter jet fuels when the
fuel is pumped through unlined steel pipelines.
Corrosion Inhibitors-Corrosion inhibitors are used to minimize corrosive
rusting of steel pipelines, tanks, etc. in contact with fuels in which traces of
water are sometimes present. A direct benefit from the use of corrosion
inhibitors is a reduction in the amount of scale and fine rust shed into the fuel as
particulate contaminant.
The use of corrosion inhibitors also provides significant improvements in the
lubricating properties of jet fuels. This helps overcome problems involving
excessive friction such as rapid component wear or seizure sometimes encoun-
tered in certain fuel pumps and other fuel system components. These problems
(which are not fully understood) are largely of a metallurgical nature and often
can be avoided by a change of component materials. However, fuels having poor
lubricating properties appear to aggravate the problem. No single reliable test has
been devised to measure the lubricating properties of jet fuels.
Because of this lack of knowledge, the specification requirements for fuel
soluble corrosion inhibitors have varied during recent years. Different specifica-
tions call for corrosion inhibitors for different reasons, and fuel users often
impose their own special requirements on basic specifications.
As a general rule, U.S. and British military jet fuels require the addition of an
approved corrosion inhibitor. Civil jet fuels, wide-cut or kerosine type, normally
do not contain corrosion inhibitors.
A number of proprietary fuel soluble corrosion inhibitors are available, mostly
of American manufacture. The basic approval list is presented as a Qualified
Products List (QPL-25017) of materials satisfying the requirements of the U.S.
military specification MIL-I-25017. This document includes for each approved
additive the minimum and relative effective concentrations together with the
maximum allowable concentration (different for each additive type).
Most additives can exhibit some undesirable side effects under certain
circumstances. Included are adverse effects on water-separating properties,
electrical conductivity, and thermal stability. For this reason, there is a
reluctance to permit the use of additives that have not been thoroughly proved
in service.
Fuel System Icing Inhibitor-A fuel system icing inhibitor (FSII) (anti-icing
additive) was used originally to overcome fuel system icing problems encoun-
tered by U.S. military aircraft. Unlike most commercial aircraft and many
British military aircraft, which have their main fuel filters heated to prevent
blockage by ice formed from water precipitated from fuels in flight, U.S. Air
Force (USAF) aircraft have no such protection, and, prior to 1960, icing of
filters and other fuel system components caused a number of accidents. FSII

prevents these problems by lowering the freezing point of any water present in
the fuel to such a degree that no ice formation can occur. The additive has only
a limited solubility in fuel and a much greater affinity for water.
FSI[ is now a mandatory requirement in most military fuel specifications,
especially those covered by NATO or SEATO standardization agreements. It
consists of a pure material "ethylene glycol monomethyl ether" (EGME) which
is known also as methyl cellosolve, methyl oxitol, methyl glycol, and
2-methoxyethanol by various chemical manufacturers.
Shortly after introducing the widespread use of FSII to combat icing
problems, the USAF experienced a great reduction in the number of
microbiological contamination problems being encountered in aircraft tanks and
ground handling facilities. Studies subsequently confirmed that this improve-
ment was due primarily to the biocidal nature of the new additive. It is now
generally accepted that the EGME component of the original additive is a very
effective biocidal if used continuously in jet fuels.
Commercial aircraft are, with minor exceptions, provided with fuel heaters
and have no requirement for an anti-icing additive; particularly in view of the
relatively high cost which would be involved. To save weight, a few
turbine-powered helicopters and corporate aircraft are not provided with fuel
heaters, but, in most cases, the operators make their own arrangements to inject
EGME into the aircraft fuel supplies when necessary.
Several Russian manufactured jet liners are not fitted with fuel heaters.
Domestically, these Russian aircraft use fuels containing an anti-icing additive
believed to be ethyl cellosolve. Elsewhere the standard methyl cellosolve
material generally is accepted.
In tropical areas, operators of some types of civil aircraft occasionally require
fuel containing FSII for its biocidal properties. In these cases, local arrangements
can be made, prior to fueling the aircraft, to inject the additive at the airfield.
Electrical Conductivity Improver (Antistatic Additive)-Static charges built
up during movement of fuel can lead to high-energy spark discharges capable of
igniting flammable fuel/air mixtures. This is true particularly in the case of
modern jet fuels because of their extreme purity (very low-natural conductivity),
the high-pumping velocities employed, and the use of microfdtration equipment
capable of producing a high rate of electrical charge separation and static
buildup in the flowing fuel. Electrical conductivity improvers are designed to
prevent this hazard by increasing the electrical conductivity of the fuel which, in
turn, promotes a rapid relaxation of any static charges.
Opinion is divided as to the benefits of an electrical conductivity improver.
The additive is not permitted in U.S. military jet fuels and has limited use on an
experimental basis in U.S. civil jet fuels at a few locations within the United
States. In Canada, an electrical conductivity improver is mandatory in jet fuels
and permitted in aviation gasoline since the hazards of static discharge are
particularly severe under very low-ambient temperature conditions. British
military jet fuel specifications permit the optional use of an electrical

conductivity improver by agreement between supplier and user. The additive is

also optional in IATA and ASTM specifications for civil jet fuels.
Only one electrical conductivity improver type currently is approved for use in
aviation fuels-Shell Antistatic Additive ASA-3. This additive comprises a
mixture of equal parts of the chromium salt of an alkylated salycillic acid
(chromium AC), calciulii didecyl sulpho succinate (calcium aerosol), and a
vinyl/methacrylate copolymer (alkadine).
ASTM Test for D-C Electrical Conductivity of Hydrocarbon Fuels (D 3114) is
a high-precision laboratory procedure that is capable of measuring conductivity
to very low levels. Other field devices covering the range from low to high
conductivity are under test.
Nonspecification Additives-No additives except those mentioned in the
preceding paragraphs are approved under current fuel specifications, but there
are others that are sometimes used for special purposes. Only one of these
(Biobor JF biocide additive) has any significant use in commercially operated
aircraft but several merit attention.
Biobor JF-Biobor JF is a mixture of dioxaborinanes used to prevent
microbiological growth in hydrocarbon fuels. Extensive use in railway diesel
fuels established its effectiveness and lack of troublesome side effects. After
further satisfactory use by several major airlines, most engine and airframe
manufacturers gave limited approval of Biobor JF use on an intermittent or
noncontinuous basis in concentrations not to exceed 270 ppm (20-ppm
elemental Boron).
Biobor JF normally is used to "disinfect" aircraft during a period when the
aircraft is left standing filled, or partially filled, with doped fuel. The fuel is then
used in the normal manner although it may be drained off or diluted with
undoped fuel before being burned in the engines. To minimize the possible
deposition of boron compounds in the engine, this treatment is only permitted
at infrequent intervals.
Antismoke additives-Although the generation of excessive exhaust smoke by
jet engines is primarily an engine combustion design problem, some reduction in
smoke density in some engines may be possible by the use of additives. Among
these are ethyl C.I. 2 and lubrizol 565. The former is approved by one major
engine manufacturer for postoverhaul test-cell operation of the engines up to 3
h. Neither is approved for flight use.
The U.S. military has conducted flight trials on several antismoke additives. In
addition, antismoke additives have been used with some success in special
prototype aircraft.
Ignition control additive-To minimize the adverse effects of spark plug
deposits in gasoline engines, several phosphorus containing additives were
developed. Typical of these are tri cresyl phosphate (TCP) and tri tolyl
phosphate (TTP) which modify lead deposits so they do not cause preignition.
Spark plug fouling was pronounced in certain older types of aircraft piston
engines, and TCP/TTP was used to overcome the problem. As these engines were

withdrawn from service and as the permitted TEL content of aviation gasoline
gradually was reduced, the problem diminished. Now it is doubtful that this
additive has any significant use.

Additive Tests
Although the type and amount of each additive permitted in aviation fuels are
limited strictly, test methods for checking concentrations are not always
specified. Where tests are not called for, a written statement of the additives
addition is accepted as evidence of its presence. The following paragraphs recap
the tests for the additives discussed previously.

Tetraethyllead
In aviation gasolines, the TEL content has such a critical influence on the
antiknock properties and deposit forming tendency of the fuel that a test for
TEL content is included in all routine laboratory tests. The procedure normally
used is ASTM Test for Lead in Gasoline, Gravimetric Method (D 526/IP 96).

Co/or
After the specified amounts of color dyes have been added to aviation
gasolines, the color usually is checked by visual inspection. However, the
Lovibond Method (IP 17), Federal Test Method 103, and ASTM Color of Dyed
Aviation Gasolines (D 2392) are called for in various specifications.

Antioxidant, Metal Deactivator, Corrosion Inhibitor

After the required amounts of antioxidant, metal deactivator, or corrosion
inhibitor have been added to aviation fuels, checks normally are not run on
concentrations, so no test methods are included in specifications for this
purpose. Occasionally, a need arises to determine the amount of corrosion
inhibitor remaining in the fuel. Several analytical methods have been developed,
but none have been standardized.

Fuel System Icing Inhibitor

FSII used in jet fuels can be lost by evaporation and also lost rapidly into any
water which might contact the fuel during transportation. Several methods are
available to determine FSII content. Included among these are Icing Inhibitor in
Aviation Turbine Fuels (IP 277), which provides a "referee" test (method C)
and, for routine purposes, a simpler version (method D).

Electrical Conductivity Improver

Electrical conductivity improver is used in such small concentrations (less than
1 ppm) that it is extremely difficult to detect by any standard analytical

procedure. Therefore, electrical conductivity improver is controlled by

measuring the resulting electrical conductivity of the fuel.
The standard field test for electrical conductivity has been ASTM Electrical
Conductivity of Aviation Fuels Containing a Static Dissipator Additive (D
2624/IP 274). Although the method was intended for the measurement of the
conductivity of fuel at rest in storage tanks, it can also be used in a laboratory or
fuel samples. However, a more precise laboratory method is ASTM D-C
Electrical Conductivity of Hydrocarbon Fuels (D 3114).

Applicable ASTM Specifications

D 910 Specification for Aviation Gasolines
D 1655 Specification for Aviation Turbine Fuels

ApplicableASTM/IPStandards
ASTM IP Title
D 56 Flash Point by Tag Closed Tester
D 86 123 Distillation of Petroleum Products
D 93 34 Flash Point by Pensky-Martens Closed Tester
D 130 154 Detection of Copper Corrosion from Petroleum
Products by the Copper Strip Tarnish Test
D 156 Saybolt Color of Petroleum Products
(Saybolt Chromometer Method)
17 Colour by the Lovibond Tintometer
D t87 10 Burning Quality of Kerosine
D 240 12 Heat of Combustion of Liquid Hydrocarbon Fuels
(General Bomb Method)
D 323 Vapor Pressure of Petroleum Products (Reid Method)
D 381 131 Existent Gum in Fuels by Jet Evaporation
D445 71 Kinematic Viscosity of Transparent and Opaque
Liquids (and the Calculation of Dynamic Viscosity)
D 484 30 Hydrocarbon Drycleaning Solvents (IP Doctor Test)
D 526 96 Lead in Gasoline, Gravimetric Method
D 611 Aniline Point and Mixed Aniline Point of Petroleum
Products and Hydrocarbon Solvents
D 873 38 Oxidation Stability of Aviation Fuels (Potential
Residue Method)
D 909 Knock Characteristics of Aviation Fuels by the
Supercharge Method
D 974 139 Neutralization Number by Color-Indicator Titration
225 Copper in Aviation Turbine Fuels and Light
Petroleum Distillates
D 1094 Water Reaction of Aviation Fuels

Applicable ASTM/IP Standards (Continued.)

ASTM IP Title
D 1159 130 Bromine Number of Petroleum Distillates and
Commercial Aliphatic Olefins by
Electrometric Titration
D 1219 Mercaptan Sulfur in Aviation Turbine Fuels
(Color-Indicator Method)
D 1266 107 Sulfur in Petroleum Products (Lamp Method)
D 1298 Density, Specific Gravity, or API Gravity of Crude
Petroleum and Liquid Petroleum Products by
Hydrometer Method
D 1319 156 Hydrocarbon Types in Liquid Petroleum Products
by Fluorescent Indicator Adsorption
227 Silver Corrosion by Aviation Turbine Fuels
D 1322 Smoke Point of Aviation Turbine Fuels
D 1405 193 Estimation of Net Heat of Combustion of
Aviation Fuels
D 1660 Thermal Stability of Aviation Turbine Fuels
273 Total Acidity in Aviation Turbine Fuel
D 1740 Luminometer Numbers of Aviation Turbine Fuels
D 1744 Water in Liquid Petroleum Products by
Karl Fischer Reagent
277 Icing Inhibitor in Aviation Turbine Fuels
D 1840 Naphthalene Hydrocarbons in Aviation Turbine Fuels
by Ultraviolet Spectrophotometry
D 2276 216 Particulate Contaminant in Aviation Turbine Fuels
289 Water Reaction of Aviation Fuels
D 2382 Heat of Combustion of Hydrocarbon Fuels by
Bomb Calorimeter (High-Precision Method)
D 2386 16 Freezing Point of Aviation Fuels
D 2392 Color of Dyed Aviation Gasolines
D 2550 Water Separation Characteristics of Aviation
Turbine Fuels
D 2624 Electrical Conductivity of Aviation Fuels
Containing a Static Dissipator Additive
D 2699 237 Knock Characteristics of Motor Fuels by the
Research Method
D 2700 236 Knock Characteristics of Motor and Aviation-Type
Fuels by the Motor Method
D 3114 D-C Electrical Conductivity of Hydrocarbon Fuels
D 3240 Undissolved Water in Aviation Fuels
D 3241 Thermal Oxidation Stability of Aviation Turbine
Fuels (JFTOT Procedure)

D 3242 Total Acidity in Aviation Turbine Fuel

D 3243 Flashpoint of Aviation Turbine Fuels by
Setaflash Closed Tester

Bibliography
Dukek, W. G., Ogston, A. R., and Winans, D. R., "Milestones in Aviation Fuels," Paper
69-779, American Institute of Aeronautics and Astronautics, New York, 1971.
Modern Petroleum Technology, Institute of Petroleum, London, 3rd edition, 1962.
Paushkin, Y. A., The Chemical Composition and Properties o f Fuels for Jet Propulsion, B.
P. Mullins, Ed., Pergamon Press, Elmsford, N.Y., 1962.
Smith, G. C., Gas Turbines and Jet Propulsion, Ilfffe Books, Ltd., London, 1967.

Fuel Specification Guides

Handbook of Products (Air BP), British Petroleum Co. Ltd., Britannic House, London.
Jet Fuel Specifications: Airlines, Military, Standards, Exxon Research and Engineering
Co., Linden, N.J.
Specifications: Aviation Fuels and Engine Oils, Shell International Petroleum Co. Ltd.,
Shell Centre, London.

APPENDIX I
Automotive (Motor) Gasoline-Unsuitability for Aviation Use
Differences in the properties and composition of motor gasoline and aviation
gasoLine make the former unsafe for use in aircraft. The main differences
between automotive and aircraft gasoline fuels are as follows:
(a) Automotive fuels have a wider distillation range than aircraft fuels. This
promotes poor distribution of the high-antiknock components of the fuel.
Further, the octane ratings of automotive and aircraft fuel are not comparable
due to the different test methods used to rate the two types of fuel. This
produces an appreciable difference in actual antiknock performance for two
fuels which have the same apparent octane number. The difference could lead to
destructive preignition or detonation.
(b) Automotive fuels are more volatile and have higher vapor pressures which
can lead to vapor lock. The greater volatility also increases the fire hazard.
(c) The antiknock compound (TEL) used in automotive fuels contains an
excess of chlorine and bromine whereas for aviation fuels, the antiknock
compound contains only the chemically correct amount of bromine. Chlorine
compounds are very corrosive and under severe conditions can lead to exhaust
valve failures.
(d) Automotive fuels do not have as high a long-term stability as aviation
gasoline and can form gum deposits which can result in valve sticking and poor
mixture distribution.
(e) Automotive fuels have solvent characteristics which are not suitable for
aircraft engines. Seals, gaskets, and flexible fuel lines may be attacked.
(f) The testing and quality protection measures applied to automotive gasoLine
are far less stringent than for aviation fuels. Therefore, there is a much greater
possibiLity of contamination occurring and less possibility of it being detected.

APPENDIX II
ol.5
INSPECTION D A T A ON A V I A T I O N T U R B I N E FUELS
(See the beck Of the form itself or
Specification DI655 Appendix A2 for instructions onuse of form)

REPORTDATE QUANTITY US. GALLONS:

CONTRACT N o.
SAMPLING LOCATION:
ORDER No
DESTINATION:
DATE SAMPLED

SAMPLE No. PRODUCT NAME:

BATCH No REMARKS:
COMPLIES WITH SPECIFICATIONS:
TANK No.

GRADE:
Method APPEARANCE Results Method cORROSION Results
I0 D 156 Color ( Saybolt) . . . . . . . . . . 500 D 130 Copper Strip (Z h at 212 F) . . . . .
20 -- Visual (B=Brighl 6 C:Cleor).. 510 IP 227 Silver Strip . . . . . . . . . . . . . . . . .
COMPOSITION STABILITY
100 D 974/3242 Acidity, Total (rag KOH/9) l l "

I10 O 1 3 1 9 Aromatics (vol ~ ) . . . . . . 610 D 16GO Coker Tube Color Code . . . . . . .

120 O(3(9 O~(ms(vo4~ . . . . . . . . . . 6~t 0 37.41 JFTOTat 260C AR (mmHg)...
130 D 1219/1323 Sulfur, Mercaptan (wt~ 612 D 3241 JFTOTat260C TubeCo~orCode.
140 D 484 Doctor Test (P:pas, N:Neg). 613 D 3241 JFTOTo1245C~P(mmHg)...
150 D 1266 Sulfur, To(ol (wl %) . . . . . . . 614 D 3241 JFTOTol 245C TubeColorCode.
VOLATILI TY CONTAMINANTS
200 D 86 Distillation tnit. BP IF) . . . . . 700 IP225 Copper Content Lug/kg) . . . . . .
205 D 86 10% Rec I F ) . . . . 710 D 581 Existent Gum (mgAOOml), ,.
210 D 86 20~ Rec IF) . . . . 720 D 2276 Particulates [rag/liter) . . . . . .
215 O 86 SO%Rec(F) . . . . l ! 721 MiI-T-S6Z4J FiHration time, mtn. . . . . . . . .
220 D 86 9 0 % Rec IF) . . . . 722 APPA vacuum~mm Hg . . . . . . . .
225 O 86 95~ Rec IF) . . . . 725 " volume fuel filtered, m l . . .
250 D 86 Final BP I F ) . , . . I 740 DI094 Water Reaction Interface Rating.
235 D 86 Residue (~ . . . . . . . . 9 741 D 1094 " " Separation Rating.
240 D 86 Lass (%) . . . . . . . . . . . 9 750 O 2550 W S IM . . . . . . . . . . . . . . . .
245 O 86 Recovery d AO0 F ~~
250 FTMS 115l E~losiveness (vol % ) . . . . . ADDITIVES Brand
260 O 56/3243 Flash Point, Tog Closed IF) 9 e ~ 800 Anti-icing (vol % ) . . . . . . 9 9 9
261 D 93 Flash Point,PenskyMartin (F), 810 AntJoxidont (Ib/lvl Bbl) . . . . . I
270 D 1298 Gravity, AP[ (60 F) . . . . . . . 820 Corrosion Inhib (Ib/M Bbl).] I
Gravity, Specific (60/60 F ) 830 Metal Deadivotor (Ib/M Bbf).
280 D 1298
Vapor Pressure (Ib Reid)... 9 .oti.to.c.og/, ........
I'll
..,.,
D 323

FLUIDITY OTHER TESTS

300 O 2386 Freezing Point (F) . . . . . . ~ ] 900 D2624/3114 Conductivity (pS/m) . . . . . . . .

310 O 445 Viscosity at -20 C (cSt)... 901 O 2624/3114 " Temperature (F) . . . .
COMBUSTION
400 D 1405 Aniline Gravity Product...
410 O 1405 Net Heat of Comb. (Btu/Ib).
420 O tT40 Luminometer No......... ii iiiiiiiiiilliiii:i.
430 D 13.22 Smoke Point . . . . . . . . . .
440 D 1840 Naphthalenes (vol %} . . . .
450 D 1655 Smoke-Volatility Index . ..
~1JITL American Society
APPROVED BY ~J r) forTestinq and Materials
Componyfheprete~tQIive Auh~Orlzed GovernmentRe~resentahve Ul I i$[$ M W C I S I , P 4 i l I , P * IIIOS
ASr=I 0 I*SS

FIG. 1-Standard form for reporting inspection data on aviation turbine fuels9

Chapter 6 Diesel Engine and

Nonaviation Gas
Turbine Fuels

Introduction
Although not totally alike, the quality criteria and methods for testing diesel
and nonaviation gas-turbine fuels are sufficiently similar to permit the two fuels
to be addressed in a single chapter. Differences that do exist will become
apparent to the reader.

Diesel Engine
The diesel engine is a high-compression, self-ignition engine. Fuel is ignited by
the heat of the high compression, and no spark plug is used. The diesel cycle
consists of charging the combustion chamber with air, compressing the air,
injecting the fuel which ignites spontaneously, expanding the burned gases, and
expelling the products of combustion.
Diesel engines may be designed to operate on a four- or a two-stroke cycle.
Each type has advantages and disadvantages, so the choice depends qpon the
application. The four-stroke cycle has better volumetric efficiency, good
combustion characteristics, and positive exhaust gas scavenging. The principal
advantage of the two-stroke cycle is compactness in relation to power output.
Diesel engines vary greatly in size, power output, and operating speeds. While
some small units develop only a few brake horsepower, at the other extreme
there are engines having cylinder diameters as large as 1050 mm (41.34 in.)
developing several thousand horsepower per cylinder. Designed sizes and
horsepower output continue to increase. Operating speeds are almost as diverse
as size and power output. They range from below 100 rpm for some larger
engines to 4000 rpm and above for those used in automotive and other vehicle
prime mover service. Diesel engines now are established fully in all forms of
surface transportation and construction as well as for a wide range of power
generation and pumping applications.
The entire range of diesel engines can be divided into three broad classification
groups indicated in Table 1.
It should not be surprising that diesel engines also vary extensively in their
requirements for fuel. Selection of the proper fuel is not a simple procedure but
depends upon many variables. Among the most important considerations are:
1. Engine size and design.

86
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86 SIGNIFICANCEOF TESTS

TABLE 1-Range of diesel engines.

Classification Speed Range Conditions Typical Applications a

Low below sustained heavy load, marine main propulsion;

speed 300 rpm constant speed electric power generation
Medium 300 to fairly high load and marine auxiliaries:
speed 1000 rpm relativelyconstant speed stationary power genera-
tors: pumping units
High 1000 rpm frequent and wide varia- road transport vehicles:
speed or above tion in load and speed diesel locomotives:
construction equipment

aThere are many other typical applications not listed.

2. Operating speed and load ranges.

3. Frequency of speed and load changes.
4. Maintenance considerations.
5. Atmospheric conditions.
6. Fuel price and availability.
Each of the foregoing factors plays a part in dictating the fuel to be chosen for a
diesel engine. The relative influence of each factor is determined by the specific
application and installation involved.

Nonaviation Gas Turbine

The simple-cycle, gas-turbine engine operates on the Brayton or Joule cycle
consisting of adiabatic compression, constant pressure heating, and adiabatic
expansion. By adding a heat exchanger to transfer heat from the turbine exhaust
gas to the combustor inlet air, fuel consumption can be reduced.
Air is compressed in the compressor through axial or centrifugal states or
both and directed toward the combustion chamber. Here, part of the air mixes
with vaporized fuel and supports combustion. The remainder of the air passes
around the flame, cooling the metal surfaces and combining with those gases
which are rapidly expanding from combustion. The resulting gas stream is then
expanded through one or more turbine wheels which drive the compressor and
provide the output power. In a simple-cycle gas turbine, the gas is then
exhausted; in a regenerative engine, the exhaust gas is directed through a heat
exchanger to heat the combustor inlet air.
The gas-turbine engines cover a range from 50 to nearly 50 000 hp. Over half
of the larger industrial gas turbines are in electric-generating use. Other uses
include gas pipeline transmission, total-energy units, and transportation. The
selection of a gas-turbine fuel oil for use in a given gas turbine requires
consideration of the following factors: availability of the fuel, design of the gas
turbine and fuel handling system, and maintenance and operating requirements.

Combustion Process

Diesel Combustion
The fuel used in all diesel engines-precombustion chamber, direct injection,
two cycle, four cycle-passes through the following processes:
1. Storage, pumping, and handling.
2. Filtering.
3. Heating (if necessary).
4. Combustion.
5. Power extraction.
6. Heat exchange and exhaust.
7. Atomization and mixing with air.
The fuel properties are significant in all these processes and particularly
influence combustion and resultant energy extraction. In any combustion
process, there are at least three basic requirements:
1. Formation of a mixture of fuel and air.
2. Ignition of the fuel/air mixture.
3. Completion of combustion of the fuel/air mixture.
In the diesel engine, these requirements are met as indicated diagrammatically
in Fig. 1. Figure 2 shows a typical pressure versus crank angle diagram for a
diesel engine combustion chamber.
Prior to the injection of the fuel, air alone is compressed and raised to a high
temperature during the compression stroke. The final compression pressure and
resultant air temperature will vary with compression ratio, speed, and engine
design, but a pressure of 31.6 kg/crn 2 (450 psi) and a temperature of 538~
(1000~ are representative values for naturally aspirated engines. Higher
pressures and temperatures occur in blown or supercharged engines. Shortly
before the end of compression, at a point controlled by the fuel injection timing
system, one or more jets of fueI are introduced into the main combustion
chamber or the precombustion chamber.
Ignition does not occur immediately on injection. The fuel droplets must first
be vaporized by heat from the compressed air. The fuel/air mixture finally
reaches a temperature at which self-ignition occurs, and the flame begins to
spread. The duration of the delay period between injection and ignition is
controlled by engine design, fuel and air inlet temperatures, degree of
atomization of the fuel, and fuel composition. This delay period is known
commonly as "ignition delay."
Injection of fuel is continued during the ignition delay. The ignition delay
period must be short in order to avoid "diesel knock" which is caused by very
rapid burning or detonation of relatively large amounts of fuel gathered in the
cylinder before combustion begins. Once the flame has spread completely, the
only fuel in the cylinder is that being injected into the burning mixture. This
fuel bums almost instantaneously. The final part of the combustion cycle is the
completion of burning after injection has ceased.

L- Injection
Mixture ~
formolionT Ignition
_1_
Final combustion - _1
-I
Delay period - ~l-
Physical _ _ ~ Chemical__~
delay delay |
Disintegration J
of stream of I I
injected fuel I
1 I'n"~176176
Mixing of I Preflame
liquid fuel oxidation of fuel/air decomposition
with air of fuel mixtures of fuel

Vaporisotion
1
l igni.tion
Local Mixture of t
of fuel ] products of
partial oxidation
or of thermal
decomposition
i Mixingof fuel with air
vopour with air
I_
L___
Temperature Temperature
and oxygen and oxygen
concentration concentration
fovouroble unfovourable
for complete for complete
combustion combustion
(chilling,
overleon and
overrich mixtures )
;
Products of J Products of ]
complete incomplete
combuslion combustion
FIG. 1-Outline o f the combustion process in the diesel engine. (M. A. Elliot, July 1949).
Combustion of diesel fuel, SAE Transactions, Vol. 3, No. 3:492.

Flame spread period ~ r---'-- Continuous bumin(jperiod

9.,-- Delay

I
Y Curve for air only

TOe I
- - 27 Degree (approx) - - * , - J

Tnjection starts Injection stops

- - Crank angle

FIG. 2 Pressure variations in a diesel engine cylinder during combustion.

The quantity of fuel, the rate at which it is injected into the engine, and the
timing and duration of the injection period all are controlled accurately by a
cam-driven injection pump. The pump delivers the fuel to the injectors at a
pressure of 130 to 2100 kg/cm 2 (1800 to 30 000 psi) depending upon the design
of the injection equipment. Variation in the fuel quantity to conform to
different speed or load conditions or both usually is by means of a governor
which admits fuel to the combustion chamber at a preset maximum rate until
the new conditions are attained. The maximum fuel rate is set to avoid black
smoke caused by an excessive amount of fuel.
The maximum amount of air that can be pumped by an engine is determined
by its design. The amount of air that can be utilized efficiently determines the
optimum injection rate of fuel and, hence, the maximum power output of the
engine. Below this maximum, the output of the engine is controlled solely by
the amount of fuel supplied.
Pressure charging is used frequently as a means for increasing the amount of
air delivered to an engine without increasing its size. A compressor, either
directly coupled to the crankshaft (a supercharger) or driven by a'turbine using
the heat energy in the exhaust gases (a turbocharger), is used to increase the
amount of combustion air available. Consequently, the engine is able to bum a
greater quantity of fuel. The amount of fuel ultimately is limited by the thermal
and mechanical stresses that can be tolerated by engine components.

Nonaviation Gas-Turbine Combustion

In a gas-turbine engine, fuel is burned continuously at peak cycle pressure to
heat the air to moderate temperatures. The combustor is essentially a direct-fired
air heater in which fuel is burned with less than one third of the available air, and
the combustion products are mixed with the remaining air to cool them to the
maximum temperature allowed by metallurgical considerations.
Although gas-turbine combustors vary widely in design arrangement, all
perform the same basic functions in much the same way. The two main methods
of fuel injection are:
Atomizer-Most combustors employ an atomizer in which fuel is forced under
high pressure through an orifice. This breaks up the liquid fuel into small
droplets which greatly increases the surface-to-volume ratio. The droplets are
then introduced to the primary zone of the combustor where they vaporize and
burn; the two processes occur simultaneously.
Prevaporizing (Vaporizing)-This method nearly always relies on direct heating
of the fuel. Fuel, together with a proportion of the primary air, a mixture too
rich to bum, is supplied to the vaporizing tubes located in the primary zone of
the combustor. The fuel is vaporized by the heat released in the primary zone,
and the resulting rich mixture is discharged into the primary zone in an upstream
direction. The remainder of the primary air is admitted into the primary zone
and burning of the mixture occurs.
Combustor inlet air temperature depends on engine pressure ratio and load
which varies from about 121 to 404~ (250 to 760~ in various nonregenerative
engines. With regeneration, combustor inlet temperatures may be 371 to 649~
(700 to 1200~ Combustor outlet temperatures range from 649 to 1038~
(1200 to 1900~ Combustor pressures can range from 3.2 kg/cm: (45 psia) to
as high as 16.5 kg/cm 2 (235 psia).

General Fuel Characteristics and Classifications

Background
The basic requirements for diesel and nonaviation gas-turbine fuels are
satisfactory ignition and combustion under the conditions existing in the
combustion chamber, suitability for handling by the injection equipment, and
convenient handling at all stages from the refinery to the engine fuel tank
without suffering degradation and without harming any surface which it may
contact normally.
Diesel and nonaviation gas-turbine fuels were originally straight-run products
obtained from the distillation of crude oil. Today with the various refinery
cracking processes, these fuels may contain varying amounts of selected cracked
distillates. This permits an increase in the volume of available fuel at minimum
cost. The boiling range of distillate fuels is approximately 150 to 400~ (300 to
755~ The relative merits of the fuel types to be considered will depend upon

the refining practices employed, the nature of crude oils from which they are
produced, and the additive package (if any) used.
The broad definition of diesel and nonaviation turbine fuels covers many
possible combinations of volatility, ignition quality, viscosity, gravity, stability,
and other properties. To characterize these fuels and thereby establish a
framework of definition and reference, various classifications or specifications
are used in different countries. One of the most widely used for diesel fuels is
ASTM Specification for Diesel Fuel Oils (D 975). Table 2 shows the detailed
requirements for diesel fuel oils as contained in ASTM D 975. The detailed
requirements of ASTM Specification for Gas-Turbine Fuel Oils (ASTM D 2880)
are shown in Table 3. A comparison of the two tables reveals many similarities
between the two types of fuel.
Neither ASTM D 975 or D 2880 are complete quality specifications. In
general, they both present certain minimum requirements necessary to assure
reasonable operation under the conditions described.

Diesel Fuels
In ASTM D 975, Grades No. 1-D and 2-D are distillate fuels which are the
types most commonly used in high-speed engines of the mobile type,
medium-speed stationary engines, and railroad engines. Grade 4-D covers the
class of more viscous distillates which are blended frequently with residual fuel
oils. No. 4-D fuels are applicable to low- and medium-speed engines employed in
services involving sustained load and predominately constant speed.
Examples of equivalent fuel standards, similar to those presented in Table 2,
that exist in European countries are DIN 51601 "Fuels for High Speed Diesels"
in West Germany and BS 2869 "Petroleum Fuels for Oil Engines and Burners" in
the United Kingdom.
The BS specification covers four classes of fuels marketed specifically as
engine fuels. Class A1 is of high quality and designed primarily as a fuel for
higher speed diesel engines; Class A2 is intended as a general purpose diesel fuel;
Classes B1 and B2 are for larger engines such as those used in marine practice.
Class B2 allows for the inclusion of small amounts of residuum.
While the foregoing classifications deal chiefly with distillate fuels, residual
fuels are used extensively in large, slow-speed, marine main propulsion engines
and stationary land-based engines principally because of lower fuel cost. More
recently, the lower cost aspect has promoted the increasing popularity of
residual fuels in some smaller, medium-speed auxiliary engines. Mixtures of
residual and distillate fuels are used in installations where a compromise is
sought between the more desirable properties of the latter and the lower cost of
the former.
A typical heavy residual fuel is illustrated in the specifications established by
American Society for Testing and Materials (ASTM) Committee D-2 to define
No. 6 fuel oil which is often referred to as "Bunker C." These specifications,
relatively few in number and broad in their limits, are shown in Table 4. Some

Carbon
Water Residue
and on 10 Distillation Temp- Viscosity at
Flash Cloud Sedi- % eratures, OF ( ~ 100~: (37.8~ Copper Z
m
Point, Poinl ment, Resid- Ash, Sulfur, d Strip Cetane 'T$

~F ~ volume uum, weight Kinematic, cSt weight Corro- Num-

(~ t~ % % % 90 % Point (or SUS) % sion ber e z
Grade of Diesel Fuel Oil Min Max Max Max Max Min Max Min Max Max Max Min m
0
"11

No. I-D Volatile distillate fuel oil 100 or m

for engines in service requiring legal .. b 0.05 0.15 0.01 ... 550 1.4 2.5 0.50 No. 3 40 /
frequent speed and load changes (37.8) (287.8) (34.4) or legal --t

No. 2-D Distillate fuel of lower 125 or

volatility for engines in industrial legal .. b 0.05 0.35 0.01 540 c 640 2.0 c 4.3 0.50 No. 3 40/.
and heavy mobile service (51.7) (282.2) (338) (32.6) (40.1) or legal

No. 4-D l:uel oil for low and 130or

medium speed engines legal . . .b 0.50 9. . 0.10 . . . . . . 5.8 26.4 2.0 ... 30-t"
(54.4) (45) (l 25)

aTo meet special operating conditions, modifications of individual limiting requirements may be agreed upon between purchaser, seller, and
manufacturer.
blt is unrealistic to specify low-temperature properties that will ensure satisfactory operation on a broad basis. Satisfactory operation should be
achieved in most cases if the cloud point (or wax appearance point) is specified at 10*F above the tenth percentile minimum ambient temperature
for the area in which the fuel will be used. The tenth percentile minimum ambient temperatures for the United States are shown in Appendix A2
of ASTM Specification D 975. This guidance is of a general nature; some equipment designs, use flow improver additives, fuel properties or
operations or both may allow higher or require lower cloud point fuels. Appropriate low temperature operability properties should be agreed on
between the fuel supplier and purchaser for the intended use and expected ambient temperatures.
CWhen cloud point less than 10~ (-12.2~ is specified, the minimum viscosity shall be 1.8 cSt and the 90 percent point shall be waived.
9d ln countries outside the United States, other sulfur limits may apply.
eWhere cetane number by ASTM Method D 613 is not available, ASTM Method D 976 may be used as an approximation. Where there is
disagreement, ASTM Method D 613 shall be the referee method.
fLow-atmospheric temperatures as well as engine operation at high altitudes may require use of fuels with higher cetane ratings.

diesel engines are operated on fuels of even lower quality than No. 6 fuel oil.
However, it should be recognized that lower quality fuels, while having the
advantage of lower fuel cost, usually require special equipment and special
lubricating oils to achieve satisfactory performance.
Additives may be used to improve diesel fuel performance. Cetane improvers
such as alkyl nitrates and nitrites can improve ignition quality. Pour-point
depressants can improve low-temperature performance. Antismoke additives
may reduce exhaust smoke which is a growing concern as more and more
attention is paid to atmospheric pollution. Antioxidant and sludge dispersants
may be used also, particularly with fuels formulated with cracked components,
in order to prevent the formation of insoluble compounds that could cause line
and filter plugging.

Nonaviation Gas Turbine Fuel

In ASTM D 2880, Grade No. 1-GT is a light distillate oil suitable for use in
nearly all gas turbines and corresponds in physical properties to No. I fuel oil
and 1-D diesel fuel oil. Grade No. 2-GT is a heavier distillate grade than No.
1-GT and is for use in turbines not requiring the clean-burning characteristics of
No. 1-GT. It is similar in properties to No. 2 fuel oil and 2-D diesel fuel oil.
Grade No. 3-GT is a low-ash fuel having the same viscosity range that brackets
No. 4, 5, and 6 fuel oils and 4-D diesel fuel oil. Grade No. 3-GT may be a heavier
distillate than Grade No. 2-GT-a residual fuel that meets the low-ash
requirements-or a blend of a distillate with a residual fuel oil. For gas turbines
operating at turbine inlet temperatures below 649~ (1200~ the vanadium,
sodium plus potassium, and calcium limits can be waived provided a silicon base
additive or equivalent is employed to prevent excessive ash deposition in the
turbine. Fuel heating equipment will be required by the gas turbine in almost
every installation using No. 3-GT fuel.
Grade No. 4-GT covers the same viscosity range as Grade No. 3-GT, but it has
no restriction on the quantity of ash. Grade No. 4-GT is limited in its magnesium
to vanadium weight ratio to a value of 3.5 max. Nearly all residual fuels will
satisfy this requirement, but an additive may be needed to inhibit the corrosive
action of the vanadium. In general, Grade No. 4-GT will form ash deposits in the
turbine so that with continuous operation there will be a progressive reduction
in power output and thermal efficiency necessitating periodic shutdown for
cleaning.

Fuel Properties and Tests

The properties of a product define its fitness to serve a stated purpose. Once
the required properties are determined, they are controlled by appropriate
testing and analysis. This section will outline significant quality criteria for diesel
and nonaviation gas-turbine fuels. Appropriate ASTM and Institute of Petroleum
(IP) methods for testing and analysis will be given.

fi)
z
q
"11

z
i'D
Ill
O
TABLE 3-Detailed requirernents for gas turbine fuel oils (ASTM D 2880. 71). "11
-I
m
03
l)istilla0on -'4
Tempera- 03
ture, Kinematic
90 % Viscosity,
Carbon point Saybolt Viscosity, sb cSt b Sodium Magne-
Water Resi- plus slum to
and due on I:urol Vana- Potas- Vana-
Flash Pour Sedi- 10% at dium slum Calcium dium
Point, Point, ment, Resi- Ash, 122 ~ At 122 ~ (V), (NA + K), (Ca), Lead (Ph), Weight Sulfur,
"F o[: volume duum, weight OF ~I-" Universal at F At 100 ~ F Gravity, ppm by ppm by ppm by ppm by Ratio weight
I'C) i~ % % % (C) (~ 100~F (38~ (50~ (38~ (50~ ~ weight weight weight weight (Ms/V) %
Desig- Grade of Gas Turbine
nation a I:uel Oil Min Max Max Max Max Min Max Min Max Max Min Max Max Min Max Max Max Max Min Max Max

No. I-GTc Volatile distillate for 100 0 0.05 0.15 0.01 ... 550 .., (34.4) .,. 1.4 2.5 ... 35 2 5 $ 5 ...... 0.5
gas turbines re- (38) (~ 18) d (288) or
quiring a fuel that or legal
burns cleaner than legal
No. 243T
No. 2-GT Distillate fuel of low 100 20 0.05 0.35 0.01 540 640 (32.6) (40.2) . .. 2.0 4.3 ... 30 2 5 10 5 . . . . . . 0.5 h
ash and medium (38) ( - 7) d (282) (338) or
volatility suitable or legal
for gas turbines not legal
requiring No. 143T
No. 3<3T e Low-volatility, low- 130 .. 9 1,0 ... 0.03 . . . . . . 45 ... 300 (5.8) ... (638) ... 2e 5e 10 e 5 . . . . . . . . .
ash fuel that may (54)
contain residual or
components legal
No. 443T Low-volatility fuel 150 ... l.O . . . . . . . . . . . . 45 9, 9 300 (5.8) . 99 (638) ... 500 I 0f lO t. 5 3.0g 3.5 g ...
containing residual (66)
c~mponents and or
having higher van- legal
adium content than
No. 3-GT

Copyright by ASTM Int'l (all rights reserved); Tue Dec 29 16:07:05 EST 2015
Downloaded/printed by
University of Washington (University of Washington) pursuant to License Agreement. No further reproductions authorized.
aNo. 1-GT corresponds in general to ASTM Specification D 396 Grade No. 1 fuel and ASTM Specification D 975 Grade No. 1-D diesel fuel in
physical properties.
No. 2-GT corresponds in general to ASTM Specification D 396 Grade No. 2 fuel and ASTM Specification D 975 Grade No. 2-D diesel fuel in
physical properties.
No. 3-GT and No. 4-GT viscosity range brackets ASTM Specification D 396 Grades No. 4, No. 5(light), No. 5(heavy) and No. 6 and ASTM
Specification D 975 Grade No. 4-D diesel fuel, which may be supplied provided metals composition requirements are met.
bViscosity values in parentheses are for information only and are not limiting. 0
-r
CRecognizing the necessity of additional requirements for certain types of gas turbines, the following may be specified for No. 1-GT fuel:
luminometer number, rain = 40.
m
Thermal stability test for 5 h at 250~ (121~ preheater temperature, 350~ (177~ filter temperature and at a flow rate of 6 lb (2.7 kg)/h:
filter pressure drop, max = 12 in. (300 mm) HG and preheater deposit code, max = 2.
dFor cold weather operation, the pour point should be specified 10~ (5.6~ below the ambient temperature at which the turbine is to be 0
Z
operated, except where fuel oil heating facilities are provided. When a pour point less than 0*F ( - 18~ is specified for Grade No. 2-GT, the 0
minimum viscosity shall be 1.8 cSt (32.0 SUS) and the minimum 90 percent point shall be waived. m
eFor gas turbines operating below 1200~F (649~ maximum gas temperature, the limitations on vanadium, sodium plus potassium, and calcium m
r-
may be waived, provided that a silicon-base additive, or equivalent, is employed,. The special requirements covering the addition of and the type of m
additive shall be specified only by mutual agreement between purchaser and seller. Z

fWhere water washing facilities are available at the point of use, these requirements may be waived by mutual agreement between the purchaser Z
and seller. m

gSpecial requirements covering the addition of the type of magnesium-containing additive, or equivalent, to be used shall be specified only by Z
mutual agreement between the purchaser and the seller.
Z
hFor products outside the United States, the maximum sulfur limit shall be 1.0 weight percent. 0
Z
/Legal requirements to be met.
<
7,
--I
g
Z
"n
C
m
r"

t.D
(31

TABLE 4-Requirements for no. 6 fuel oil a

Saybolt Viscosity, s Kinematic

Flash Water and Viscosity,
Point, Sediment, Universal, Furol, cSt,
~ volume 100OF 122OF 122OF
(~ % (38~ (50~ (50~

Fuel oil grade Min Max Max Min Max Min Max Min

No. 6 140 2.00 b (9000) (900) 300 45 (638) (92)

Preheating required (60) . . . . C . . .C . . C C

for burning and

handling

aThese data taken from ASTM Specification D 396 Table 1. Detailed Requirements for
Fuel Oils.
bThe amount of water by distillation plus the sediment by extraction shall not exceed
2.00 percent. The amount of sediment by extraction shall not exceed 0.50 percent. A
deduction in quantity shall be made for all water and sediment in excess of 1.0 percent.
CViscosity values in parentheses are for information only and not necessarily limiting.

Cetane N u m b e r

In the majority of diesel engines, the ignition delay period is shorter than the
duration of injection. Under such circumstances, the total combustion period
can be divided into the following four stages:
I. Ignition delay.
2. Rapid pressure rise.
3. Constant pressure or controlled pressure rise.
4. Burning on the expansion stroke.
The rapid pressure rise results from the large number of ignition points and the
accumulation of fuel during the ignition delay period. Following this stage, the
rate of combustion can be controlled to a much greater degree by controlling the
injection rate, since the fuel is being injected into flame. Because the rapid
pressure rise represents uncontrolled and inefficient combustion, it is desirable
to limit ignition delay to a minimum. This limitation can be accomplished
mechanically by the selection of a spray pattern configuration properly tailored
to the combustion chamber. Ignition delay also can be reduced by the use of
high-fuel injection pressures and high-fuel/air turbulence to promote rapid fuel
jet breakup and thorough fuel distribution.
The nature of the fuel is also an important factor in reducing the ignition
delay. Physical characteristics such as viscosity, gravity, and midboiling point are
influential. Hydrocarbon composition also is important as it affects both the
physical and combustion characteristics of the fuel. Straight-chain paraffins
ignite readily under compression, but branched-chain paraffins and aromatics
react poorly. Since the ignition delay characteristics of diesel fuels directly
influence the interval of uncontrolled combustion during injection and, as a

result, the overall engine performance, this property is of primary importance.

Thus, it becomes desirable to have a numerical basis for evaluating the fuel
ignition delay and measuring or predicting this property.
The cetane number of a diesel fuel is the numerical result of an engine test
designed to evaluate fuel ignition delay. To establish the cetane number scale,
two reference fuels were selected. One, normal cetane, has excellent ignition
qualities and, consequently, a very short ignition delay. A cetane number 100
was arbitrarily assigned to this fuel. The second fuel, alphamethylnaphthalene,
has poor ignition qualities and was assigned a cetane number of zero. In 1962,
alphamethylnaphthalene was replaced as a primary reference fuel by hepta-
methylnonane which has a cetane number of 15 as determined by use of the two
original primary reference fuels.
To determine the cetane number of any fuel, its ignition delay is compared in
a standard test engine with a blend of reference fuels. This engine and the
prescribed test method are described in ASTM Test for Ignition Quality of Diesel
Fuels by the Cetane Method (D 613).
The cetane number of a diesel fuel is defined as "the whole number nearest to
the value determined by calculation from the percentage by volume of normal
cetane (Cetane No. = 100) in a blend with heptamethylnonane (Cetane No. =
15) which matches the ignition quality of the test fuel when compared by this
method." The matching blend percentages to the first decimal are inserted in the
following equation to obtain the cetane number
Cetane No. = percent n-cetane + 0.15 (percent heptamethylnonane).
The shorter the ignition delay period, the higher the cetane number of the fuel
and the smaller the amount of fuel in the combustion chamber when the fuel
ignites. Consequently, high-cetane number fuels generally cause lower rates of
pressure rise and lower peak pressures. Both of these tend to lessen combustion
noise and to permit improved control of combustion resulting in increased
engine efficiency and power output.
In addition to these advantages, higher cetane number fuels tend to result in
easier starting, particularly in cold weather, and faster warm-up. Reduced
exhaust smoke and odor are associated also with higher cetane numbers.
High-speed diesel engines normally are supplied with fuels in the range of 45
to 55 cetane number (their requirements may be as low as 35). Table 5
summarizes the typical inspections of various marketed diesel fuels characterized
primarily on the basis of use. As can be seen, the cetane number ranges from 50
for kerosine to 38 for marine distillate fuel.

Cetane lndex
Since the determination of cetane number by engine testing requires special
equipment as well as being time consuming and costly, alternate methods have
been developed for calculating estimates of cetane number. The calculations are
based upon equations involving values of other known characteristics of the fuel.

z
t~
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O
TABLE 5-Typical inspections of diesel fuels.
-4
Ill

Fuel Type -4
t~

Fuel Property Kerosine Premium Diesel Railroad Diesel Marine Distillate Diesel

Cetane number 50 47 40 38
Boiling range, ~ (~ 325 to 550 (163 to 288) 360 to 675 (182 to 357) 350 to 675 (176 to 357) 350 to 500(176 to 250)
(90 percent)
Viscosity, SSU at 100OF (380C) 33 35 36 47
Gravity, ~ 42 37 34 26
Sulphur, weight percent 0.12 0.30 0.50 1.2
Uses high speed city buses high speed buses, medium speed buses, low speed buses, heavy
trucks, tractors, railroad, marine, and marine and large
light marine engines stationary engines stationary engines

One of the most widely used methods is based on the Calculated Cetane Index
formula. This formula represents a method for estimating the cetane number of
distillate fuels from American Petroleum Institute (API) gravity and midboiling
point. The index value as computed from the formula is designated as ASTM
Calculated Cetane Index of Distillate Fuels (D 976/IP 218). Since the formula is
complicated in its manipulation, a nomograph based on the equation has been
developed. This nomograph, together with the equation, is shown in Fig. 3. An
example illustrating the use of the chart is also presented. It must be recognized
that the calculation of cetane index is not an optional method for expressing
cetane number. Rather, it is a supplementary tool for predicting cetane number
with considerable accuracy when used with due regard for its limitations. The
following are among the limitations of calculated cetane index.
1. It is not applicable to fuels containing additives for raising cetane number.
2. It is not applicable to pure hydrocarbons, synthetic fuels, alkylates, or coal
tar products.
3. Correlation is fair for a given type of fuel but breaks down if fuels of
widely different composition are compared.
4. Appreciable inaccuracy in correlation may occur when used for crude oils,
residuals, or products having end points below 260~ (500~

Diesel Index
The diesel index is derived from the API gravity and ASTM Test for Aniline
Point and Mixed Aniline Point of Petroleum Products and Hydrocarbon Solvents
(D 611). Aniline point is the lowest temperature at which the fuel is completely
miscible with an equal volume of aniline. The formula for diesel index is as
follows

Diesel index = aniline point (~ API gravity @ 60~

100
This equation is seldom used because the results can be misleading, especially
when applied to blended fuels.

Gravity
Gravity is an indication of the density or weight per unit volume of the diesel
fuel. ASTM Test for Density, Specific Gravity, or API Gravity of Crude
Petroleum and Liquid Petroleum Products by Hydrometer Method (D 1298/IP
160) shows that the principal use of specific gravity is to convert weights of oil
to volumes or volumes to weights. Specific gravity also is required when
calculating the volume of oil at a temperature different from that at which the
original volume was measured.
Although specific gravity by itself is not a significant measure of quality, when
considered with other tests, it may give useful information. For a given volatility
range, high-specific gravity is associated with aromatic or naphthenic hydro-

I~I~ D 9 7 6 - ( ~ ) 2 1 8

CALCULATED CETANE INDEX oc ~

CALC CI :
0 49083+ I.O6577(XI -OOOtOS3Z IX} z
x : 97.833 {LOG MID 8 PTe. "F)z + 2 208~ (APl) LOG.MID.a PT.,'F +0.01247 (AP~]z
~90

- 4255b {LOG MIO el P~ .'F) -4.7SOS (API} +41915S 3E0__ ~80

54
CORRECTION FOR BAROMETRIC PRESSURE :70
M~D,B
F. P ' { . ~ E C ' h O N ~) FOR
EACH I0 MM OIFF. 350 - 6O
TEMP RANGE IN PRESSURE
374-410
4r0-446
446-482
i oz
06
I II 340- ~
-650
482-516 I 15 Z-40
318-534 119
I 334-590 I 24 :-30
3 9 0 - 626 1 28 330- O(~
626-662 1.32 LEO --
48 662 - 6 9 8 1.37 - ,~
I TEMPERATURE FOR50% RECOV(REDAT :~o
76OMM Hg BAROMETRrCPRESSURE 320--
t-"
46 ~ TOBE ABOEOFORPRESSURESBELOW - -C~OO~
T60 MM Hg OR SUBTRACTED FOR
PRESSURES ABOVET60 MM Hg ~i0_ 90

300-- 70 O

42 - 70 60

9 .--" _--550 ~:
40- 65 ..- :
- "" ~-40 ('~
60 x .--"" " 280- :

55 UJ ..- : o;
,~ ..... 270- :2~ B
,~
~- - 36" .---- . - so ~ -,o ~.~
~.

- ....... ,.o 260- -5oo

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_ ......

32-

3o- :,o i
240-
i - 30

2e~ -25 -450

230-
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26"
i Z0 "

24- 220-
~ -3o
i EXAMPLE:
MID 8 PT.550*~ AT 700MM Hg
?o
22. A PI GRAVITY 33.0
CORRECTqON FOR MIO B. PT+, 1.19= 6 9 7.14 210 l0
C0RREC~EO .to e p'r ,~o.r +?.14.r .~S;'.I4"~"
CALC.C(T*NE INDEXCNOMOGRAPH) : 5f. 4
CALC CETAN( INOEX(FORUULAI = Sl.,~
20 404)
N O T E - - T h e Calculated Cetanr I n d e x equation represents a useful t o o l f o r e~timotmg cetane n u m b e r . Due t o inherent
|imitations in its application, I n d e x v a l u e s m a y n o t be a v a l i d s u b s t i t u t e f o r A S T M Cetane Numbers as d e t e r m i n e d in a
testengine.
FIG. 3-Nomograph .for calculated cetane index {ECS-1 Meter Basis-Method D 613}.

carbons and low-specific gravity with paraffinic hydrocarbons. The specific heat
energy, British thermal unit per pound, potentially available from the fuel
decreases with an increase in density or specific gravity. However, the pounds
per gallon increase with density as does the potential total British thermal unit
per gallon.
API gravity (ASTM D 1298/IP 160) is an arbitrary figure which permits
calcualtions to be made in whole numbers. It is related to the specific gravity in
accordance with the following formula

API gravity, deg = 141.5 - 131.5

sp gr (60/60~

Distillation
Particularly in medium- and high-speed engines, distillation (or volatility)
characteristics of a diesel fuel exert a great influence on its performance.
Distillation characteristics are measured with a procedure, ASTM Test for
Distillation of Petroleum Products (D 86/IP 123), in which a sample of the fuel
is distilled and the vapor temperatures recorded for the percentages of
evaporation or distillation throughout the range.
The average volatility requirements of diesel fuels vary with engine speed, size,
and design. However, fuels having too low volatility tend to reduce power
output and fuel economy through poor atomization, while those having too high
volatility may reduce power output and fuel economy through vapor lock in the
fuel system or inadequate droplet penetration from the nozzle. In general, the
distillation range should be as low as possible without adversely affecting the
flash point, burning quality, heat content, or viscosity of the fuel. If the 10
percent point is too high, poor starting may result. An excessive boiling range
from 10 to 50 percent evaporated may increase warm-up time. A low 50 percent
point is desirable to minimize smoke and odor. Low 90 percent and end points
tend to ensure low carbon residuals and minimum crankcase dilution.
The temperature for 50 percent evaporated, known as the midboiling point,
usually is taken as an overall indication of the fuel distillation characteristics
when a single numerical value is used alone. For example, in high-speed engines a
50 percent point above 302~ (575~ might cause smoke formation, give rise to
objectionable odor, cause lubricating oil contamination, and promote engine
deposits. At the other extreme, a fuel with excessively low 50 percent point
would have too low a viscosity and heat content per unit volume. Therefore, a
50 percent point in the range of 232 to 280~ (450 to 535~ desirable for the
majority of higher speed type diesel engines. This temperature range usually is
broadened for larger, slower speed engines.
The distillation test for gas-turbine fuel shows the volatility of the fuel and the
ease with which it can be vaporized. A low-volatility fuel results in poor ignition
and combustion characteristics. Arctic and antarctic operations, as well as winter
conditions, may require additional heat for vaporization or an improved means

of atomization for heavier distillates and cold fuels. Distillation temperature is

not directly significant to the operation of gas turbines designed for Grade Nos.
3-GT and 4-GT. In gas turbines that are susceptible to carbon deposition and
smoke formation, the more volatile fuels may provide better performance.

Viscosity
Viscosity, ASTM Test for Kinematic Viscosity of Transparent and Opaque
Liquids (and the Calculation of Dynamic Viscosity) (D 445/IP 71), may be
described as a measure of a liquid's resistance to flow. It usually is measured by
recording the time required for a given volume of fuel at a constant temperature
to flow through a small orifice of standard dimensions. The viscosity of diesel
fuel is important primarily because of its effect on the handling of the fuel by
the pump and injector system.
Fuel viscosity exerts a strong influence on the shape of the fuel spray. High
viscosities can cause poor atomization, large droplets, and high-spray jet
penetration. With high viscosities, the jet tends to be a solid stream instead of a
spray of small droplets. As a result, the fuel is not distributed in, or mixed with,
the air required for burning. This results in poor combustion, accompanied by
loss of power and economy. In small engines, the fuel spray may impinge upon
the cylinder walls, washing away the lubricating oil film and causing dilution of
the crankcase oil. Such a condition contributes to excessive wear.
Low-fuel viscosities result in a spray which is too soft and does not penetrate
far enough in the combustion chamber for good mixing. Combustion is impaired
and power output and economy are decreased. Low viscosity can lead to
excessive leakage past the injection pump plunger. Fuel metering becomes
inaccurate and engine efficiency is reduced. Wear of the fuel system components
may increase because lubricating properties of fuels tend to decrease with
viscosity.
Fuel viscosities for high-speed engines range from 1.8 to 5.8 cSt (32 to 45
SUS) at 37.8~ (100~ Usually the lower viscosity limit is established to
prevent leakage in worn fuel injection equipment as well as to supply lubrication
for injection system components in certain types of engines. During operation at
low-atmospheric temperatures, the viscosity limit sometimes is reduced to 1.4
cSt (30 SUS) at 37.8~ (100~ to obtain increased volatility and sufficiently
low-pour point. Fuels having viscosities greater than 5.8 cSt (45 SUS) usually are
limited in application to the slower-speed engines. The very viscous fuels
commonly used in large stationary and marine engines normally require
preheating for proper pumping, injection, and atomization.
High-viscosity fuels used in gas turbines can result in poor ignition and
combustor characteristics and cause excessive pressure losses in the piping
system. Even normally free-flowing fuels become thicker, and eventually solid,
as temperature decreases. For heavier industrial fuels, fuel temperature must be
controlled to assure viscosity suitable for atomization.

Heat of Combustion
The heat of combustion of a fuel, ASTM Test for Heat of Combustion of
Liquid Hydrocarbon Fuels (General Bomb Method) (D 240), is the amount of
heat produced when the fuel is burned completely. There are two heats of
combustion, or calorific values, for every petroleum fuel-gross and net. When
hydrocarbons are burned, one of the products of combustion is water vapor. The
difference between the two calorific values is that the gross includes the heat
given by the water vapor in condensing, while the net value does not include this
heat.
The power available from an engine under constant, part-throttle, running
conditions and with a constant rate of fuel supply is governed by the calorific
value of the fuel. A fuel of low-calorific value yields less heat on combustion
and, therefore, less power than the same amount of a fuel with high-calorific
value. To maintain power output with the low-calorific value fuel, more of it
would have to be used. The importance of this quality depends on whether the
user purchases fuel on a weight or volume basis.
Calorific values can be calculated with an accuracy sufficient for normal
purposes from the specific gravity of the product. One relationship which can be
used is

Calorific value (gross British thermal units per pound) =

(12 400 to 2 100 d 2) x 1.8
where d is the specific gravity at 60/60~ (15.6/15.6~

Cloud Point
Under low-temperature conditions, paraffinic constituents of a fuel may be
precipitated as a wax. The wax settles out and blocks the fuel system lines and
filters causing malfunctioning or stalling of the engine. The temperature at which
the precipitation occurs depends upon the origin, type, and boiling range of the
fuel. The more paraffinic the fuel, the higher the precipitation temperature and
the less suitable the fuel for low-temperature operation.
The temperature at which wax is first precipitated from solution can be
measured by ASTM Test for Cloud Point of Petroleum Oils (D 2500/IP 219) or
by ASTM Test for Wax Appearance Point of Distillate Fuels (D 3117). The
cloud point of a fuel is a guide to the temperature at which it may clog filter
systems and restrict flow. Cloud point is becoming increasingly important for
fuels used in high-speed diesel engines because of the trend toward finer filters.
The finer the filter, the more readily it will become clogged by small quantities
of precipitated wax. Larger fuel lines, filters of greater capacity, and filters
located to receive engine heat reduce the problem and therefore widen the cloud
point range of fuels which can be used.

Pour Point
The pour point, ASTM Test for Pour Point of Petroleum Oils (D 97/IP 15), of
a fuel is an indication of the lowest temperature at which the fuel can be
pumped. Pour points often occur 4.5 to 5.5~ (8 to 10~ below the cloud
points, and differences of 8 to ll~ (15 to 20~ are not uncommon. Fuels, and
in particular waxy fuels, will flow below their tested pour point in some
circumstances. However, pour point is a useful guide to the lowest temperature
at which a fuel can be used.
No wax precipitation problems are encountered at temperatures above the
cloud point and satisfactory operation is unlikely at temperatures below the
pour point. The level between these two temperatures at which trouble-free
operation is just possible will depend upon the design and layout of the fuel
system. A system that contains small, exposed lines and small area fine filters in
cold locations will be more prone to early failure than one where the lines are
unrestricted and sheltered and where any fine filters are located so that they
readily pick up engine heat.
Sometimes additives are used to improve the low-temperature fluidity of diesel
fuels. Such additives usually work by modifying the wax crystals so that they are
less likely to form a rigid structure. Thus, although there is no alteration of the
cloud point, the pour point may be lowered dramatically. Unfortunately, the
improvement in engine performance as a rule is less than the improvement in
pour point. Consequently, the pour-point temperatures cannot be used to
indicate engine performance with any accuracy.
Attempts to develop suitable flow tests have been to date only moderately
successful due primarily to the limited amount of firm field operability data on
which to base the work. Consequently, there has been a great reluctance to
depart from the known and accepted cloud and pour-point tests as the major
low-temperature performance criteria. Nevertheless, low-temperature operability
tests based on the plugging of cold filters have now been accepted by France
(AFNOR-549), Germany (DIN 00 51 770), and Sweden (SIS 155 122). ASTM is
examining the test for suitability, and moves to develop an agreed European
standard are in progress.

Flash Point
The flash point of a fuel is the temperature to which the fuel must be heated
to produce an ignitable vapor-air mixture above the liquid fuel when exposed to
an open flame. The most common procedure used for determining the flash
point of fuels is ASTM Test for Flash Point by Pensky-Martens Closed Cup
Method (D 93/IP 34).
In practice, flash point is important primarily from a fuel handling standpoint.
Too low a flash point will cause fuel to be a fire hazard, subject to flashing, and
possible continued ignition and explosion. In addition, a low-flash point may
indicate contamination by more volatile and explosive fuels such as gasoline.
Insurance companies, government agencies, and private users set mandatory

minimum limits on flash point because of fire hazard considerations. These

limits must be taken into account when establishing fuel specifications. In spite
of its importance from a safety standpoint, the flash point of a fuel has no
significance to its performance in an engine. Auto-ignition temperature is not
influenced generally by variations in flash point nor are other properties, such as
fuel injection and combustion performance.

Sulfur
Diesel Engines-Sulfur can cause wear in diesel engines as a result of the
corrosive nature of its combustion by-products and increase the amount of
deposits in the combustion chamber and on the pistons. The sulfur content of a
fuel, ASTM Test for Sulfur in Petroleum Products (General Bomb Method) (D
129/IP 61) and ASTM Test for Sulfur in Petroleum Oils (Quartz-Tube Method)
(D 1551), depends on the origin of the crude oil from which the fuel is made
and on the refining methods used. Sulfur can be present in a number of
forms-as mercaptans, sulfides, disulfides, or heterocyclic compounds such as
thiophenes-all of which affect wear and deposits.
Fuel sulfur tolerance by a diesel engine depends largely upon whether the
engine is of the low- or high-speed type and the prevalent operating conditions.
Low-speed engines can tolerate more sulfur than their high-speed counterparts
because they operate under relatively constant speed and load conditions. Under
these conditions lubricating oils, cooling water, and combustion zone tempera-
tures show little fluctuation. These steady temperatures make low-speed engines
more tolerant to sulfur.
High-sulfur fuels for diesel engines are undesirable from a purely technical
standpoint regardless of engine type. However, less harm will occur from fuel
sulfur when engines are operated at high-power outputs and operating
temperatures than at low temperatures. Under the lower temperature conditions
that result from stopping and starting or decrease of load or speed or both,
moisture condensation is apt to occur within the engine. The sulfur in the fuel
then combines with the water to form acid solutions which corrode metal
components and increase wear of moving parts.
Active sulfur in fuel tends to attack and corrode injection system components.
Sulfur compounds also contribute to combustion chamber and injection system
deposits.
Fuel sulfur is measured both on the basis of quantity and potential corrosivity.
The quantitative measurements can be made by means of a combustion bomb
(ASTM D 129/IP 61). The measurement of potential corrosivity is determined
by means of a corrosion test such as the copper strip procedure described in
ASTM Detection of Copper Corrosion from Petroleum Products by the Copper
Strip Tarnish Test (D 130/IP 154). The quantitative determination is an
indication of the corrosive tendencies of the fuel combustion products while the
potential corrosivity indicates the extent of corrosion to be anticipated from the
unburned fuel, particularly in the fuel injection system.

It is not unusual for residual type fuels used in the larger, slower-speed engines
to have a sulfur content of 3.0 percent by weight or even higher. On the other
hand, fuel for high-speed use generally has a sulfur content of 0.4 percent by
weight or less to avoid excessive wear. Recommended practices are to maintain
the sulfur content as low as practicable.
Modem heavy duty engine oils of high detergency and those containing reserve
alkalinity properties minimize the effects of diesel fuel sulfur. However, several
factors should be considered before the decision is made to use low-cost,
high-sulfur content diesel fuel:
1. Increased cost of higher quality lubricating oil required.
2. Possible increased engine and fuel system wear.
3. Probable fuel system modifications required if a residual fuel is to be
considered.
Gas Turbines-There is evidence that high-sulfur levels adversely affect the
carbon forming tendency in gas-turbine combustion chambers and that the
presence of large amounts of oxides of sulfur in the combustion gases promotes
corrosion. The ASTM Specification for Gas Turbine Fuel Oils (D 2880) calls for
sulfur levels no greater than 0.5 percent by weight.
Although the amount and type of sulfur compounds that appear in gas-turbine
fuels vary with crude source, total sulfur content is usually between 0.2 and 0.4
percent which is well within acceptable limits. Direct corrosivity of sulfur
compotmds is measured by the copper strip test (ASTM D 130/IP 154).
Mercaptan sulfur content is limited to low levels because of objectionable
odor, adverse effects on certain fuel system elastomers, and corrosiveness toward
fuel system metals. Mercaptan sulfur is normally determined by ASTM Test for
Mercaptan Sulfur in Aviation Turbine Fuels (Color-Indicator Method) (D
1219/IP 104) or by the Doctor test method, ASTM Specification for
Hydrocarbon Drycleaning Solvents (D 484/IP 30).

Carbon Residue
The ASTM Test for Conradson Carbon Residue of Petroleum Products (D
189/IP 13) is quoted widely in fuel specifications. The carbon residue is a
measure of the carbonaceous material left in a fuel after all the volatile
components are vaporized in the absence of air. At one time, there was believed
to be a definite correlation between Conradson carbon results in diesel fuels and
deposit formation on injector nozzles, but this view now is thought to be an
oversimplification.
The type of carbon formed is as important as the amount. Small quantities of
hard, abrasive deposits can do more harm than larger amounts of soft, fluffy
deposits. The latter can be eliminated largely through the exhaust system.
Carbon residue tests are used primarily on residual fuels since distillate fuels
which are satisfactory in other respects do not have high Conradson carbon
residue. Because of the considerable difference in Conradson carbon residue

results between distillate and residual fuels, the test can be used as an indication
of contamination of distillate fuel by residual fuel.
The significance of the Conradson carbon test results also depends on the type
of engine in which the fuel is being used. Fuels with up to 12 percent weight
Conradson carbon residue have been used successfully in slow-speed engines.
In gas-turbine fuels, carbon residue is a rough approximation of the tendency
of a fuel to form carbon deposits in the combustor. Combustion systems
designed for use on Grade Nos. 3-GT and 4-GT are insensitive to this problem,
but other gas turbines may require a limit on the carbon residue.
Carbon deposits in gas turbines are undesirable because they form heat
insulated spots in the combustor that become very hot. Adjacent metal is kept at
a relatively low temperature by the cooling air. The "hot spot" formed by
carbon deposit creates a large temperature gradient with resultant high stress,
distortion, and perhaps eventual cracking of the combustor shell.
Carbon deposits may also contribute to nonuniformity of operation and flow
pulsation. If pieces of the carbon deposit are broken off and carried through the
turbine, blade erosion (efficiency loss) or partial blocking of the nozzles may
occur. Carbon deposits in a combustor usually are accompanied by a smoky
discharge and a low value for the heat release factor.
Carbon deposits also occur on the fuel injectors. This disrupts the mixture
formation and, consequently, combustion.

Ash

Small amounts of nonburnable material are found in fuels in two forms: (1)
solid particles, and (2) oil or water-soluble metallic compounds. These materials
are designated as ash. The solid particles are for the most part the same material
that is designated as sediment in the water and sediment test.
The quantitative determination for ash is made by ASTM Test for Ash from
Petroleum Products (D 482/IP 4). In this test, a small sample of fuel is burned in
a weighed container until all of the combustible matter has been consumed. The
amount of unbumable residue is the ash content, and it is reported as percent by
weight of the fuel.
Since diesel fuel injection components are made with great precision to
extremely close fits and tolerances, they are very sensitive to any abrasive
material in the fuel. Depending on their size, solid particles can contribute to
wear in the fuel system and plugging of the fuel filter and fuel nozzle. In
addition, abrasive ash materials can cause wear within the engine by increasing
the overall deposit level and adversely affecting the nature of the deposits.
The soluble metallic compounds have little or no effect on wear or plugging,
but they can contain elements that produce turbine corrosion and deposits as
described in later paragraphs.

Neutralization Number
ASTM Test for Neutralization Number by Color-Indicator Titration (D 974/IP
139) is a measure of the inorganic and total acidity of the fuel and indicates its
tendency to corrode metals which it may contact.

Stability
On leaving the refinery, the fuel will inevitably come into contact with air and
water. If the fuel includes unstable components, which may be the case with
fuels containing cracked products, storage in the presence of air can lead to the
formation of gums and sediments. These gums and sediments can cause filter
plugging, combustion chamber deposit formation, and gumming or lacquering of
injection system components with resultant sticking and wear.
An accelerated stability test, ASTM Test for Stability of Distillate Fuel Oil
(Accelerated Method) (D 2774), often is applied to fuels to measure their
stability. A sample of fuel is heated for a fixed period at a given temperature,
sometimes in the presence of a catalyst metal, and the amount of sediment and
gum formed is taken as a measure of the stability.
The thermal stability test measures the tendency of a fuel to form deposits in
the fuel system of a gas turbine. In certain types of gas turbines where the fuel
system operates at high-fuel temperature, the thermal stability must be specified.

Water and Sediment

One of the most important characteristics of a fuel is the water and sediment
content, ASTM Test for Water and Sediment in Crude Oils and Fuel Oils by
Centrifuge (D 1796/IP 75). High-water and sediment content is the result of
poor handling and storage practices from the time the fuel leaves the refinery
until the time it is delivered to the engine injection system.
Water can easily find its way into fuels as a result of breathing in moisture
laden air in storage facilities. When sudden drops in atmospheric temperature
take place, condensation of moisture occurs. Also, leakage of rain into fuel
transportation and storage facilities, leakage of water during shipment by tanker,
and the presence of water accumulated in tanks used for storage and handling
can cause water contamination.
Sediment generally consists of carbonaceous material, metals, or other
inorganic matter. There are several causes of this type of contamination:
1. Rust or dirt present in tanks and lines.
2. Dirt introduced through careless handling practices.
3. Dirt present in the air breathed into the storage facilities with fluctuating
atmospheric temperature.
Particularly during storage and handling at elevated temperatures, instability
and resultant degradation of the fuel in contact with air contribute to the
formation of organic sediment.

Water can contribute to filter blocking and cause corrosion of the injection
system components. In addition to clogging of the filters, sediment can cause
wear and create deposits both in the injection system and in the engine.

Composition
The chemical composition of a typical fuel is extremely complex because an
enormous number of compounds are normally present. It usually is neither
practicable nor profitable to perform individual compound analyses. However, it
is sometimes helpful to determine the percentages of broad classes of
compounds such as aromatics, paraffins, naphthenes, and olefins. A variety of
test methods have been proposed. One that has been approved for fuels that boil
below 315~ (606~ is ASTM Test for Hydrocarbon Types in Liquid Petroleum
Products by Fluorescent Indicator Adsorption (D 1319/IP 156).

Appearance and Odor

The general appearance, color, and clarity of a distillate fuel are useful
controls against contamination by residuals, water, or fine solid particles.
Although the small amount of water or solids required to produce an
unsatisfactory hazy fuel is usually insufficient to affect the performance of the
fuel, customer acceptance is important. Therefore, it is prudent to check by
visual inspection that clear fuel is being delivered.
Similarly, customer acceptance is important with regard to odor, and it is
usually politic to ensure the fuel is reasonably free of contaminants, such as
mercaptans, which impart unpleasant odors to the fuel.

Vanadium, Sodium, Calcium, Lead

Vanadium can form low-melting compounds, such as vanadium pentoxide
which melts at 69 I~ (1275~ and which causes severe corrosive attack on all of
the high-temperature alloys used for gas-turbine blades and diesel engine valves.
For example, to reduce the corrosion rate at 871~ (1600~F) on AISI Type 310
steel to a level comparable with the normal oxidation rate, it is necessary to limit
vanadium in the fuel to less than 2 ppm. At 10 ppm, the corrosion rate is three
times the normal oxidation rate, and at 30 ppm, it is 13 times the normal
oxidation rate. However, if there is sufficient magnesium in the fuel, it will
combine with the vanadium to form compounds with higher melting points and
thus reduce the corrosion rate to an acceptable level. The resulting ash will form
deposits in the turbine, but the deposits are self-spalling when the turbine is shut
down. For gas turbines operating below 649~ (1200~ the corrosion of the
high-temperature alloys is of minor importance, and the use of a silicon-base
additive will further reduce the corrosion rate by absorption and dilution of the
vanadium compounds.
Sodium and potassium can combine with vanadium to form eutectics which
melt at temperatures as low as 565~ (1050~ and with sulfur in the fuel to

yield sulfates with melting points in the operating range of the gas turbine. These
compounds produce severe corrosion, and for turbines operating at gas inlet
temperatures above 649*(2 (1200~ no additive has been found which
successfully controls such corrosion without forming tenacious deposits at the
same time. Accordingly, the sodium-plus-potassium level must be limited, but
each element is measured separately. Some gas-turbine installations incorporate
systems for washing oil with water to reduce the sodium-plus-potassium level. In
installations where the fuel is moved by sea transport, the sodium-plus-potassium
level should be checked prior to use to ensure that the oil has not become
contaminated with sea salt. For gas turbines operating below 649*C (1200~
the corrosion due to sodium compounds is of minor importance and can be
further reduced by silicon-base additives. A high-sodium content is beneficial
even in these turbines, because it increases the water-solubility of the deposits
and thereby increases the ease with which gas turbines can be water-washed to
obtain recovery of the operating performance.
Calcium is not harmful from a corrosion standpoint; in fact, it serves to inhibit
the corrosive action of vanadium. However, calcium can lead to hardbonded
deposits which are not self-spalling when the gas turbine is shut down and not
readily removed by water washing of the turbine. The fuel washing systems used
at some gas-turbine installations to reduce the sodium and potassium level also
will lower significantly the calcium content of fuel oil.
Lead can cause corrosion, and, in addition, it can spoil the beneficial inhibiting
effect of magnesium additives on vanadium corrosion. Since lead only is found
rarely in significant quantities in crude oils, its presence in the fuel oil is
primarily the result of contamination during processing or transportation.

Applicable ASTM Specifications

D 396 Specification for Fuel Oils
D 975 Specification for Diesel Fuel Oils
D 2880 Specification for Gas Turbine Fuel Oils

Applicable ASTM/IP Standards

ASTM IP Title

D 86 123 DistiUation of Petroleum Products

D 93 34 Flash Point by Pensky-Martens Closed Tester
D 97 15 Pour Point of Petroleum Oils
D 129 61 Sulfur in Petroleum Products (General Bomb Method)
D 130 154 Detection of Copper Corrosion from Petroleum
Products by the Copper Strip Tarnish Test
D 189 13 Conradson Carbon Residue of Petroleum Products
D 240 12 Heat of Combustion of Liquid Hydrocarbon Fuels
(General Bomb Method)

D 445 71 Kinematic Viscosity of Transparent and

Opaque Liquids (and the Calculation of
Dynamic Viscosity)
D 482 4 Ash from Petroleum Products
D 611 2 Aniline Point and Mixed Aniline Point of Petroleum
Products and Hydrocarbon Solvents
D 974 139 Neutralization Number by Color-Indicator Titration
D 976 218 Calculated Cetane Index of Distillate Fuels
D 1298 160 Density, Specific Gravity or API Gravity of
Crude Petroleum and Liquid Petroleum Products
by Hydrometer Method
D 1319 156 Hydrocarbon Types in Liquid Petroleum Products
by Fluorescent Indicator Adsorption
D 1551 63 Sulfur in Petroleum Oils (Quartz-Tube Method)
D 1796 75 Water and Sediment in Crude Oils and
Fuel Oils by Centrifuge
D 2274 Stability of Distillate Fuel Oil (Accelerated Method)
D 2500 219 Cloud Point of Petroleum Oils
D3117 Wax Appearance Point of Distillate Fuels

Bibliography
blaleev,V. L., Internal Combustion Engines, McGraw-Hill,New York, 1945.
Stinson, K. W., Diesel Engineering Handbook, Diesel Publications, Inc.,Stamford,Conn.,
1963.
Taylor, E. S., The Internal Combustion Engine, InternationalTextbook Co., Scranton, Pa.,
1938.

Chapter 7 Heating and Power

Generation Fuels

Introduction
Mthough most petroleum products can be utilized as fuels, the term "fuel
oil," if used without qualification, may be interpreted differently in various
countries. For example, in Europe fuel oil generally is associated with the black,
viscous, residual material which remains as the result of refinery distillation of
crude oil either alone or in a blend with lighter components, and it is used for
steam generation for large, slow-speed diesel engine operation and industrial
heating and processing. In the United States, the term "fuel oil" is applied to
both the residual type material and the distillate type products such as domestic
heating oil, kerosine, and burner fuel oils.
Because fuel oils are complex mixtures of compounds of carbon and
hydrogen, they cannot be classified rigidly or defined exactly by chemical
formulas or definite physical properties. For purposes of this chapter, the term
"fuel oil" will include all petroleum oils heavier than gasoline that are used in
burners. Because of the wide variety of petroleum fuel oils, the arbitrary
divisions or classifications which have become widely accepted in industry are
based more on their application than on their chemical or physical properties.
Thus, it is not uncommon to find large variations in properties among petroleum
products sold on the market for the same purpose. However, two broad
classifications are generally recognized: (1) "distillate" fuel oils and (2)
"residual" fuel oils. The latter are often referred to as heavy fuel oils and may
contain cutter stock or distillates.
Distillate fuel oils are petroleum fractions that have been vaporized and
condensed. They are produced in the refinery by a distillation process in which
petroleum is separated into its fractions according to their boiling range.
DistiUate fuel oils may be produced not only directly from crude oil, that is,
"straight-run," but also from subsequent refinery processes such as thermal or
catalytic cracking. Domestic heating oils and kerosine are examples of distillate
fuel oils.
On the other hand, residual or heavy fuel oils are composed wholly or in part
of undistilled petroleum fractions from crude distillation (atmospheric or
vacuum), visbreaking, or other refinery operations. The various grades of heavy
fuel oils generally are produced to meet definite specifications in order to assure
suitability for their intended purpose. Residual oils are classified usually by
viscosity in contrast with distillates which normally are defined by boiling range.

112
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CHAPTER 7 ON HEATING AND POWER GENERATION FUELS 1 13

Figure 1 depicts the approximate boiling ranges of various distillate fuels in

comparison with gasoline. It should be recognized that the designations and uses
shown tend to vary in different countries. For convenience, the products will be
introduced and discussed under the general headings of kerosine, domestic
heating oils, and residual or heavy fuel oils.

Kerosine
Following the discovery of oil in 1859, kerosine became the major petroleum
product and was used, initially, for illumination and, subsequently, for heating.
While modern technology has diminished the importance of kerosine, it is still
utilized as a primary source of light in some lesser developed countries and for
standby or emergency lighting in the more advanced areas of the world. Because
it is cheap, portable, and flexible, kerosine also is used for domestic space and
water heating, refrigeration, heating of garages and greenhouses, incubation and
chicken brooders, and cooking. The discussion of kerosine in this chapter will
focus on its two primary uses-illumination and heating.
For heating and illumination purposes, kerosine is obtained by fractional
distillation of crude oil between approximately 149~ (3000F) and 302~
(575~ and constitutes a potential 5 to 20 percent volume yield depending on
the crude source. (In the United States less than 2 percent of the crude oil is
utilized for kerosine.) To decrease smoking, paraffinic stocks are used normally
in the manufacture of kerosine for lighting and heating. For the same reason,
aromatic stocks and cracked components are avoided.
When low-sulfur paraffinic crudes are fractionated to yield the proper boiling
range cut for kerosine, only a drying operation may be required before
shipment. Usually, however, some objectionable odors (mercaptans) are present,
and these are removed by caustic washing or converted to odorless compounds
by sweetening processes.
Kerosine from naphthenic or high-sulfur crudes requires hydrotreating, acid
treatment and water wash, or extraction with a solvent and caustic wash and
clay brightening to remove undesirable aromatics or sulfur compounds.
Following treatment, the kerosine streams are blended to meet specifications,
and the finished product is ready for marketing.

Domestic Heating Oils

Domestic heating oils are also distillate products. Their approximate boiling
range generally is from 160~ (320~ to 343"C (650~ They can include
components from three sources: (1) virgin stocks cut directly from crude, (2)
oils manufactured by catalytic cracking of heavier stocks, and (3) thermally
cracked streams. The percentages of these components blended into the heating
oil pool will vary considerably among individual refineries and between various
countries. For example, domestic heating oil in most areas outside North

OF 0

400
750
No. 2
700
Fuel
Oil
350
No. 1
650 Fuel
Oil
600
300

500
/A
45Q
~ M .250

4OO
Gasoline
350
--200

300

250 150

Note i. Residual Oils are classified on

the basis of viscosity
200
Note 2, No. 1 Fuel 0il is also kerosine i00
150 range oil or No. 1 burner oil

Note 3. No. 2 Fuel Oil is also gas oil,

100 domestic heating oil or No. 2
burner oil 50

i0
0
0

FIG. I-Range of distillation/'or distillate products. (1972 U.S. Bumines Survey].

America normally consists of straight-run gas oil from the distillation of the
crude; in the United States, the straight-run gas oil fraction is usually blended
with the appropriate boiling-range material from catalytic cracking processing.
With few exceptions, the components cut to the proper boiling range for
domestic heating oil require some chemical treatment (for example, additional
treatment may be required to remove or convert mercaptans to nonodorous
disulfides). Following the chemical treatment, the oils usually are washed with
water to remove all traces of the treating residues. As a finishing step, the oil is
dried by clay filtration or coalescing.
Domestic heating oils derived from heavier catalytic and thermal stocks may
require more severe treatment to remove olefins and other unstable compounds.
This is accomplished commonly by catalytic hydrogen treating.

Wherever applicable, such as in the United States, the various heating oil
streams finally are blended to meet manufacturing specifications. At this point, a
stabilizing inhibitor is often added. To provide the flow properties needed in
cold climates, pour-point depressant additives or wax crystal modifiers may be
used, or low pour-point kerosine may be blended with the fuel oil.

Residual or Heavy Fuel Oils

Residual fuel oils have a minimum flash point of 60~ (140~ and viscosities
that generally vary between 30 and 300 SFS at 50~ (122~ The oil viscosity
required to obtain satisfactory atomization varies according to the type of
burner used and is approximately 40 SFS or 80 cSt for steam atomizing burners
and 180 and 200 SUS or 39 to 43 cSt min for mechanical atomizing burners.
Therefore, it is necessary to heat the oil in order to achieve the required viscosity
reduction. This is done in a heat exchanger, consisting of a tube assembly
through which the oil flows, placed inside a shell containing the heating medium.
Usually the medium, at a pressure of 20 psig (1.406 kg/cm 2) or less, is steam.
Generally, the heating is done in two steps. The first step heats the oil as it is
withdrawn from the storage tank, or, in some cases, the whole tank of oil is
heated to about 37.80C (100~ so that its viscosity is within the pumping range
of 400 to 500 SFS or 850 to 100 eSt. In the second step, transfer pumps deliver
the oil from storage to the burner heating and pumping equipment at which
point it is raised to the required temperature and pressure for atomization.

Crude Oil as a Power Generation Fuel

While crude oil is not typically classified as a fuel oil, attention has begun to
focus on its potential as a power generation fuel. Stimulated by the energy
shortage, utilities have burned crude oil under power station boilers and as fuel
for gas turbines that drive standby generators. Other factors that influenced the
utilities' decision to use crude oil in this capacity were environmental
considerations, safety, cost, and availability of crude.
The specifications for crude oil as a power generation fuel have not been
established, but several known critical properties should be considered.
Examples include flash point, sulfur, ash, and metal content. The relatively
low-flash points normally associated with crude oils dictate that the storage and
handling facilities should be explosion proof, vapor proof, and vapor retaining.
To meet stack emissions standards in the United States without resorting to
scrubbers or other removal equipment, the crude oil must have low-ash and
low-sulfur contents. Low-metal contents are necessary to ensure adequate blade
performance when crude is used as a turbine fuel oil.
Additionally, crude oil used as a power generation fuel must meet obvious
requirements such as pumpability, and, in the case of turbine use, it must
comply with the turbine manufacturers specifications.

The standard tests applied to bumer fuels, which will be discussed later in this
chapter, are used to test crude oils to be used as fuel. In addition, vapor pressure
is determined by the ASTM Test for Vapor Pressure of Petroleum Products
(Reid Method) (D 323). Metal contents are measured by the ASTM Test for
Trace Metals in Gas Turbine Fuels (Atomic Absorption Method) (D 2788).

BurningEquipment
To understand fuel oil tests and their significance, it is necessary to have a
fundamental knowledge of the various types of burning equipment associated
with kerosine, domestic heating oils, and residual oils. The following paragraphs
provide a brief review of the subject.

Kerosine Burners
Although the appliances in which kerosine is used vary widely in design and
efficiency, there are three main burner types-wick-fed yellow flame, wick-fed
blue flame, and the pressure burner.
The wick-fed yellow flame type burner consists essentially of an oil reservoir
into which one end of a wick is immersed. The other end passes through a wick
guide and projects upward from it. A draft deflector and a chimney with air inlet
are provided. Oil flows by capilliary action to the top of the wick where it bums
and produces a luminous yellow flame. The flame size may be adjusted by
turning the wick up or down, thus exposing more or less area. Either fiat or
tubular wicks are used. Apart from its domestic use in kerosine lamps and small
portable stoves for heating and cooking, the wick-fed yellow flame type burner
in simple form is still used in brooders and incubators in the poultry industry.
Other applications include miners' safety lamps and certain railwhy signal lamps.
In the wick-fed blue flame, or kindler, type burner a long drum or chimney is
mounted over the burner to induce the air for combustion. The burner itself
includes a circular wick and a flame spreader. A well-known application of the
wick-fed blue flame method is the perforated sleeve vaporizing burner. This
design is known commonly as the "range burner" because of its early widespread
use in kitchen ranges. (Kerosine is sometimes referred to as "range oil.")
A typical range burner consists of a fiat, cast iron, or pressed steel base with
concentric inner-connected grooves and concentric perforated metal sleeves
between which combustion takes place. Kerosine is maintained at a depth of 1/8
to 1/4 in. (0.32 to 0.64 cm) in the grooves. Asbestos wicks, lighted manually, are
used to provide heat for oil vaporization and ultimate ignition of the oil vapors.
As the base heats up, the entering oil vaporizes from the surface, and the flame
lights from the wicks. Combustion air is induced by natural draft. The flame is
blue, and operation is essentially silent, odorless, and smokeless. A flue usually is
provided to remove combustion products. Constant level valves, or other devices
such as an inverted bottle based on the "chicken feeder" principle, are required
for the kerosine feed.

Appliances of the wick-fed, blue flame type are used primarily for heating and
cooking purposes. They also are used with incandescent mantles for lighting. The
design is such that intimate mixing of air and oil vapor takes place. This results
in more complete combustion, whereby the oil bums with an almost
nonluminous blue flame.
Blue flame type kerosine hotwater heaters and vaporizing pot burners will be
discussed in the section on domestic heating oil burners, since they can also bum
domestic heating oils.
With the pressure burner design, the oil reservoir is fitted with a pump which
enables pressure to be maintained. This pressure forces the oil up into a central
tube, through a previously heated vaporizing coil, and out through a jet. The
issuing oil vapor then mixes with air drawn in from the outside, and the mixture
passes to the burner where combustion takes place.
The principle of the pressure-type burner is employed in the Primus stove,
various kinds of blow-lamps, certain pressure burners fitted with mantles for
illumination, and for a variety of minor industrial applications.

Domestic Heating Oil Burners

For domestic heating oil to bum readily and satisfactorily, it must be
vaporized and mixed with the amount of air required to provide a proper
combustible mixture. This vaporization can be accomplished either through the
application of heat or atomization into very fine particles. Domestic heating oil
burners are classified according to the manner in which the vaporization and
subsequent burning occurs.
One of the simplest domestic burners is the vaporizing pot burner. These
burners are used in room space heaters, water heaters, and for cential heating in
warm air furnaces. Both natural and mechanical drafts are employed.
A typical pot burner consists of a metal pot perforated with holes for the
entrance of combustion air. Oil flows into the bottom of the pot by gravity and
is vaporized from the hot surface. After mixing with primary air that enters the
lower ports and additional secondary air in the upper section of the pot, the
vapors finally bum at the top of the vessel. Between periods of demand or
"high-fire" operation, most pot burners idle at a "low-fire" condition. Using
only primary air, the flames bum in the bottom section of the pot at a fraction
of the high-feed rate and provide the ignition source required for automatic
operation.
A typical water heater fired with a natural draft-pot burner requires a
relatively high draft (0.06 in. of water or more) to provide adequate combustion
air. Fuel flow is controlled by the thermostat to give high-fire operation for
heating and low-fire operation when the water is at design temperature.
By far the most common of the domestic heating oil burners in the United
States and the one fast growing in popularity in other countries is the
high-pressure atomizing gun burner. It is the most rugged and among the
cheapest of the domestic heating oil burners. In this type burner, oil is supplied

to a high-pressure atomizing nozzle, at 80 to 125 psig. (5.625 to 8.79 kg/cm2).

The high-pressure oil is accelerated in tangential slots to a high velocity. Upon
leaving the orifice, the oil breaks into a fine, cone-shaped spray of droplets.
Besides the atomizing function, the nozzle also meters the oil.
In the high-pressure gun burner, pump pressure is controlled by a pressure
regulating valve which bypasses excess oil to the pump inlet or tank. Combustion
air is supplied by a fan mounted on the same shaft as the pump. The air flows
through the blast tube in which the nozzle is centered. The ignition electrodes
are located slightly behind the spray cone. When power is supplied, the fan and
pump begin to rotate and sparking begins between electrodes. The regulating
valve opens when atomizing pressure is reached. By this time, the air stream is
blowing the center of the spark into the oil spray, and the oil is ignited.
The low-pressure atomizing burner is a more expensive device but offers some
advantages over the high-pressure gun. Atomization is accomplished in a nozzle.
Oil is supplied at relatively low pressure (1 to 15 psig, 0.07 to 1.055 kg/cm2). In
some cases, a premixed oil and air foam is supplied to this type of nozzle instead
of an oil stream. The high velocity of the primary air stream is used to shear off
the incoming oil at right angles. A finer spray results than is obtainable from
high-pressure nozzles, and this creates a lower smoking tendency. Between 2 and
15 percent of the combustion air is supplied as primary air. Secondary air
usually is provided around the nozzle as in the high-pressure gun burner. The oil
is metered by means of a metering pump or an orifice in the oil line.
Since there are no oil passages as small as those required for the high-pressure
nozzle, the low-pressure type of burner is less prone to plug. This enables the
low-pressure burner to function at 1 to 2 litres (0.26 to 0.53 gal) an hour while
the high-pressure burner, because of a plugging tendency, cannot operate
satisfactorily below 2 to 3 litres (0.53 to 0.79 gal) an hour.
Vertical atomizing burners produce a flame in the shape of an inverted
umbrella and bum in a bowl-shaped hearth. The oil may be atomized from a
spinning cup or with a conventional high-pressure nozzle. Sufficient air flow is
provided along the walls of the combustion chamber to prevent flame
impingement.
The wall-flame rotary vaporizing burner differs radically in principle from the
atomizing gun burners. In this equipment, oil is vaporized from a hot metal
hearth ring and mixed with air before buming from a set of grills. Its major
advantages are higher efficiency and quieter operation. However, the wall-flame
rotary burner is more critical of both adjustment and oil quality.
There are various designs of wall-flame rotary burners. In a common type, oil
flows by gravity through a metering valve to the central rotor. Centrifugal force
throws the oil in a coarsely atomized spray from two rotary distributor tubes to
the metal hearth ring. In operation, the ring runs hot enough to vaporize the oil.
Combustion air enters the center of the fan and is forced also towards the hearth
ring. The air-oil vapor mixture passes upwards through a set of stabilizing grills
from which the flame bums.

During start-up, the hearth ring is not hot enough to vaporize the oil. As the
rotor starts, oil wets the ring, and sparking begins between the ring and the
electrode. A small flame appears at this point and slowly spreads around the
hearth ring. As the metal becomes hotter, the flame grows and finally jumps to
the top of the grill. Improper adjustment or poor oil quality will cause the
formation of deposits on the hearth ring surface. These interfere with cold
starting and may result in burner failure.

Residual Oil Burning Equipment

In general, residual oil burning equipment is categorized according to the
method by which the fuel is atomized. Described in the following paragraphs are
air, steam, mechanical atomizing burners, and rotary type burners.
Air atomizing burners are used largely in industrial furnaces. Because
atomizing air mixes intimately with the oil and comprises part of the required
combustion air, burning begins more quickly and is completed sooner with this
type than with any other type of burner. This results in a shorter flame and
permits a smaller combustion space.
Inside-mix air atomizing burners are designed so that all atomizing air enters at
the air inlet and is controlled simultaneously with the oil by a single control
lever. Primary air enters a whiff chamber tangentially, which imparts a rotating
motion to the air. As the air approaches the oil nozzle, it attains maximum
velocity because of the venturi shape of the throat. The impact of the air
atomizes the oil as it emerges from the nozzle. The resultant air-oil mixture
leaves the mixing nozzle in the form of a divergent cone. It comes into contact
with the secondary air from an outer nozzle and is further atomized, thus
assisting the mixing process.
Steam atomizing burners are two basic types-inside mix and outside mix. As
the names suggest, the primary difference lies in where the mixing occurs. In the
inside-mix types, the steam and oil mix within the burner nozzle prior to
entering the furnace. Additionally, the flame from inside-mix burners may be
either fiat or conical, depending upon disposition of the burner openings, while
the outside mix burners, which were the first type of heavy oil burners, have a
flat flame.
Both the outside and inside mix burners are relatively fixed-ratio nozzles
which operate best at relatively constant fuel and air supply rates. Because of
this limitation, simple inside and outside mix burners are being used less
frequently. More sophisticated atomizing burners that yield efficient combustion
over a range of firing rates and loads even with very low fuel grades have become
available.
In the mechanical atomizing burner, atomization of the fuel oil is achieved by
forcing high-pressure, high-velocity oil into the furnace through a small bore
orifice or sprayer plate. Required pressure is approximately 300 psi (21.1
kg/cm 2) or more.

The important part of any mechanical atomizing burner is the sprayer plate.
The oil passes through slots in the plate at high velocity. The tangential
arrangement of the slots imparts a rotating motion to the oil. The resulting
centrifugal force causes the oil to break up into a hollow atomized cone as it
enters the furnace through the central orifice.
The firing range of boilers equipped with mechanical atomizing burners can be
changed by: (1) changing the number of burners in service, (2) replacing the
sprayer plates with plates having another size central orifice, (3) altering the
burner design so that more or less oil is allowed to flow through the same size
sprayer plate, and (4) changing the oil pressure and method of control in
conjunction with a burner design alteration similar to that described in (3).
In the rotary type burners, atomization is achieved through centrifugal force
imparted to the oil by a cup rotating at high speed. The atomized oil issues from
the rotating cup in the form of a hollow cone. The primary air supply enters the
furnace concentrically with this cone and mixes with the oil to form a conical
spray. Rapid mixing of the atomized oil and primary air is obtained. The air
supplied by the primary air fan is a minor part of the air required for
combustion. The secondary air is supplied by either the draft induced by the
stack or an additional forced-draft fan and enters the furnace through an air
register in the furnace wall.
The rotary burner may consist of a drive motor connected to a shaft that
drives the rotating cup, the fuel oil pump and the primary air fan, or the primary
air and fuel oil might be supplied by an independently driven unit. The oil
viscosity required for the rotating cup burner varies between 150 and 350 SUS
(32 to 76 cSt).

Fuel Oil Classification and Specifications

Because the quality and general performance requirements for various
applications of fuel oils differ widely, many countries have adopted general
quality limitations for various fuel grades. These serve as guides in the
manufacture, sale, and purchase of the oils. While these quality definitions are
sometimes called "specifications," they are more properly "classifications"
because of their broad, general nature. In addition to these classifications or
general specifications, there may be more precise specifications of quality
requirements for any given application. These may be dictated by competitive
considerations, customer needs, or government agencies.
The general specifications or classifications are usually the least restrictive type
and serve primarily as a common basis for agreement between producer,
distributor, and consumer. These classifications divide the basic types of oils into
broadly defined grades. Broad tolerances permit a customer to select a suitable
grade for his purpose, but they do not define the ideal fuel for a particular
application. At the same time, the consumer is assured of, at least, minimum
performance quality, and there is no undue restriction on the supply of
acceptable products.

As an example, the detailed requirements for ASTM Specification for Fuel

Oils (D 396) are shown in Table 1. Since ASTM D 396 is revised periodically, the
current Annual Book of ASTM Standards should be consulted if an up-to-date
specification is needed.

Fuel Oil Laboratory Tests and Their Significance

Any property prescribed in a product's specification should be related to
product performance or of value in the refining or handling of the product.
Specific tests have been designed to determine to what degree a given product
meets stated specifications. The test procedures commonly applied to heating
and power generation fuels and their significance are summarized in the
following paragraphs.

API and Specific Gravity or Density

The gravity of a fuel oil is an index of the weight of a measured volume of the
product. There are two scales in use in the petroleum industry: specific
gravity-ASTM Test for Density, Specific Gravity, or API Gravity of Crude
Petroleum and Liquid Petroleum by Hydrometer Method (D 1298/IP 160)-and
American Petroleum (API) gravity-ASTM Test for API Gravity of Crude
Petroleum and Petroleum Products (Hydrometer Method) (D 287/IP 192).
Specific Gravity of a fuel oil is the ratio of the weight of a given volume of the
material at a temperature of 60~ (15.6~ to the weight of an equal volume of
distilled water at the same temperature, both weights being corrected for the
buoyancy of air. Specific gravity is seldom used in the United States, but it is in
general use in some foreign countries.
API Gravity of a fuel oil is based on an arbitrary hydrometer scale which is
related to specific gravity in accordance with the formula

API gravity, deg = 141.5 - 131.5

sp gr at 60/60~

This scale generally is used for most transactions in the United States as well as
in refinery practice.
ASTM Standard D 1250/IP 200 contains tables showing equivalent specific
gravity, pounds per gallon, and gallons per pound at 60~F for each tenth of a
degree API from 0 to 100 ~API.
Density is the mass (weight in vacuo) of a unit volume of fuel oil at any given
temperature (60~ as determined in ASTM D 1298/IP 160).
Gravity by itself is of limited significance as an indication of fuel oil quality. It
is used by the refiner in the control of refinery operations and has significance to
a customer who needs information on net energy release to use in combustion
system calculations.
On a weight basis, the heating value of petroleum fuels decreases with
increasing specific gravity (decreasing API gravity), since the weight ratio of

TABLE 1-Detailed requirements for fuel oils a (ASTM D 396).

Z
Car- O
bon m
Water Resi- Distillation o
and due Temperatures, "rl
Sedi- on lO ~ (~ S a y b o l t Viscosity, se Kinematic Viscosity, c S t e Cop- .-I
Flash Pour ment, % per m
Point, Point, vol- Bot- Ash, 10 Fu~ol at Gray- Strip Sul- r
~ ~F ume toms, weigt~t % 90 % U n i v e r ~ l at !.22~F At 100OF At 122"1: ity, Cot- fur, -4
(~ (~ % % % Point Point IO0~F (38~ (50~ (38~ (50~ ~ rosion %

Grade of Fuel Oil Min Max Max Max Max Max Min Max Min Max Min Max Min Max Min Max Min Max Max

No. 1 100 or 0c 0.05 0. i5 ... 420 .. 550 . . . . . . . . . . . . 1.4 2.2 ..... 35 No, 3 0.5
Dist~late oil intended for legal (215) (288) or
vaporizing pot-type burners and (38) legal
other burners requiring this grade
of fuel

No. 2 I00 or 20 c 0.05 0.35 ., ...d 540 c 640 (32.6) (37.9) ...... 2.0c 3.6 . . . . . 30 9 9 0.5 b
Distillate oil for general purpose legal (-7) (282) (338) or
heating for use in hurnels n o t (38) legal
requiring No. 1 fuel oil

No. 4 130 or 20 c 0.50 ... 0.10 . . . . . . . . . (45) (i25) . . . . . . 5.8 26.4g . . . . . . . . . legal
Preheating n o t usually required legal (-7)
for handling or b u r n i n g (55)

No. 5 (Light)
Preheating may be required 130 or ... 1.00 . ,. 0.10 . . . . . . . . . (>125) (300) . . . . . . >26.4g 658. . . . . . . . . . . . . legal
depending on climate and equip- legal
ment (55)

No. 5 (Heavy)
Preheating m a y be ~ q u i r e d for 130or ... 1.00 ,.. 0.i0 ......... (~>300) (900) (23) (40) >65 194~ (42) (81) ...... legal
b u r n i n g and, in cold climates, legal
m a y be required for handling (55)

No. 6
Preheating required for burning 140 ...h 2,00f . . . . . . . . . . . . . . . (>900) (9000) (>45) (300) ... 9 >'92 638 g ...... legal
and handling (60)

Copyright by ASTM Int'l (all rights reserved); Tue Dec 29 16:07:05 EST 2015
Downloaded/printed by
University of Washington (University of Washington) pursuant to License Agreement. No further reproductions authorized.
alt is the intent of these classifications that failure to meet any requirement of a given grade does not automatically place an oil in the
next lower grade unless in fact it meets all requirements of the lower grade.
bin countries outside the United States other sulfur limits may apply.
CLower or higher pour points may be specified whenever required by conditions of storage or use. When pour point less than 0*F is
specified, the minimum viscosity for Grade No. 2 shall be 1.8 cSt (32.0 SUS) and the minimum 90 percent point shall be waived.
C)
t/The 10 percent distillation temperature point may be specified at 440~F (226~ maximum for use in other than atomizing burners. "1"
eViscosity values in parentheses are for information only and not necessarily limiting.
Ill
fThe amount of water by distillation plus the sediment by extraction shall not exceed 2.00 percent. The amount of sediment by
extraction shall not exceed 0.50 percent. A deduction in quantity shall be made for all water and sediment in excess of 1.0 percent.
O
gWhere low-sulfur fuel oil is required, fuel oil falling in the viscosity range of a lower numbered grade down to and including No. 4 may Z
be supplied by agreement between purchaser and supplier. The viscosity range of the initial shipment shall be identified and advance "1"
notice shall be required when changing from one viscosity range to another. This notice shall be sufficient time to permit the user to m
make the necessary adjustments. .--t
hWhere low sulfur fuel oil is required, Grade 6 fuel oil will be classified as low pour (60~F max) or high pour (no max). Low-pour fuel
oil should be used unless all tanks and lines are heated.
z
o

m
z
m
~n

-t

z
"11
c
m
r-

carbon (low-heating value) to hydrogen (high-heating value) increases as the

specific gravity increases. On a volume basis, the increasing specific gravity more
than compensates for the decreasing heating value per unit weight, with the net
result that fuels having high-specific gravity yield more heat energy per unit
volume than those of low-specific gravity.

Flash and Fire Point

The flash point of a fuel is a measure of the temperature to which the fuel
must be heated to produce an ignitable vapor-air mixture above the liquid fuel
when exposed to an open flame. The "fire point" of a fuel is defined as the
temperature at which an oil in an open container gives off vapor at a sufficient
rate to continue to bum after a flame is applied. Flash point is normally
included in industry specifications for fuel oil.
Flash point is used primarily as an index of fire hazards. As an example, the
U.S. Department of Transportation shipping regulations use flash point as the
criterion to establish labeling requirements. Consequently, most industry
specifications or classifications place limits on the flash point to ensure
compliance with fire regulations, insurance, and legal requirements.
A reduction in the normal flash point of an oil may indicate contamination by
more volatile products such as gasoline. Therefore, determination of flash point
can be useful in detecting such contamination and thereby avoiding serious
safety hazards.
Depending upon the apparatus and method of test used, the determined flash
point of a fuel may vary. In all cases, however, it is an empirical value because
the conditions of the test do not match all possible conditions of commercial
handling of the product.
The ASTM Test for Flash Point by Pensky-Martens Closed Tester (D 93/IP 34)
and the ASTM Test for Flash Point by Tag Closed Tester (D 56) are normally
employed for determining the flash point of fuel oils, because these procedures
more nearly approach the conditions of storage of the fuel in tanks.
In addition, a Rapid Flash Test by the Setaflash Tester is receiving increased
usage in the United States. Reference to Table 1 will show the flash points
specified in the ASTM Standard.

Viscosity
The viscosity of a fluid is a measure of its resistance to flow and is expressed in
various units depending upon the equipment and method used for determina-
tion. These units include Saybolt Universal seconds, Saybolt Furol seconds, and
kinematic viscosity centistokes.
The Saybolt Universal, ASTM Test for Saybolt Viscosity (D 88), and Saybolt
Furol, ASTM Conversion of Kinematic Viscosity to Saybott Universal Viscosity
or to Saybolt Furol Viscosity (D 2161), viscosities are used widely in the United
States. In the United States, viscosities of the lighter fuel grades are determined

by use of the Saybolt Universal viscometer at 100~ (37.8~ and kinematic

viscosity at the same temperature. Saybolt Furol viscosity generally is defined at
122~ (50~ for the heavier fuels.
The use of these empirical procedures for fuel oils is being superseded by the
kinematic system, ASTM Test for Kinematic Viscosity of Transparent and
Opaque Liquids (and the Calculation of Dynamic Viscosity) (D 445/IP 71), with
a test temperature of 122~ (50~ ASTM D 445/IP 71 is now shown as the
preferred viscosity procedure in ASTM D 396.
The determination of residual fuel oil viscosity is complicated by the fact that
some fuel oils containing significant quantities of wax do not behave as simple
Newtonian liquids in which the rate of shear is directly proportional to the
shearing stress applied. At temperatures in the region of 100~ (37.8~ residual
fuels tend to deposit wax from solution. This wax deposition exerts an adverse
effect on the accuracy of the viscosity result unless the test temperature is raised
sufficiently high for all wax to remain in solution. Although the present U.S.
reference test temperature of 122~ (50~ is adequate for use with the majority
of residual fuel oils, there is some opinion in favor of the higher 180~ (82.2~
temperature used by the British, particularly in view of the increasing availability
of the more waxy fuel oils from the newer North African crudes. A number of
difficulties related to anomalous viscosities also would be avoided through
adoption of the kinematic system using a test temperature of 180~ (82.2~
Viscosity is one of the more important heating oil characteristics. It is
indicative of the rate at which the oil will flow in fuel systems and the ease with
which it can be atomized in a given type of burner. Since the viscosities of
heavier residual fuel oils are high, this property tends to be particularly relevant
to its handling and utilization characteristics. The viscosity of a heavy fuel
decreases rapidly with increasing temperature. For this reason, heavy fuels can
be handled easily and atomized properly by the application of preheat. If no
preheating facilities are available, lighter or less viscous oils must be used, and, if
the preheating equipment is inadequate, it may be necessary to burn a lighter oil
during cold weather.
Overly viscous oil can produce problems throughout the system. Besides being
difficult to pump, the burner may be hard to start and flashback or erratic
operation may be encountered. Viscosity also affects the output or delivery of a
spray nozzle and the angle of spray. With improper viscosity at the burner tip,
poor atomization can result in carbonization of the tip, carbon deposition on the
walls of the fire box, or other conditions leading to poor combustion.
Typically, the lower limit of viscosity for easy pumpability is reached at about
5000 SUS (1100 cSt). Difficulties in moving the oil in fuel oil systems will be
encountered below the temperature at which this viscosity is reached.
For good atomization in pressure and steam atomizing burners, a viscosity
range of 100 to 200 SUS (21 to 43 cSt) at the burner is considered desirable. A
viscosity at the burner of 80 to 90 SUS (16 to 18 cSt) is recommended
frequently with low-pressure air atomizing burners. Rotary cup burners are less

critical to atomizing viscosity and can operate satisfactorily with viscosities at

the burner cup as high as 350 to 400 SUS (75 to 87 cSt).

Pour Point
Pour point, ASTM Test for Pour Point of Petroleum Oils (97/IP 15), is defined
as the lowest temperature at which the oil will flow just under standard test
conditions. Anticipated storage conditions and fuel application are usually the
primary considerations in the establishment of pour-point limits. (Storage of the
higher viscosity fuel oils in heated tanks will permit higher pour points than
would otherwise be possible.)
While the failure to flow at the pour point normally is attributed to the
separation of wax from the fuel, it also can be due to the effect of viscosity in
the case of very viscous oils. In addition, pour points, particularly in the case of
residual fuels, may be influenced by the previous thermal history of the oils. As
an example, any loosely knit wax structure built up on cooling of the oil can be
normally broken by the application of relatively little pressure. Thus, the
usefulness of the pour-point test in relation to residual fuel oils is open to
question, and the tendency to regard pour point as the limiting temperature at
which a fuel will flow can be misleading unless correlation is made with
low-temperature viscosity.
Although the pour-point test is still included in many specifications, it is not
designated for the heavier fuels in ASTM D 396 Grades 5 (light and heavy) and
Grade 6. The technical limitations of pour point have motivated efforts to devise
a satisfactory alternative for the pour-point test in assessing the low-tempera'
ture pumpability characteristics of heavy fuel oils. Pour-point procedures
involving various preheat treatments prior to the pour-point determination and
the use of viscosity at low-temperatures have been proposed. ASTM Test for
Maximum Fluidity Temperature of Residual Fuel Oil (D 1659) is one such
procedure used as a "go-no-go" method in the United States. However, all of
these alternative methods tend to be time consuming and, as such, do not find
ready acceptance as routine control tests for assessing low-temperature pump-
ability or fluidity.

Cloud Point
Distillate fuels, especially, begin to form wax crystals and become cloudy in
appearance as they are cooled towards the pour point. The temperature at which
this begins to occur is called the cloud point, ASTM Test for Cloud Point of
Petroleum Oils (D 2500/IP 219). Cloud points often occur at 4 to 5~ (7 to 9~
above the pour point, and temperature differentials of 8*(2 (15~ are not
uncommon. Basically, the temperature differential between cloud and pour
point depends upon the nature of the fuel components, but the use of wax
crystal modifiers or pour depressants tends to accentuate these differences.
As the temperature continues to decrease below the cloud point, the

formation of wax crystals is accelerated. These crystals clog fuel filters and lines
and thus reduce the supply of fuel to the burner. Since the cloud point is at a
higher temperature than the pour point, it can be considered even more
important than the pour point in establishing distillate fuel oil specifications for
cold weather usage.

Sediment and Water Content

The tests for water and insoluble solid contents of distillate fuel oils are
important to the consumer and among those most commonly applied.
Contamination by water and sediment can lead to filter and burner problems
and the production of emulsions which are removable only with difficulty. The
corrosion of storage tanks also may be associated with water bottoms that
accumulate from atmospheric condensation and water contamination.
Water content can be determined by a distillation procedure, ASTM Test for
Water in Petroleum Products and Bituminous Materials by Distillation (D 95/IP
74), and sediment can be estimated by a method, ASTM Test for Sediment in
Crude and Fuel Oils by Extraction (D 473/IP 53), which involves toluene
extraction of the oil through a refractory thimble where the insoluble sediment
is retained in the thimble. Total water and sediment can be determined together
by a centrifuge procedure, ASTM Test for Water and Sediment in Crude Oils and
Fuel Oils by Centrifuge (D 1796/IP 75), but separate determinations of water
and sediment generally are more accurate.

Ash Content
Ash content may be defined as that carbonaceous, matter-free residue that
remains after combustion of the oil in air at a specified, high temperature. To
measure ash content, a joint ASTM/IP test method, ASTM Test for Ash from
Petroleum Products (D 482/IP 4), is used.
Ash forming materials found in residual fuels are derived normally from the
metallic salts found in crude oils. Since crude oil constituents ultimately
concentrate in the distillation residue, distillate fuels tend to contain only
negligible amounts of ash. However, both distillate and residual fuels may pick
up ash contributors during transportation from the refinery. Water transporta-
tion, in particular, presents many opportunities for fuel oils to be contaminated
with ash producers such as sea water, dirt, scale rust, etc.
The total ash content in different residual fuels is similar normally and less
than 0.2 percent by weight. In composition, the ash will vary among residual
fuels, largely as a function of their crude oil antecedents, but metallic
compounds such as sodium, vanadium, nickel, iron, and silica generally are
present.
Depending on the use of the fuel, ash composition has a considerable bearing
on whether or not detrimental effects will occur. Ash in heavy fuel oils can cause
slagging or deposits and high-temperature corrosion in boilers; it may attack

refractories in high-temperature furnaces, kilns, etc., and it may affect the

finished product in certain industrial processes such as ceramic and glass
manufacture.
Since most of the ash in heavy fuels occurs naturally, it usually is difficult for
the refiner to remove it economically. Therefore, methods have been developed
for counteracting the effects of ash. These include the use of additives,
modifications in equipment design, and the application of fuel processing
methods such as water washing.

Carbon Residue

The ASTM Test for Ramsbottom Carbon Residue of Petroleum Products (D

524/IP 14), sometimes called "carbon residue," measures the relative coke-
forming propensities or the carbonaceous residue or both and mineral matter
remaining after destructive distillation of a fuel oil under certain specified
conditions. The carbon residue of burner fuel serves as a rough approximation of
the tendency of the fuel to form deposits in vaporizing pot-type and sieve-type
burners, where the fuel is vaporized in an air-deficient atmosphere.
Little is known concerning the relationship of carbon residue to fuel
performance when applied to residual fuel oils. Pressure jet and steam atomizing
type burners are not very sensitive to the carbon residue of the fuel used. In
well-designed installations incorporating such burners, and where combustion
efficiency is maintained at a high level, it is unlikely that difficulties would
normally arise in burning residual fuel oils. Under such circumstances, therefore,
it is debatable whether the carbon residue test has any real significance relative
to the combustion characteristics of residual fuel.
With distillate fuel oils, high-carbon residue appears to cause rapid carbon
buildup and nozzle fouling in certain types of smaller automatic heating units. In
the vaporizing pot-type burner described previously, the oil is brought into
contact with a hot surface, and the oil vapor subsequently is mixed with
combustion air. Any carbonaceous residue formed by the decomposition of the
oil or by any incomplete vaporization is deposited in or near the vaporizing
surface with resultant loss in burner efficiency. Such a burner, therefore, can be
operated satisfactorily only on distillate fuel oils having low-carbon forming
tendencies.
To improve the accuracy of carbon residue determination for light distillate
fuel oils which form only small amounts of carbonaceous deposits, the carbon
residue value is measured on the 10 percent residue obtained by an adaptation of
a standard distillation procedure ASTM Test for Distillation of Petroleum
Products (D 86/IP 123).
The carbon residue test is, therefore, a useful means for approximating the
deposit forming tendencies of distillate type fuel oils used in home heating
installations. For this purpose, maximum values for Ramsbottom carbon residue
(10 percent residue) are given as 0.15 weight percent for ASTM Grade 1 and
0.35 weight percent for ASTM Grade 2 as shown in Table 1.
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CHAPTER 7 ON HEATING AND POWER GENERATION FUELS 129

Sulfur Content
The sulfur content of fuel oils can be determined by a variety of methods. The
ASTM Test for Sulfur in Petroleum Products (General Bomb Method) (D 129/IP
61) and ASTM Test for Sulfur in Petroleum Oils (Quartz-Tube Method) (D
1551/IP 63) have long been established. Other more rapid techniques are also
available. These include ASTM Test for Sulfur in Petroleum Products (High-
Temperature Method) (D 1552) and ASTM Test for Sulfur in Petroleum
Products (X-Ray Spectrographic Method) (D 2622).
Fuel oils contain varying amounts of sulfur depending on the crude source,
refining processes, and fuel grade. The high-boiling range fractions and the
residual fuels usually contain higher amounts of sulfur which is generally
regarded as an undesirable constituent because of its potential to create
corrosion and pollution problems.
In boiler systems, the conversion of even a small fraction of the sulfur to
sulfur trioxide during combustion of the fuel can cause low-temperature
corrosion problems if this gas is allowed to condense and form corrosive sulfuric
acid on cool metal surfaces of the equipment. In combination with sodium and
vanadium complexes, the sulfur from the fuel contributes to the formation of
deposits on external surfaces of superheater tubes, economizers, and air heaters.
These deposits cause corrosion of equipment and loss of thermal efficiency.
While desulfurization is being used to reduce the sulfur limits of residual fuel
oils, efforts have also been directed towards other means of reducing the effects
of acid condensation. One effective procedure is to operate with a minimum of
excess air. Another means of reducing low-temperature corrosion is to maintain
the cooler metal surfaces of the equipment above the acid dew point; however,
this reduces thermal efficiency. Injection of ammonia into the flue gases or the
addition of neutralizers are also methods used for this purpose, but these are
costly when used in the required concentrations.
Combustion of sulfur-containing fuel oils produces sulfur oxides which have
been identified as atmospheric pollutants. To meet clean air standards in densely
populated industrial areas, stack emission control devices and sulfur scrubbing
procedures may be required.
ASTM D 396 sets maximum sulfur limits for Grades 1 and 2 fuels but does not
include any such limits for the heavier grades. Where sulfur content is considered
critical, agreement on limits generally is made between the supplier and
consumer to meet locally established standards.
when refinery desulfurization processes are used to lower the sulfur content of
residual fuels, a lower viscosity fuel (Grade 4 or 5) is usually produced. Also, to
meet sulfur limits, fuels of higher pour points (60~ or 15.6~ or higher) are
being marketed, when the latter fuels are used, adequate preheating facilities are
required to assure fluidity and pumpability.

Distillation
The distillation procedures (ASTM D 86/IP 123) measure the amount of liquid
vaporized and subsequently condensed as the temperature of the fuel in the
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130 SIGNIFICANCE OF TESTS

distillation flask is raised at a prescribed rate. A record is made of the volume of

distillate collected at specified temperatures or, conversely, the temperature at
each increment of volume distilled (usually 10 percent increments). The
temperature at which the first, drop of condensate is collected is called the
"initial boiling point." The "end point" usually is the highest temperature
recorded as the bottom of the flask becomes dry. If oils are heated above 370~
(700*F), they tend to crack and give unreliable results. The test usually is
stopped when this point is reached. Some distillations may be run under a high
(10 mm) vacuum in order to avoid cracking, ASTM Test for Distillation of
Petroleum Products at Reduced Pressure (D 1160). Under these conditions,
heavy fuel oils may be distilled up to temperatures equivalent to 510~ (950~
at atmospheric pressure. However, distillation tests generally are not applied to
the heavy fuel oils.
The distillation test is significant for the distillate fuels. When heating
installations that use vaporizing burners or atomizing burners are operated with
distillate fuels oils, it is essential that the fuels contain sufficient volatile
components to ensure that ignition and flame stability can be accomplished
easily. In addition, the volatility of the fuel must be uniform from batch to
batch if frequent resetting of burner controls is to be avoided and maximum
performance and efficiency are to be maintained.
Table 1 outlines distillation limits for domestic fuel oils-Grades 1 and 2. No
distillation limits are established for the other grades of fuels.

Corrosion
Tests for corrosion are of a qualitative type and are made to ascertain whether
fuel oils are free of a tendency to corrode copper fuel lines and brass or bronze
parts used in the burner assemblies. The method specified for Grade 1 (distillate)
burner fuel is ASTM Copper Corrosion from Petroleum Products by the Copper
Strip Tarnish Test (D 130/IP 154).
The copper strip corrosion test is conducted by immersing a polished copper
strip in a sample of fuel contained in a chemically clean test tube. The tube is
then placed in a bath maintained at a temperature of 50~ (122~ for 3 h. After
washing, the strip is then examined for evidence of corrosion and judged by
comparisons with the corrosion scale as reflected in the ASTM Copper Strip
Corrosion Standards which are lithographed reproductions of copper strips
subjected to degrees of corrosion that may be caused by products to which
Method D 130 applies.

Additional Tests
Heat Content-The heat content or thermal value of the fuel is the amount of
heat given off as a result of its complete combustion. The results are usually
expressed as "Kilogram-Calorie" or "British Thermal Unit (Btu)/lb." One kg" cal
is equivalent to 1.8 Btu/lb. Heat content determination is made in a bomb

calorimeter under specified conditions, ASTM Test for Heat of Combustion of

Liquid Hydrocarbon Fuels (General Bomb Method) (D 240/IP 12).
The heat content or thermal value test is one which involves careful
standardization of equipment and rigid adherence to prescribed details of
operation. When properly run, the test can yield highly accurate results.
However, it is time consuming and costly to perform on a routine basis.
For normal purposes the heat content or thermal value of a particular fuel can
be calculated with sufficient accuracy from other known data. For example, the
heat of combustion of distillate fuels has been related to the specific gravity,
sulfur content, and aniline point. The heat content of residual fuels is also
related to the gravity. (Tables for estimation of net heat of combustion that are
applicable to No. 1 burner oil are contained in ASTM Estimation of Net Heat of
Combustion of Aviation Fuels (D 1405).)
The heat content or thermal value is not quoted in most fuel oil specifications
since it is not directly controllable during manufacture.
Stability-In essence, stability can be defined as the capability of a fuel to
resist change in composition. Instability is manifested by a change in color, the
formation of gummy materials or insoluble elements, waxy sludge or asphaltic
deposition on the bottom of storage tanks, etc.
The storage stability of fuel oils may be influenced by many factors. Among
these are crude oil origin, hydrocarbon composition, and refinery treatment.
Fuels containing unsaturated hydrocarbons and catalytically cracked compo-
nents are inherently less stable chemically and have a greater tendency to form
sediment on ageing than the straight-run fuels. The presence of reactive
compounds of sulfur, nitrogen, and oxygen may also contribute to a fuel oil
instability.
Much speculation exists regarding the mechanism of sludge deposition. It may
be a consequence of such factors as oxidation, polymerization, and the method
of production of the fuel which can result in the formation of insoluble
compounds that eventually settle to the tank bottoms and form sludge. The
instance of such deposition in light residual fuel oils used in large heating
installations may be reflected by clogging of external cold ffdters, blockage or
restriction of pipelines, and combustion difficulties.
Asphaltic deposition may result from the mixing of fuels of different origin
and treatment, each of which may be perfectly satisfactory when used alone.
Such fuels are said to be incompatible. Straight-run fuels from the same crude oil
normally are stable and mutually compatible. Fuels produced from the thermal
cracking and visbreaking operations may be stable by themselves but can be
unstable or incompatible if blended with straight-run fuels and vice versa.
Instability can be a serious problem that ranges in severity from simple
customer dissatisfaction with an off-color fuel to a cause of serious equipment
malfunctions. Therefore, test procedures are necessary to predict fuel stability
and ensure a satisfactory level of performance by the fuel oil.
A common test is ASTM Test for Stability of Distillate Fuel Oil (Accelerated

Method) (D 2274). This method measures the stability of distillate fuel oils
under accelerated oxidizing conditions. It should be recognized that any
correlation between this test and field storage may vary significantly under
different field conditions or with distillates from different sources.
A widely used test to measure the tendency of residual fuel oils to deposit
asphaltic matter is U.S. Federal Test Method 3461.1 (NBTL Heater Test). Using
this method the fuel oil is circulated over an internally heated steel tube for 20 h
at an oil temperature of 93.3~ (200~ The tube is then examined for asphaltic
deposition and rated "stable," "borderline," or "unstable." To assess the
compatibility characteristics of the fuel oil, it is blended in equal proportions
with each of two reference fuels-one being paraffinic and the other being
asphaltic or thermally cracked. Each blend is subjected to the NBTL Heater
Test. To be satisfactory in service, the fuel oil by itself must be "stable," and the
blended fuels must be assessed as "borderline" or better.
Although no universally accepted procedures are available for assessing the
tendency of fuel oils to deposit sludge while in storage, various empirical
methods are available within individual petroleum companies.
Maximum Fluidity Temperature-When the determination of fluidity tempera-
ture or maximum fluidity temperature of residual fuel oil is required, ASTM
Method D 1659 is applicable. This complicated test defines:
1. Fluidity temperature for a given preheating treatment as the lowest
temperature to 5~ (3~ at which a fuel will flow 2 mm in 1 min in a 12.5-mm
U-tube under a maximum pressure of 15.2 cm of mercury, and
2. Maximum fluidity temperature as the highest single fluidity temperature
found after preheating the fuel to 100, 120, 140, 160, 180, and 200~ (38, 49,
60, 71,82, and 93~
Thermal Stability of U.S. Navy Special Fuel Oil-ASTM Test for Thermal
Stability of U.S. Navy Special Fuel Oil (D 1661) covers the determination of the
preheated fouling characteristics of fuel oil. The method was developed as an
alternate for both the conventional thermal stability and the compatability
(NBTL) tests in the U.S. Military Specifications MIL-F-859 for fuel classified as
"Burner Fuel Oil-U.S. Navy Special." The test is of 6 h duration and consists of
circulation of the fuel sample over the surface of a steel thimble containing a
sheathed heating element maintained at 350~ (177~ At the end of this test
period, the thimble is removed and examined for sediment formation and
discoloration on the surface.
Spot Tests-To measure compatibility of fuel oil blends, ASTM Test for
Compatibility of Fuel Oil Blends by Spot Test (D 2781) is often used. The
method covers two spot test procedures for rating residual fuel oil with respect
to its compatibility with a specific distillate fuel oil. Procedure "A" indicates the
degree of asphaltene deposition that may be expected in blending components.
This procedure is used when wax deposition is not considered a fuel application
problem. Procedure "B" indicates the degree of wax and asphaltene deposition
in the mixture at room temperature. This procedure is used when wax
deposition is considered a fuel application problem.
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CHAPTER 7 ON HEATING AND POWER GENERATION FUELS 133

The method is applied to a 50-50 blend of the component fuel oils. A drop of
the blend is allowed to spread on chromatographic paper of a specified grade.
The spot thus formed is compared with a series of numbered reference spots.
Characterizing features of the spots are defined in the method.

Domestic Heating Off Performance Evaluation

To evaluate domestic heating oil performance, two ASTM methods are
available. Each method provides a means for comparison of burning equipment
and for assessment of burning characteristics of the oils. Both can be used either
as laboratory or as field procedures.
ASTM Test for Smoke Density in the Flue Gases from Distillate Fuels (D
2156) is used to evaluate smoke density in the flue gases from burning distillate
fuels. Since excessive smoke density adversely affects the efficient operation of
domestic heating installations, the test is necessary if the smoke production is to
be held at an acceptable level.
The second method, ASTM Test for Effect of Air Supply on Smoke Density in
Burning Distillate Fuel (D 2157), is applicable only to equipment incorporating
pressure atomizing and rotary wall-flame burners. In this method, efficiency of
operation is related to clean burning of the fuel. The extent to which
combustion air can be reduced without producing an unacceptable level of
smoke is indicative of the maximum efficiency for a particular installation at arty
acceptable smoke level.

Kerosine Performance Evaluation

Selection of Burner
Although the performance of a particular fuel oil depends to some extent on
its inherent properties, with normal kerosine, performance is more dependent on
burner design than on hydrocarbon type composition. Consequently, selection
of a burner in which to assess the burning quality of an oil assumes great
importance.
For kerosine performance evaluation, simple wick-fed yellow flame burners
are used because kerosine type and quality are more critical in these units.
Kerosines which are mainly paraffinic bum well in wick-fed yellow flame lamps
with a poor draft, while kerosine containing high proportions of aromatics and
naphthenes bum with a reddish or even smoky flame under the same conditions.
Predominantly aromatic kerosines can burn brilliantly in a wick-fed blue flame
lamp with good draft characteristics, while the paraffinic type may burn with a
flame of comparatively low-illuminating value.
Since combustion is more complete in the wick-fed blue flame burner than in
the yellow-flame type, the former shows less differentiation between kerosine
types. Even less differences between oil types are exhibited with pressure
burners, which can operate satisfactorily with a wide range of kerosines.
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134 SIGNIFICANCE OF TESTS

Burning Characteristics
lnitial Flame Height-Smoke Point-As the wick of a yellow-flame type lamp
is turned up, a point is reached where smoking occurs. Therefore, the degree of
illumination possible depends mainly on the height of the nonsmoking flame
obtainable. This height varies according to the hydrocarbon type composition of
the kerosine. The maximum height of flame obtainable without smoking, termed
the "smoke point," is greatest with paraffins, considerably lower with
naphthenes, and much lower still with aromatics.
Even if full advantage is not taken to utilize maximum nonsmoking flame
heights, the characteristics of high-smoke point ensures that there will be less
tendency for smoking to occur in the event that a sudden draft causes extension
in flame height.
Although a low-smoke point is undesirable, in that it may not yield a
satisfactory range of smokeless performance, a high-smoke point alone is no
guarantee that a kerosine has generally satisfactory burning characteristics.
ASTM Test for Smoke Point of Aviation Turbine Fuels (D 1322) is the only
test for the determination of smoke point used in the United States. This
method consists of burning a sample in an enclosed lamp with scale. The
maximum flame height that can be achieved without smoking is estimated to the
nearest 0.5 mm.
Constancy of Feed to Wick-The maintenance of the initial degree of
illumination in a lamp depends on the constancy of flow of the kerosine to the
wick as well as on the conditions of the wick. The quantity of oil flowing up a
wick is related to the height of the top of the wick above the level of oil in the
container and the viscosity and surface tension of the oil. Viscosity is more
significant in this respect than surface tension because viscosity varies more in
magnitude with different kerosines and changes in temperature.
When a kerosine warms-up during the initial burning period, the flame size
tends to increase slightly as a result of increase in evaporation rate and decrease
in viscosity. In the case of lamps not provided with constant level feed, the
viscosity becomes significant, since the height of unimmersed wick increases
with the consumption of the kerosine. If the viscosity is too high, the feed of
kerosine and, consequently, the flame height and stability can be reduced
seriously. The presence of moisture in a wick also hinders the upward flow of
kerosine and causes a drop in flame height and a decrease in kerosine
consumption.
Formation of Char on Wick-After a kerosine has been burning for some time,
the condition of the exposed wick of a lamp begins to be affected by the
formation of a carbonaceous incrustation or char. This is not significant unless it
affects the flame or the mechanism for adjusting the wick.
The char may be either hard and brittle or soft, and the amount and
appearance will vary according to the nature and properties of the kerosine
burned. It may be of irregular formation, which causes flame distortion by
producing localized deposits known as "mushrooms" on the surface of the wick,

or it may be formed in such an amount and manner as to restrict the size of the
flame and, in serious cases, extinguish it.
The formation of char depends mainly on the chemical composition and
purity of the kerosine and can be affected by the nature of the wick and the
design and operating conditions of the lamp. Possible causes of high-char
formation may be:
1. Insufficient refining, resulting in the presence of deleterious impurities in
the oil.
2. The presence of high-boiling residues that do not vaporize easily on the top
of the wick and thereby cause decomposition and carbonization. Contamination
with even minute amounts of heavier products, such as lubricants or fuel oil, can
cause serious high-char formation.
Formation of Lamp-Glass Deposits-There should not be any appreciable
formation of deposits or "bloom" on the lamp-glass chimney during burning
under normal operating conditions. Such bloom, when it does appear, may
either be white, gray, brown, or blue in color and should not be confused with
the brownish-black or black deposits caused by a smoky flame.
Certain factors such as the design, composition, temperature of the glass
chimney, and the purity of the atmosphere can have a bearing on bloom
formation. However, this formation is due primarily to the deposition of sulfur
compounds derived from the sulfur content of the oil.

Standard Burning Tests

ASTM Test for Burning Quality of Kerosine (D 187/IP 10) provides a good
assessment of the burning characteristics discussed previously with the exception
of maximum flame height. The tests are applied generally to kerosine used as an
illuminant or as a fuel for space heaters, cookers, incubators, etc.
In both methods, the oil is burned for 24 h in a standard lamp with a flame
initially adjusted to specified dimensions. The details of operations are carefully
stated and cover test-room conditions, volume of sample, wick nature,
pretreatment of the wick and glass chimney, method of wick trimming, and the
removal of the char.
At the conclusion of the tests, the kerosine Consumption is calculated, and a
qualitative assessment of the appearance of the glass chimney is made. In the IP
method, the amount of char formed on the wick is determined, and the char
value is calculated as milligrams per kilogram of kerosine consumed. The ASTM
method utilizes only qualitative assessment of the wick, and no quantitative
determination of char value is made.
Aside from the intrinsic significance of char value with respect to oil quality,
real differences in such values in a series of kerosines enable a relative
comparison of burning quality to be made. Even traces of high-boiling
contaminants greatly increase the char-forming tendencies of kerosines.
For an assessment of the maximum flame height at which a kerosine will burn,
a Smoke Point Test (IP 57) may be used. In this test, a sample is burned in a

special lamp in which flame height is varied against the background of a

graduated scale and adjusted until the smoky tail of the flame just disappears.

Burning Test for Long-Time Burning Oils

Burning tests for long-time burning oils are used to evaluate the burning
properties of oils for use in railway signal lamps and similar kinds of lamps for
which long periods of uninterrupted and unattended burning may be necessary.
In Burning Test-7 Day, (IP 11), the oil is burned for 7 days in one of two
specified signal lamps under strictly controlled conditions. The flame height and
condition of the lamp are recorded every 24 h during the test. At the end of the
test, the total consumption and, if required, the char value are determined.
The corresponding ASTM Test for Burning Quality of Long-Time Burning Oil
for Railway Use (D 219) utilizes a standard semaphore lamp. The test is
continued until 650 ml of oil are burned. This usually requires approximately 5
to 6 days. At the end of the test, the change in the height of the flame and the
condition of the wick and chimney are recorded. There is no provision for
char-value determination.

Applicable ASTM Specification

D 396 Specification for Fuel Oils

Applicable ASTM/IP Standards

ASTM IP Title

11 Burning Test-7-day
D56 Flash Point by Tag Closed Tester
57 Smoke Point
D 86 123 Distillation of Petroleum Products
D88 Saybolt Viscosity
D93 34 Flash Point by Pensky-Martens Closed Tester
D 95 74 Water in Petroleum Products and Bituminous Materials
by Distillation
D 97 15 Pour Point of Petroleum Oils
D 129 61 Sulfur in Petroleum Products by the Bomb Method
D 130 54 Detection of Copper Corrosion from Petroleum
Products by the Copper Strip Tarnish Test
D 187 10 Burning Quality of Kerosine
D 219 Burning Quality of Long-Time Burning Oil
for Railway Use
D 240 12 Heat of Combustion of Liquid Hydrocarbon
Fuels (General Bomb Method)
D 287 192 API Gravity of Crude Petroleum and
Petroleum Products (Hydrometer Method)

D 445 71 Kinematic Viscosity of Transparent and

Opaque Liquids
D 473 53 Sediment in Crude and Fuel Oils by
Extraction
D 482 4 Ash from Petroleum Products
D 524 14 Ramsbottom Carbon Residue of Petroleum Products
D 1160 Test for Distillation of Petroleum Products
at Reduced Pressures
D 1250 200 Petroleum Measurement Tables
D 1298 160 Density, Specific Gravity or API Gravity of
Crude Petroleum and Liquid Petroleum Products
by Hydrometer Method
D 1322 Smoke Point of Aviation Turbine Fuels
D 1405 Estimation of Net Heat of Combustion of
Aviation Fuels
D 1551 63 Sulfur in Petroleum Oils (Quartz-Tube Method)
D 1552 Sulfur in Petroleum Products (High-Temperature
Method)
D 1659 Maximum Fluidity Temperature of Residual Fuel Oil
D 1661 Thermal Stability of U.S. Navy Special Fuel Oil
D 1796 Water and Sediment in Crude Oils and
Fuel Oils by Centrifuge
D 2156 Smoke Density in the Flue Gases from
Distillate Fuels
D 2157 Effect of Air Supply on Smoke Density
in Burning Distillate Fuel
D 2161 Conversion of Kinematic Viscosity to Saybolt
Universal Viscosity or to
Saybolt Furol Viscosity
D 2274 Test for Stability of Distillate Fuel Oil
(Accelerated Method)
D 2500 219 Cloud Point of Petroleum Oils
D 2622 Sulfur in Petroleum Products (X-Ray Spectrographic
Method)
D 2781 Compatibility of Fuel Oil Blends by Spot Test

Bibliography
Francis, W., Fuels and Fuel Technology, 2 Vols., Bergman Press, Oxford, England, [965.
Kewley, J. and Gilbert, C. L., Kerosine, Vol. IV, Scienceof Petroleum, 1938.
Modern Petroleum Technology, Institute of Petroleum, London, England, 3rd edition,
1962.
Petroleum Products Handbook, V. B. Guthrie, Ed., McGraw-Hill,New York, 1960.

Chapter 8--Lubricating Oils

Introduction
The major function of lubricating oils is the reduction of friction and wear by
the separation of surfaces, metallic or plastic, which are moving with respect to
each other. The oils also act as carriers for many special chemicals such as
corrosion inhibitors, antiwear agents, load-carrying friction modifiers, and foam
suppressors. Performance requirements can also include cooling and the
dispersion and neutralization of combustion products from fuels. The high
quality and improved properties of present-day lubricants have enabled engineers
to design machines with higher power-to-weight ratios which generally have
higher stresses, loads, and operating temperatures than before. Thus, it has been
possible to develop automobile engines, turbines, gear sets, etc. capable of higher
speeds and higher specific power output per pound of machinery. In a very
different field, lubricants with increased resistance to the effects of radiation
have been developed for nuclear power stations.
New base oil refining methods yield stock oils which are more responsive to
additive treatment. Research in the field of additives has, in turn, produced
lubricant formulations which can operate under the higher piston-ring belt
temperatures of super-charged automotive diesel engines and provide the
dispersion required to prevent the formation of low-temperature sludges in
gasoline engines for stop-start, short distance motoring.
In spite of the increasing temperatures, loads, and other requirements imposed
on lubricants, mineral oils are likely to continue to be employed in the
foreseeable future for the majority of automotive, industrial, and marine
applications. However, in the aviation field, synthetic lubricants are used
extensively. There are also a growing number of critical automotive, industrial,
and marine applications where the use of synthetic lubricants can be justified on
the basis of total performance cost or fire resistance.

Assessment oi" Quality

New uses and formulation technology for lubricating oils necessitate a

constant review of the methods for assessing the quality of both new and used
lubricating oils. The traditional physical and chemical tests are still applied, but
these are being supplemented and, in some cases, replaced by instrumental
techniques based on physico-chemical methods which include infrared absorp-
tion, ultraviolet absorption, emission spectroscopy, X-ray absorption, and
fluorescence methods. It is convenient to consider these tests in five categories.
138
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CHAPTER 8 ON LUBRICATING OILS 139

The first three determine the characteristics and compositions of lubricants, and
the last two are laboratory tests that simulate service conditions.
Physical Tests-Physical tests are comparatively simple laboratory procedures
which define the nature of the product by measuring physical properties.
Examples are viscosity, flash point, specific gravity, color, and appearance.
Chemical Tests-Chemical tests define the composition of the lubricating oil
by determining the presence of such elements as sulfur, chlorine, phosphorus,
and metals which often are related significantly to the additive content of the
lubricant.
Physico-Chemical Tests-Tests in this classification are either (1) those which
determine the presence of elements using instrumented physical procedures, (2)
those which give information on the molecular structure of the components of
the lubricant, or (3) those which give pH, acidity, and alkalinity values.
Physico-chemical tests are used generally to characterize products for specific
applications, provide quality control at blending plants, and check the suitability
of used lubricants for further service.
Laboratory Bench Tests-Laboratory bench tests subject the lubricating oil to
individual environmental conditions which are designed normally to exceed the
appropriate service requirements. These include such glassware tests as thermal
stability, oxidation stability, and corrosion resistance which are used frequently
for screening formulations during the development of a new product.
Also falling in this category are test machines for measuring wear and
load-carrying properties. Examples are the 4-Ball, Timken, FZG, and Falex
machihes.
Engine and Rig Tests-Mechanical tests are used to assess the effects on various
properties of lubricating oils that will be produced by the environment in which
the lubricant will function. The equipment is set up in a prescribed manner on
laboratory stands, and tests are carried out under carefully controlled condi-
tions. Such tests generally are designed to correlate as far as is possible with
actual service, but, for new products, laboratory mechanical testing usually is
followed by field evaluation.

Significance of Tests
Physical tests, chemical tests, laboratory bench tests, and engine tests are
extremely valuable as tools for attempting to predict how a specific lubricant
formula will perform in full size machinery under many different operating
conditions. They must always be used and interpreted, however, with the full
realization that they are not infallible or foolproof. The ultimate decision as to
the success or failure of a lubricating fluid can be made only on the basis of its
behavior in the end-use item such as production engines, pumps, gear drives,
hydraulic systems, etc. It is usually on the basis of this ultimate performance
that many equipment manufacturers will "recommend" a brand name product
for use in their equipment.

Composition and Manufacture

Petroleum base lubricating oils are present in the residue boiling above 370~
(698~ from the atmospheric distillation of selected crude oils of both
paraffinic and naphthenic types. This residue is further distilled, under
conditions of high vacuum, into a series of fractions to provide light to heavy
lubricating oil stocks. The number of fractions depends on the type of crude oil
and the requirements of the refiner, but four to five is a typical number. These
basic stock oils are further refined, usually by solvent extraction and solvent
dewaxing but sometimes by hydrofinishing, to produce oils suitable for
incorporation into finished lubricants. The individual refined stock oils from one
or more crude sources are blended in various proportions to provide lubricating
oils suitable for a wide range of applications. The blending process can be by
mechanical or air agitation and can be either by a batch or continuous in-line
method.
Only for the less severe uses is it possible to employ nonadditive mineral oils.
In the majority of cases to meet specific applicational requirements, chemical
additives are used to enhance the properties of base oils. Additives are used to
improve such characteristics as oxidation resistance, change in viscosity with
temperature, low-temperature flow properties, corrosion and radiation resis-
tance, and load-carrying capacity. Lubricants frequently contain a number of
additives to achieve a balance of properties suitable for the intended application.
These must be compatible with the base oils, other additives present, and
additives which are commonly used by others who manufacture products
intended for similar uses. Thus, the proper selection of the components for this
lubricating oil formulation requires knowledge of the most suitable crude
sources for the base oils, the type of refining required, the types of additives
necessary, and the possible interactions of these components on the properties
of the finished lubricating oil.
Control of product quality at the blending plant is usually based on a
supplier's own internal standards. The number of tests applied varies with the
complexity of the product and the nature of the application. The more
important tests (viscosity, flash point, color, etc.) usually are performed on
every batch. Other tests may be on a statistical basis dependent on data
developed at the individual blending plant. A newer method of control testing
includes infrared spectroscopic analysis which can be presented in the graphical
form of a "fingerprint" and is specific for the blend of mineral oils and additives
in a particular formulation. Comparison of the "fingerprint" with a known
standard can be used as a check on the composition.

General Properties
Before describing the quality criteria for some of the more important types of
lubricating oils, it will be fruitful to discuss general properties common to most
lubricating oils and the methods used to determine these properties. In this

discussion, pertinent American Society for Testing and Materials and Institute of
Petroleum (ASTM/IP) test methods will be listed.

Viscosity
The viscosity of a lubricating oil is a measure of its flow characteristics. To
meet a particular application, viscosity is generally the most important
controlling property for manufacture and selection. While the viscosity of a
mineral oil changes with temperature, it usually does not change with shear-rate,
unless specific nonshear stable additives are used to modify viscosity/tempera-
ture characteristics-an aspect that is discussed more fully in the section on
Automotive Engine Oils.
At very high pressures (several thousand psi) the viscosity of mineral oils
increases considerably with increase in pressure. The extent of the viscosity
change depends on the crude source of the oil and on the molecular weight of
the constituent components. Kinematic viscosity is measured by timing the flow
of a fixed amount of oil through a calibrated glass capillary tube under gravita-
tional force at a standard temperature, ASTM Test for Kinematic Viscosity
of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity)
(D 445/IP 71). The unit of viscosity used in conjunction with this method is the
centistoke. This unit may be converted into the other viscosity systems (Saybolt,
Redwood, Engler) by means of suitable tables.
Because the main objective of lubrication is to provide a film between
load-bearing surfaces, the selection of the correct viscosity for the oil is aimed at
a balance between a viscosity high enough to prevent the lubricated st~rfaces
from contacting and low enough to minimize energy losses through excessive
heat generation caused by having too viscous a lubricant.
The "classical" hydrodynamic theory for moderately loaded bearings predicts
complete separation between metallic surfaces with a comparatively thick layer
of fluid oil, while highly loaded gears are considered to be in a state of boundary
lubrication in which opposing surface irregularities cause metal-to-metal contact
to occur. Modem elastohydrodynamic theory for lubricated surfaces takes into
account that, because of the high pressure generated, the viscosity of the oil
increases considerably and elastic deformation of the surfaces occur. Under these
conditions, it has been shown that the lubricant film approaching "boundary"
conditions is thicker than previously was supposed.
The viscosity of a new oil is of fundamental importance with respect to
performance in a specific type of equipment or machine element and always
described or specified by the buyer, the seller, or both.
The Society of Automotive Engineers (SAE) numbers (10W, 20, 30, 40, etc.)
are well-known, widely used, and almost universally accepted as a concise but
satisfactory way of describing the viscosity characteristics of oils used in the
crankcase or gear drive of automotive equipment.
Describing the required, or desired, viscosity characteristics of an oil to be
used in the bearing, gears, or hydraulics of industrial machinery or equipment

has proven to be much more complicated than the simple use of the SAE grade
numbers. Many differing reference temperatures have been employed in the past;
many viscosity units (Saybolt Universal Seconds, Redwood, Degree Engler, etc.)
have been promoted, but there has been little or no agreement as to the viscosity
limits or the number of grades which are needed by industry. Since 1968,
however, there has been a strong move underway by the leading lubricant
producers, major machinery manufacturers, and large consumers to adopt a
uniform practice. In that year the ASTM and the American Society of
Lubrication Engineers (ASLE) Recommended Practice for Viscosity System for
Industrial Fluid Lubricants was published as ASTM Standard D 2422.
Simultaneously, the British Standards Institute published an identical standard
(BS-4231). These two standards recommend a series of viscosity grades, each
being approximately 50 percent more viscous than its preceding grade. Both
standards described the viscosity of each grade in centistokes at 37.8~ (100~
and established an allowable deviation of plus or minus 10 percent from the
nominal. The use of this uniform system proved to be satisfactory in the United
States and the United Kingdom, but it was somewhat out of step with the rest of
the world. Consequently, in 1972 efforts by Technical Committee 28 of the
International Standardization Organization produced agreement on a reference
temperature of 400C (104~
Viscosity increase in a used oil, that is, an oil in service, usually indicates that
the oil has deteriorated by oxidation or contamination, while a decrease usually
indicates dilution by a lower viscosity oil or a fuel. Viscosity blending charts
may be used to estimate the amount of dilution. The extent of the viscosity
change permissible before corrective action is required differs in various
applications.
The ASTM Viscosity-Temperature Charts for Liquid Petroleum Products (D
341) are useful for estimating the viscosity of an oil at the various temperatures
which are likely to be encountered in service.

Viscosity Index
The viscosity of petroleum base oils decreases with a rise in temperature, but
this rate of change depends on the composition of the oil. The viscosity index is
an empirical number which indicates the effect of change of temperature on the
viscosity of an oil. It compares the rate of change of viscosity of the sample with
the rates of change of two types of oil having the highest and lowest viscosity
indices at the time (1929) when the viscosity index scale was first introduced. A
standard paraffinic oil was given a viscosity index (VI) of 100 and a standard
naphthenic oil a VI of O. Equations were evolved connecting the viscosity and
temperature for these two types of oil, and, from these equations, tables were
prepared showing the relationship between viscosities at 100~ (37.8~ and
2100F (98.9~ for oils with a VI between 0 and 100. With these tables and the
viscosities at 100 and 210"F of an oil, the viscosity index can be calculated. A
high-viscosity index denotes a low rate of change of viscosity with temperature.

The use of additives and modem refining techniques allows oils to be

produced with high-viscosity indices regardless of the type of crude oil from
which they originated. At the same time, viscosity improvement additives can
produce oils with viscosity indices greater than 100. Initially, this problem was
solved by simply extrapolating the original tables, but, as VIs rose ever higher,
this produced anomalies.
In 1964, ASTM adopted an extension to the tables based on an equation
developed for the purpose. Values derived from this equation are designated VI E
to distinguish them from the original VI. This method has since been adopted by
IP under the joint designation ASTM Calculating Viscosity Index from
Kinematic Viscosity at 40 and 100~ (D 2270[IP 226). This replaces the former
method ASTM D 567[IP 73. (Viscosity indices below 100 have not been
affected by this revision.)
The viscosity index of an oil is of importance in applications where an
appreciable change in the temperature of the lubricating oil could affect the
start-up or operating characteristics of the equipment. The automatic trans-
mission for passenger vehicles is an example of equipment where high-viscosity
index oils using VI improvers are employed to minimize differences between a
viscosity low enough to permit a sufficiently rapid gear shift when starting under
cold conditions and a viscosity adequate at the higher temperatures encountered
in normal running.

Cloud and Pour Points

Petroleum oils contain components with a wide range of molecular sizes and
configurations and thus do not have a sharp freezing point. They become
semiplastic solids when cooled to sufficiently low temperatures.
The cloud point of a lubricating oil is the temperature at which paraffinic wax
and other readily solidifiable components begin to crystallize out and separate
from the oil under prescribed test conditions, ASTM Test for Cloud Point of
Petroleum Oils (D 2500/IP 219). Cloud point is of importance when narrow
clearances might be restricted by accumulation of solid material (for example
suction line strainers, small size oil-feed lines or filters).
The pour point is the lowest temperature at which the oil will just flow under
specified test conditions, ASTM Test for Pour Point of Petroleum Oils (D 97/IP
15), and is roughly equivalent to the tendency of an oil to cease to flow from a
gravity-fed system or container. Since the size and shape of the container, the
head of the oil, and the physical structure of the solidified oil all influence the
tendency of the oil to flow, the pour point of the oil is a guide to, and not an
exact measure of, the temperature at which flow ceases under the service
conditions of a specific system.
The pour point of wax-containing oils can be reduced by the use of special
additives known as pour-point depressants which inhibit the growth of wax
crystals. It is a recognized property of oils of this type that previous thermal

history may affect the measured pour point. ASTM Method D 97/IP 15 includes
a section which permits some measurement of this thermal effect on waxy oils.
The importance of the pour point, to the user of lubricants, is limited to
applications where low temperatures are likely to influence oil flow. Obvious
examples are refrigerator lubricants and automotive engine oils in cold climates.
Any pump installed in outside locations where temperatures periodically go
below freezing should utilize lubricants with a pour point below such
temperatures.

Flash and Fire Points

The flash-point test gives an indication of the presence of volatile components
in an oil, and it is the temperature to which the oil must be heated under
specified test conditions to give off sufficient vapor to form a mixture with air
which will ignite in the presence of an open flame.
The fire point is the temperature to which the product must be heated under
somewhat similar test conditions to cause the vapor/air mixture to bum
continuously on ignition. The ASTM Test for Flash and Fire Points by Cleveland
Open Cup (D 92/IP 36) can be used to determine both flash and fire points of
lubricating oils, and it is the most generally used method for this purpose in the
United States. In the United Kingdom, the ASTM Flash Point by Pensky-
Martens Closed Tester (D 93/IP 34) and open flash points (IP 35) are used
widely.
Not only for the hazard of fire, but also as an indication of the volatility of an
oil, the flash and fire points are significant in cases where high-temperature
operations are encountered. In the case of used oils, the flash point is employed
to indicate the extent of contamination by fuels or a more volatile oil. The flash
point also can be used to assist in the identification of different types of base off
blends.

Relative Density [Specific Gravity) and AP1 Gravity

Relative density and American Petroleum Institute (API) gravity are alternate
but related means of expressing the weight of a measured volume of a product.
Relative Density, ASTM Test for Density, Specific Gravity, or API Gravity of
Crude Petroleum and Liquid Petroleum Products by Hydrometer Method (D
1298/IP 160), also known as specific gravity, is used widely outside the United
States. In the United States, API gravity is used throughout the petroleum
industry. The API gravity, ASTM Test for API Gravity of Crude Petroleum and
Petroleum Products (Hydrometer Method) (D 287/IP 192), is based on a
hydrometer scale which may be readily converted to the relative density basis by
use of tables or formulas.
Both types of gravity measurements are used as manufacturing control tests.
In conjunction with other tests, gtavimetric measurements are used also for
characterizing unknown oils, since they correlate approximately with hydro-

carbon composition and, therefore, with the nature of the crude source of the
oil.

Color
The color of a sample of lubricating oil is measured in a standardized glass
container by comparing the color of the transmitted light with that transmitted
by a series of numbered glass standards, Test for ASTM Color of Petroleum
Products (ASTM Color Scale) (D 1500). The test is used for manufacturing
control purposes and is important since the color is readily observed by the
customer. The color of a lubricating oil is not always a reliable guide to product
quality and should not be used indiscriminately by the consumer in writing
specifications for purchases. Where the color range of a grade is known, a
variation outside the established range indicates possible contamination with
another product.

Automotive Engine Oils

Properties
The crankcase oil of automotive gasoline and diesel engines is used to lubricate
the pistons, cylinders, bearings, and valve train mechanism. In European cars
with transverse engines, the engine and gearbox or automatic transmission may
be served by a common lubricant. Thus, the duty performed by an automotive
engine oil is highly complex, and the oil needs to be formulated appropriately.
As examples, the oil must contain sufficient oxidation inhibitors because even
the best mineral oils react with oxygen at high temperatures to form sludge and
varnish. Good detergent-dispersants are needed to suspend sludge and varnish
forming materials until they are removed by draining the oil. Water and
combustion acids form during operation, and the corrosive wear and rusting
which they cause must be counteracted with corrosion inhibitors which are
usually designed to impart alkalinity to the oil. Modern high-performance
engines have high-tappet loadings which require special antiwear additives in the
lubricating oil. The compatibility of the various additives is also an important
consideration.
Crankcase oil also has an impact on the control of exhaust emissions in today's
ecology-conscious world. The operation of the positive crankcase valve, which
eliminates blow-by gas emitting to the atmosphere, is influenced by the quality
of the oil used. Crankcase oils also can influence combustion chamber deposits,
spark plug life, valve operation, engine wear, and other factors influencing
exhaust emissions.
To meet a particular weather condition, the viscosity of the engine oil is a
main controlling property for manufacture and selection. Engine oils generally
are recommended by automotive builders according to the SAE viscosity
classification. This classification sets the limits for the viscosity at 210~

(98.9"C) for all grades of oil. It also includes viscosity limits of 0~ (- 17.8"C) for
light and intermediate grades.
Multigrade engine oils for year-round service are sufficiently fluid at a low
temperature to permit easy starting of the engine in winter conditions and still
have an adequate viscosity at operating temperatures to provide reasonable
lubrication and oil consumption. The viscosity index of multigrade oils is
typically in the range 120 to 160, while single grade oils are usually between 85
to 105. The improved viscosity/temperature characteristics of multigrade oils
enables, for example, an SAE 20W-50 oil to be formulated which spans SAE
20W viscosity characteristics at low temperatures and SAE 40 to 50 characteris-
tics at the working temperature. Multigrade oils do not behave as Newtonian
fluids primarily because of the presence of polymeric viscosity index improvers.
The result is that the viscosity of multigrade oils generally is higher at 0~
(-17.8~ than is predicted by extrapolation from 210*F (98.9~ and 100~
(37.8~ viscosity values. The extent of the deviation varies with the type and"
amount of the viscosity index improver used. To correlate better with actual
engine conditions, the SAE classification is based on a measured viscosity at 0~
(- 17.8~ using a laboratory test apparatus known as ASTM Test for Apparent
Viscosity of Motor Oils at Low Temperature Using the Cold-Cranking Simulator
(O 2602).
A number of factors are at work in an engine to change the viscosity of the oil.
Multigrade oils are subject to mechanical shearing. The extent of this is
dependent on the type of VI improver used, since the base oil is relatively shear
stable. The viscosity of automotive engine oils in service may also be decreased
by fuel dilution and water but increased by oxidation and combustion products.
Detergent/dispersant oils can keep these contaminants in suspension, but
undesirable sludges can be deposited within the engine if oil drain periods are
extended indiscriminately. Recommendations for oil-change intervals are usually
made by the engine builder, or, in the case of commercial vehicle fleets with
known patterns of operation, the user may establish his own optimum change
periods which are dependent on the level of quality of the lubricating oil
employed.

Engine Test Specifications and Procedures

Engine test methods used in the development of new formulations, and for
purchase specifications, have originated from the following sources:
1. API/ASTM/SAE engine service classifications.
2. Institute of Petroleum tests.
3. Coordinating European Council (CEC) tests.
4. Caterpillar Tractor Company ~ heavy duty, supercharged engine tests.
5. Military specifications (U.S. Army and Navy, British Ministry of Defense,
NATO, etc.).
Originally, the API defined the type of service for which an engine oil was
t Caterpillar has dropped their oil certification program.

designed, and the "MS" sequence tests were used to describe each type ("MS"
denoted a service condition which was most severe for gasoline engines). A new
joint API/ASTM/SAE system of nomenclature was accepted in 1972 as a guide
to the selection of engine oils for different service conditions.
Gasoline engine service conditions are designated by the letters SA, SB, SC,
SD, and SE. Diesel engine oils are designated by CA, CB, CC, and CD. Currently,
these original letter designations indicate increasing levels of severity; however,
as additional categories are adopted, this may not hold true. Performance criteria
have been established for each designation using procedures which include the
Caterpillar Tractor Company diesel engine tests and published engine tests
known as Sequences IIA, liB, IIC, IliA, IIIB, IIIC, IV, V, VB, and VC. The
designation and performance criteria are fully described in the SAE Technical
Report J183a and ASTM Research Report on Engine Oil Performance
Classification (D2-1002). The engine tests used to evaluate engine oil perfor-
mance are included in ASTM Multicylinder Test Sequences for Evaluating
Automotive Engine Oils (STP 315E) and ASTM Single Cylinder Engine Tests for
Evaluating the Performance of Crankcase Lubricants (Abridged Procedures)
(STP 509). Caterpillar Series 3 performance level engines are accepted widely for
superior heavy-duty supercharged diesel engines using comparatively high-sulfur
fuels.
Important U.S. Army specifications include the MIL-L-46152 and MIL-L-
2104C specifications which are also used as performance references for
commercial automotive engine oils. U.S. automotive manufacturers specify SE
engine oils during their warranty periods for cars and trucks.
Engine tests for the evaluation of lubricants are developed in Europe through
the IP and the CEC. Methods in current use include the Caterpillar 1G, Petter
AVI, Petter Wl, and Ford Cortina.
Although military specifications are used widely for civilian purchasing
specifications, it should be recognized that the two uses are by no means
identical. Formulations developed by reputable suppliers usually have quality
levels in excess of the minimum standards required by military specifications and
a more satisfactory all-round balance of properties for mixed fleet, all-duty
service.

Examination of Used Oils

Diesel fuel dilution, resulting from low temperature or short distance
stop/start operation, can be estimated from measurements of the flash point of
the oil which is lowered by small quantities of fuel as determined by ASTM Test
for Diesel Fuel in Used Lubricating Oils by Gas Chromatography (D 3524).
Gasoline dilution can be measured by a distillation procedure, ASTM Test for
Dilution of Gasoline-Engine Crankcase Oils (D 322/IP 23), or determined by
ASTM Test for Fuel Dilution in Gasoline Engine Oils by Gas Chromatography
(D 3525).
Low-temperature service conditions may also result in water vapor from

combustion products condensing in the crankcase. This can be measured by

distillation techniques, ASTM Test for Water in Petroleum Products and
Bituminous Materials by Distillation (D 95/IP 74).
The extent and nature of the contamination of a used automotive engine oil
by oxidation and combustion products can be ascertained by determining the
amounts of materials present in the lubricating oil which are insoluble in normal
pentane and benzene, ASTM Test for Insolubles in Used Lubricating Oils (D
893). Both are expressed as percent by weight. Pentane insolubles include some
oil-soluble resinous matter and all oil insoluble materials. Benzene insolubles
include material from external contamination such as dirt, fuel carbon, and
material from degradation of fuel, oil and additives, and engine wear and
corrosion materials.
Where highly detergent/dispersant oils are under test, coagulated pentane
insolubles and coagulated benzene insolubles may be determined by using
methods similar to those just described but employing a coagulant to precipitate
the very finely divided materials which may otherwise be kept in suspension by
the detergent/dispersant additives.
Size discrimination of insoluble matter may be used to distinguish between
finely dispersed, relatively harmless matter and the larger potentially harmful
particles in oil. The method employs filtration through membranes of known
pore size. Membrane (millipore) fdtration techniques are readily available and
expected to be published shortly as standard test procedures.
The metallic constituents (barium, calcium, magnesium, tin, silica, zinc,
aluminum, sodium, or potassium) of new and used lubricating oils can be
determined by a comprehensive system of chemical analysis. For new lubricating
oils, ASTM Test for Sulfated Ash from Lubricating Oils and Additives (I3 874/1P
163) can be employed to check the concentration of metallic additives. These
standard chemical procedures are time-consuming to carry out, and-where the
volume of samples justifies the purchase of such equipment-emission spectro-
graphs, X-ray fluorescence spectrometers, atomic absorption, and other instru-
ments which are much more rapid are available. (See Applicable ASTM/IP
Standards.)
The amount of reserve alkalinity remaining in the used oil can be determined
by using ASTM Test for Total Base Number of Petroleum Products by
Potentiometric Perchioric Acid Titration (D 2896/IP276). Essentially, tiffs is a
titration method where, because of the nature of the used oil, an electrometric,
instead of a color, end-point is used.

Marine Diesel Engine Oils

From the lubrication viewpoint, marine diesel engines are of two principal
types. These are trunk-piston engines, in which the crankcase oil also lubricates
the bearings and cylinders, and crosshead engines, in which the cylinders are
separately lubricated. Marine diesel engines can also be classified as low-,
medium-, and high-speed types with speeds of 0 to 50, 250 to 1000, and over

1000 rpm, respectively. The lower speed engines are less sensitive to fuel quality
and can operate satisfactorily on residual fuels with high-sulfur contents, while
the higher speed engines are generally more similar in design to automotive
engines and use distillate fuels. Medium-speed engines vary in their fuel
requirements according to the design.
The oil used in trunk-piston engines must have a viscosity suitable for
lubricating the bearings and the cylinders. The trend in marine diesel engine
design is towards smaller and lighter engines of higher specific output so that
proportionally less space in a ship is required for the propulsion unit.
Turbo-charging is used more frequently as a means of increasing the amount of
power obtained from a given size of engine. This increases the heat input and oils
with comparatively high levels of detergents, and antioxidants are required to
maintain satisfactory engine cleanliness. The oxidation stability of trunk-piston
engine oils can be measured by the single-cylinder CRC L-38 and the Petter W-1
tests. Detergency level is determined by one of the single-cylinder Caterpillar
procedures.
Alkaline additives are required in the formulation of marine engine oils to
neutralize potentially corrosive acids formed as a result of blow-by gases entering
the crankcase. These additives must be capable of maintaining the alkalinity of
the oil throughout the life of the charge. This is particularly important when
high-sulfur (above 1 percent) residual fuels are used. Samples of oil drawn from
the crankcase can be tested to assess the reserve of alkalinity remaining by
determining the total base number of the oil. Other tests performed on the used
engine oil, which serve as a guide to the suitability of the oil for further service,
are the viscosity, flash point, pentane and benzene insolubles, and sulfated ash.
In the crosshead type engines, the crankcase oil lubricates the bearings and
may also be used to cool the pistons. As well as having the appropriate viscosity,
the oil also must have satisfactory oxidation resistance and good antifoam and
anticorrosion properties. Small amounts of acidic contaminants entering the
crankcase oil from the cylinders can be neutralized by using crankcase oils with a
low level of alkalinity.
The cylinders of crosshead diesel engines are lubricated separately on an
all-loss basis. The oil is injected into the cylinders through feed poihts around
the cylinder and distributed by the scraping action of the piston rings. Excess oil
collects in a scavenge space and runs off to the exterior of the engine. The oil
used for this purpose is exposed to particularly high temperatures. As crosshead
engines usually operate on residual fuels which frequently contain relatively high
levels of sulfur, it is important that the cylinder oil has a sufficiently high level
of alkalinity to neutralize acidic combustion products formed and thus to
minimize the occurrence of corrosive wear. Some low-specific output engines are
prone to exhaust-port blocking with carbonaceous combustion products and
may also require special lubricating oils to reduce this tendency. Crosshead
cylinder oils may be true solutions, in which the additives are dissolved in the
oil, or they may contain finely divided additives suspended in the oil.

The deposit-forming tendencies due to thermal instability can be assessed by

the Panel Coking Test when used in conjunction with other tests, and the
available alkalinity of these oils can be measured.
The high-speed engines for fishing vessels, pleasure craft, or auxiliaries in larger
vessels require lubricating oils of a type similar to the higher detergency level
automotive diesel engine lubricants. In some cases, automotive grades are
recommended for use in these marine engines. However, since the sulfur
contents of the fuels normally used in marine applications are higher than those
of the fuels used for automotive purposes, it is important to ensure that the
reserve of alkalinity is sufficient to neutralize the additional amounts of
corrosive acids which may be formed.

Industrial and Railway Engine Oils

A wide range of sizes and designs are employed for industrial engines, but the
types of lubricants used and their related test procedures are similar to those
described under the sections on automotive and marine engines. Crankcase
systems for land-based engines may be larger in capacity than for marine
purposes, and the oil charge, in these cases, would be expected to extend for
longer periods of operation.
Engines with large cylinder bores (above 15.2 cm 3 or 6 in. diameter) usually
have higher cylinder wall temperatures and require oils with high viscosities.
Intermediate size engines generally use SAE 30 and 40 grade oils, while for the
large engines SAE 50 oils may be recommended.
Because of space limitations locomotive engines have higher specific ratings
than their industrial counterparts. The resultant higher bearing and cylinder
temperatures, coupled with operating practices that include long idling periods
followed by rapidly increased speed and load, make the lubricant performance
criteria for locomotives relatively severe.
The importance of keeping railway locomotives in service for as long as
possible before overhaul has led to the use of the regular checking of oil samples
for the presence of wear metals. For this purpose direct reading spectrographs,
requiring a minimum of operator time, have been developed. A sudden increase
in the amount of a particular metallic element present in the oil may indicate an
incipient bearing failure.
New railway diesel oil formulations must pass specific tests of the railway
diesel engine manufacturers and using railroads. Ultimate acceptance of an oil is
based on extended satisfactory service performance.

Gas-Turbine Lubricants
Gas-turbine engines, originally developed for aviation use, are now being
employed increasingly for industrial, marine, and automotive applications. The
electricity generation industry, for example, uses a considerable number of gas
turbines for standby and peak lopping purposes. Although more and more

installations have begun to depend on this type engine for full time service, the
requirement to conserve fuel resources may reverse this trend.
From the lubrication viewpoint, the most important features of gas turbines
are the large volumes of high-temperature combustion gases which flow through
the engine and the comparatively high-unit loads on the gearing as a result of the
need to reduce weight to a minimum, particularly with turbines in aircraft.
These features dictate the use of a lubricant of high-thermal and oxidative
stability combined with good load-carrying properties. The latter property is
particularly important where the engine oil also has to lubricate reduction
gearboxes, such as those used for turbo-propeller or helicopter transmissions.
For aviation purposes, British and U.S. military specifications have had a
strong influence in establishing quality criteria and performance levels for
gas-turbine lubricants. The continuous development of engines for military and
commercial use has resulted in increasingly high-bearing temperatures dictating
the adoption of synthetic fluids rather than mineral oils.
Synthetic aircraft turbine lubricants were first used in the United States in
1952. The U.S. Air Force composed the first military performance specification,
MIL-L-7808. Various changes in performance of qualified fluids have resulted in
several revisions of this specification as indicated by a letter suffix, that is,
MIL-L-7808 A, B, C, D, and F.
Pratt and Whitney engine tested most MIL-L-7808 type fluids in 1957 and
subsequently formed their own qualified products list for commercial applica-
tions. General Electric Company (GM) and the Allison Division of General
Motors Corporation also formed qualified products lists. The U.S. Navy and
Pratt and Whitney initiated aircraft-turbine lubricant improvement programs in
1961. Their programs are generally referred to as Type "llA '' and Type II,
respectively. The military specification covering Type "1 89 turbine lubricants is
MIL-L-23699 (WEP), published by the U.S. Navy in early 1963. The Pratt and
Whitney specification covering Type II aircraft-turbine lubricants is PWA 521-B
Type II, published in mid-1963. The most significant difference between these
two specifications is that MIL-L-23699 (WEP) requires qualified fluids to be
shear-stable whereas the Pratt and Whitney specification does not. Otherwise,
both specifications require almost identifical performance.
The Type I synthetic lubricants were produced to meet the requirements of
engines in the 1950s, but, with further advances in engine design together with
the demand for increased periods between engine overhauls, the more thermally
and oxidative stable Type "1 89 and II lubricants were developed. Some of the
physical and performance characteristics of the Type I, "1 89 and II synthetic
lubricants are shown in Table 1.
These specifications also include requirements for resistance to oxidation and
corrosion. Other important properties of aviation gas-turbine lubricants are low
volatility, foam resistance, seal compatibility, and hydrolytic stability.
Because of the safety aspect and the need to prolong periods between engine
overhauls, the inservice condition of aviation lubricants is usually monitored by

z
t')
m
TABLE 1 -Physical and performance characteristics o f type I, 189 and H synthetic lubricants. O
-t
Ill
t,O
General Limiting Low Load Carrying Use
Commercial Military Viscosity Temperature (Ryder Gear Test) Temperature t~
Designation Designation cSt at 210*F Viscosity lb/in. Bulk Oil

Type I MIL-L-7808-F 3.0 (min) 13 000 cSt 1900 to 2200 to: 3000F
max at -65~

Type "1%" MIL-L-23699 5.0 (min) 13 000 cSt 2400 to 2700 to: 400~F
(WEP) (USN) max at - 4 0 ~

Type II None a 5.0 (rain) 13 000 cSt 1900 to 2400 to: 400~
max at - 4 0 ~

apratt and Whitney, PWA 5 2loB.

drawing regular samples for analysis. Metals analysis by emission spectroscopy

can check whether or not any particular metal shows a sudden change in
concentration in the used oil. This can indicate increased wear of a particular
engine component and a possible need for replacement.
Industrial and marine gas-turbine installations vary in their severity of
operating conditions relative to each other and aircraft service. They may run
satisfactorily on high.quality, steam.turbine mineral oils or may need synthetic
oils according to the particular service requirements. Automotive gas-turbine
engines are being developed with the objective of using mineral oils, but, in most
cases, high-bearing temperatures, particularly from heat soak along the drive
shaft immediately after stopping the engine, have necessitated the use of either
synthetic oils or mineral oil/synthetic oil blends. In certain installations aboard
ship or in industry, the very real danger of a fire from leakage of the lubricant
may require the use of a fire-resistant fluid.

Gas Engine Oils

In areas where natural or liquefied petroleum gas (LPG) is available at a
reasonable price level, these gases are finding increasing use as fuels for industrial
engines. Gas engines range from large, relatively low output, low-temperature
engines to small, high-speed, supercharged engines. Lubricant requirements vary
with the engine design and operating conditions from uninhibited mineral oil,
through mildly alkaline oxidation-inhibited detergent oils, to ashless highly
detergent oils. Combustion in the large, low-output engines using natural gas or
LPG fuels is relatively dean, and, since crankcases for these engines usually
contain large quantities of oil, the operating conditions for the lubricant tend to
be comparatively mild. For example, under certain conditions, an oil charge life
of several years may be achieved.
The principal difference between the requirements of gas and other internal
combustion engine oils is the necessity to withstand the degradation that can
occur to the oil from accumulation of oxides of nitrogen which are formed by
combustion. The condition of lubricating oils in large gas engines can be
followed by measuring oil viscosity increase and determining changes in the
neutralization number. Analytical techniques such as infrared spectroscopy and
membrane filtration also can be used to check for nitration of the oil and
buildup of suspended carbonaceous material.
The smaller gas engines generally operate at higher crankcase oil temperatures
than occurs in the larger types, and lubricant degradation in these engines can be
traced by viscosity, neutralization number, and insolubles determinations.
In many areas, the comparatively high-fuel cost for gas engines dictates that
they operate at the maximum efficiency. In the case of two-cycle gas engines,
relatively small amounts of port plugging (about 5 percent) can increase fuel
costs to such an extent that engine overhaul becomes necessary. In these engines,
port plugging can be caused by carbonaceous lubricant deposits and solid
impurities in the combustion air. The lubricant should minimize port plugging

from either of these causes and thus help to increase operation time between
overhauls.

Gear Oils
The range of uses for gear oils is extremely wide and includes industrial,
automotive, marine, and aviation applications. Gears can vary from large, open
types used in quarrying to very small instrument gears used for the control of
aircraft. However, the primary requirement is that the lubricant provide
satisfactory low wear and control or minimize other forms of damage such as
pitting, scuffing, or rusting by maintaining a lubricant film between the moving
surfaces.
Although gears are of many types including spur, helical, worm, bevel, hypoid,
etc., they all function with some combination of rolling and sliding motion. The
contact between the mating surfaces may be either along a line (as in the case of
spur gear) or at a point (as for nonparallel, nonintersecting helical gear shafts).
Although deformation of the metal will broaden the dimensions of the line or
point contacts to areas of contact under service conditions, these areas are small
in relation to the load on them. Therefore, the unit loadings of gear-tooth
surfaces are relatively high compared with ordinary bearing surfaces. Gear teeth
often transmit peak loads of 250 000 psi, whereas sleeve bearing loads are
usually in the range of 10 to 500 psi and seldom exceed 3000 psi.
Where the gear loadings are comparatively light, straight mineral oils may be
used as the lubricant, but, with increased unit loading, it is necessary to
incorporate antiwear additives. For very highly loaded conditions in which shock
is also experienced, special antiweld compounds are included in gear oil
formulations.
It is necessary for a satisfactory balance to be maintained between the
properties desired in the lubricant and the components used. For example,
overactive chemical additives may promote undesirable wear by chemical attack.
This type of wear is known as corrosive wear and results from the progressive
removal of chemical compounds formed at the elevated temperatures on the
tooth surface. Other types of gear wear are caused by fatigue, abrasion, and
welding. In the case of metal fatigue, contact between the surfaces is not
necessary for its occurrence. If the gear surfaces are subjected to stresses that are
above the fatigue endurance limit of the metal, subsurface cracks can develop
which may lead eventually to surface failure. Abrasion of the gear surface is
caused either by the harder surface of the two cutting into the other or a hard
contaminant or wear particle acting as the abrasive medium. Welding occurs
when the severity of the load is high enough to cause complete breakdown of
the lubricant film, and metal-to-metal contact occurs which results in transfer of
metal between the surfaces. The correct choice of lubricant and satisfactory
standards of cleanliness will minimize these wear effects.
Various methods are used to apply gear lubricants. Application may be by drip
feed, splash, or spray. For large open gears, the lubricant must possess a

sufficiently high viscosity and good adhesive properties to remain on the metal
surface. This is particularly the case for applications such as strip coat mining
and in the cement industry where gears may have to operate under wet and dirty
conditions.
Large industrial gear sets using spur or helical gears operating under moderate
loads are usually lubricated by circulating systems. The heavier viscosity turbine
oils are generally suitable for this application. In enclosed systems, the
temperatures reached may be high enough to necessitate the use of oils of good
oxidation resistance. The oils should also possess satisfactory antifoam proper-
ties as well as good antirust and demulsibility characteristics. Where higher
loadings are encountered in industrial gears, lead, sulfur, and phosphorus
compounds commonly are used to improve the load-carrying capacity of the
lubricant.
For highly loaded spiral bevel, worm, or hypoid gears where sliding contact
predominates over rolling contact between gear teeth, lubricating oils with
special extreme pressure additives are used. Sulfur, chlorine, lead, and
phosphorus compounds are used widely for this purpose.
The amount of active elements in new and used gear oils can be determined by
"wet" analytical methods described previously, but there are also a number of
instrumental techniques which enable the results to be obtained much more
rapidly. Among these tests are polarographic, flame photometric, and X-ray
fluorescence methods.
The analytical techniques described for measuring the elements associated
with the load-carrying compounds present in gear oils do not identify the
specific additives used; nevertheless, they are useful for controlling the quality of
the finished products at blending plants. The same techniques can be used to
determine similar additives and contaminants that may be present in used oils.
Since active sulfur is desirable for some extreme-pressure applications, ASTM
Detection of Copper Corrosion from Petroleum Products by the Copper Strip
Tamish Test (D 130/IP 154) can indicate whether the formulation has a
satisfactory level of sulfur activity. The copper strip test is used widely for the
quality control of gear oils at blending plants.
Mechanical tests are used for assessing the extreme pressure, friction, and
antiwear properties of gear oils in the laboratory. Examples of these are the
Institute of Automotive Engineers (IAE) and Ryder gear rigs, the Timken
Lubricant Tester, the SAE, David Brown and Caterpillar Disc (or Roller), 4-Ball,
Falex, and Almen machines. The selection of the appropriate test machine
depends on the application being considered. In spite of the variety of
equipment available, the correlation of laboratory tests with practice is not
precise, and, hence, the final evaluation of the lubricant needs to be made under
controlled field conditions.
A number of industry and military specifications exist for automotive extreme
pressure gear lubricants. Examples of these are the U.S. military MIL-L-2105 and
2105B specifications. The MIL-L-2105 specification is still used to indicate the

performance level of oils, although the specification is now obsolete. The

MIL-L-2105B specification describes an axle oil with a higher extreme pressure
performance level, which is measured in the CRC L-42 Car Axle High-Speed
Shock Test, and the CRC L-37 Truck Axle High-Torque Test. Also included in
this specification are a Thermal and Oxidation Stability Test, the CRC I.-33 Axle
Moisture Corrosion Test, a Copper Corrosion Test, and a Channel Point Test to
assess the low-temperature flow properties of the oil. The British Ministry of
Defense Specification CS 3000B is based on the performance of a blended oil in
full scale axle tests as well as a comprehensive series of laboratory bench tests
including oxidation, foam, and storage stabilities. The axle tests specified are the
High Torque Test (IP 232) and a modified High Speed Shock Test (IP 234).
In the case of farm tractor and highway construction equipment transmission
lubricants, the fluid may be required to perform more than one function. For
example, several tractor manufacturers recommend oils for use as both hydraulic
and transmission fluids.
Several larger tractor models are now fitted with oil-immersed "wet" brakes.
The oil used for this purpose may require special frictional characteristics to
avoid the occurrence of severe vibration or "chatter" when braking is applied.
Special additives are incorporated in oil formulations to meet this requirement.
Most major tractor manufacturers require approval of fluids for use in their
tractors which is based on meeting physical and bench test specifications plus
satisfactory performance in tractor tests conducted by the tractor manufacturer.

Automatic Transmission Fluids

The fluids used to lubricate automatic transmissions for passenger cars should
facilitate the satisfactory operation of such components as the torque converter,
planetary or differential gearing, wet clutches, servo-mechanisms, and control
valves. The viscosity characteristics of the oil are extremely important. Since a
minimum change of viscosity with temperature is desirable, viscosity index
improvers are incorporated. Low viscosity improves the efficiency of the torque
converter, but the lower limit is dictated by the viscosity required to protect the
gearing. It is usual to employ fluids in the range of SAE 5W to 20W for
automatic transmissions.
The shearing forces exerted by the automatic transmissions components, such
as the pumps and clutches, tend to reduce the viscosity of the polymeric
viscosity improvers incorporated in these fluids. It is important, therefore, that
automatic transmission fluids have adequate shear-stability. To determine shear
stability, full-scale road, dynamometer, or laboratory bench tests may be used
with the viscosity compared before and after shearing. Because of the
comparatively high temperatures reached in service, oils with very good
oxidation and thermal stability are also necessary.
The two most important specifications for automatic transmission fluids in the
United States have been the Ford M2C33E(F) and the GM "Dexron." The
Dexron II and M2C33G specifications supercede the GM Dexron and Ford

M2C33E(F) specifications, respectively. The new specifications place greater

emphasis on oxidation stability, frictional durability, and antiwear and thermal
stability characteristics of the fluid.
Because of the complex range of functions performed, automatic transmission
fluids are highly complex products. Additives are used to enhance their
performance. Load-carrying additives are used to protect the gearing and thrust
washers. Smooth clutch engagements dictate the use of additives for foam
control. Specific additives may be used to control the frictional properties of the
lubricant since, with most automatic transmissions, static and dynamic friction
properties are important for satisfactory operation of the clutches and brake
bands. During selection of additives, a prime consideration is additive intercom-
patibility.

Steam-Turbine Oils
The primary purpose of lubricating oils for steam-turbine circulating systems is
to provide satisfactory lubrication and cooling of the bearings and gears. It is
also a common practice to design the turbine to have the lubricating oil also
function as a governor-hydraulic fluid. The viscosity of the oil is important for
both of these functions, but the loading of the gear is the major factor in the
choice of lubricant. A sufficiently thick film of oil must be maintained between
the load-bearing surfaces; the higher the load on the gears, the higher the
viscosity required. However, as the circulated oil also acts as a coolant for the
bearings, it is necessary to have as low a viscosity as possible consistent with the
lubrication requirements.
Since steam-turbine oils generally are required to function at elevated
temperatures (for example, 71.1~ or 160~ it is most importani that the
oxidation stability of the oil is satisfactory; otherwise, the service life of the oil
will be unduly short, ASTM Test for Oxidation Characteristics of Inhibited
Steam-Turbine Oils (D 943). Oxidation inhibitors are added to the base oil to
improve this characteristic. Lack of oxidation stability results in the develop-
ment of acidic products which can lead to corrosion (particularly of bearing
metals) and also affect the ability of the oil to separate from water. Oxidation
also causes an increase in viscosity and the formation of sludges which restricts
oilways, impairs circulation of the oil, and interferes with the function of
governors and oil relays. Correctly formulated turbine oils have excellent
resistance to oxidation and will function satisfactorily for years without
changing the system charge.
Turbine-oil systems usually contain some free water as a result of steam
leaking through glands and then condensing. Marine systems may also have salt
water present due to leakage from coolers. Because of this, rust inhibitors are
almost always incorporated in the formulation. Rust preventing properties may
be measured by ASTM Test for Rust-Preventing Characteristics of Steam-
Turbine Oil in the Presence of Water (D 665/IP 135).
The presence of water in turbine systems tends to lead to the formation of

emulsions and sludges containing water, oil, oil oxidation products, rust par-
ticles, and other solid contaminants which can seriously impair lubrication. The
lubricating oil, therefore, should have the ability to separate from water readily
and resist emulsification. Approximate guides to the water-separating character-
istics can be gained by ASTM Test for Emulsion Characteristics of Petroleum
Oils and Synthetic Fluids (I3 1401/IP 79).
Although systems should be designed to avoid entrainment of air in the oil, it
is not always possible to prevent. The formation of a stable foam increases the
surface area of the oil which is exposed to small bubbles of air thus assisting
oxidation. The foam can also cause loss of oil from the system by overflow.
Defoamants are usually incorporated in turbine oils to decrease their foaming
tendency. Foaming tendency can be measured by ASTM Test for Foaming
Characteristics of Lubricating Oils (D 892/IP 146). Air release is also an
important property if a soft or spongy governor system is to be avoided. A
careful choice of type and amount of defoamant will provide the correct balance
of foam protection and air release properties.
Marine turbine gearing design has advanced to the stage where increased
loading has permitted a decreased size of the gear train. This saving in space is
very desirable, particularly in naval vessels, but turbine oils for such applications
may also require a moderate level of extreme-pressure properties. Load-carrying
properties for turbine oils may be measured by ASTM Test for Load-Carrying
Capacity of Fluid Gear Lubricants (D 1947), which uses a Ryder gear rig, or by
IP 166 which utilizes an IAE gear rig.

Hydraulic Oils
The operation of many types of industrial machines can be controlled
conveniently by means of hydraulic systems which consist essentially of an oil
reservoir, a pump, control valves, piping, an actuator, and sometimes an
accumulator. The wide range of hydraulic applications encountered necessitates
the use of a variety of pump designs including gear, vane, axial, and radial piston
types which, in turn, utilize various metallurgical combinations. The hydraulic
fluid is required to transmit pressure and energy, minimize friction and wear in
pumps, valves and cylinders, minimize leakage between moving components, and
protect the metal surfaces against corrosion.
To obtain optimum efficiency of machine operation and control, the viscosity
of the oil should be low enough to minimize frictional and pressure losses in
piping. However, it also is necessary to have a sufficiently high viscosity to
provide satisfactory wear protection and minimize leakage of the fluid.
High-viscosity index fluids help to maintain a satisfactory viscosity over a wide
temperature range. The antiwear properties of high-quality hydraulic oils usually
are improved by the incorporation of suitable additives in the formulation.
Since the clearances in pumps and valves tend to be critical, it is important to
provide adequate filtration equipment (full flow or bypass or both) to maintain
the system in as clean a condition as possible and thus minimize wear. The oil

should have good oxidation stability to avoid the formation of insoluble gums or
sludges; it should have good water separation properties, and, because air may be
entrained in the system, the oil should have good air-release properties and
resistance to foaming. Similarly, good rust protection properties will assist in
keeping the oil in a satisfactory condition.
While petroleum oils, properly formulated, are excellent hydraulic fluids, they
are flammable, and their use should be avoided in applications where serious
fires could result from oil leakage contacting an open flame or other source of
ignition. Fire-resistant fluids should be used in such applications. The major fire
resistant fluids are (1) the synthetics (phosphate esters, silicones, and silicates),
(2) the synthetics-petroleum oil blends (to reduce cost), (3) the water-glycol
solutions, and (4) the petroleum oil invert emulsions (water-in-oil).
Over the years, a number of tests have been used to evaluate the fire-resistant
properties of such fluids under a variety of conditions. Most tests involve
dripping, spraying, or pouring the liquid into a flame or on a hot surface of
molten metal. ASTM recently has developed and published a method in which
the fluid is sprayed as a mist into the flame of a laboratory burner, ASTM Test
for Mist Spray Flammability of Hydraulic Fluids (D 3119).
Fire-resistant fluids, or safety devices on hydraulic systems, are used widely in
the coal mining industry. The use of such fluids also is expanding in the metal
cutting and forming, lumber, steel, aluminum, and aircraft industries.

Other LubricatingOils
While many of the properties which have been discussed earlier apply to other
types of lubricating oils, there are a number of industrial applications for which
special performance requirements are demanded. The following are examples.

Air Compressor Oils

In addition to possessing the correct viscosity for satisfactory bearing and
cylinder lubrication, very good oxidation resistance is required to avoid
degradation of the lubricant in the presence of heated air. This is particularly
important where discharge temperatures are high, since carbon and oxidized oil
deposits may autoignite if exposed continuously to temperatures above 300~
The fire potential that exists under these conditions make low volatility and
high-autoignition values equally or more important than high-flash or fire points.
As an added safeguard against compressor fires, a fire resistant fluid (phosphate
ester) should be considered.
In air compressor lubrication, condensed water is present frequently. For this
reason, the oil must possess properties that ensure that the oil rather than water
wets the metal surfaces. Also, to avoid the accumulation of invert water-in-oil
emulsions in the after coolers, the water should separate out rather than form an
emulsion.

Refrigerator Compressor Oils

The efficiency of compression-refrigeration systems can be influenced directly
by the properties of the lubricant. This is because the oil used for cylinder
lubrication tends to be carried over into the system where it can have a
detrimental effect on the efficiency of the evaporator and associated equipment.
The lubricating oil, therefore, must effectively minimize friction and wear in the
compressor and prevent the formation of undesirable deposits. In addition, the
lubricant should have no adverse effects on the operation of the condenser,
expansion valve, or evaporator. Low-temperature viscosity must be balanced
against the need to protect the cylinder against wear. Adequate oxidation
resistance and thermal stability to resist the high temperatures encountered at
the compressor discharge are also necessary. In ammonia systems, it is important
that the pour point of the oil is below the evaporator temperatures to avoid the
congealing of the oil on evaporator heat-transfer surfaces. With Freon systems, a
low-Freon floc point of the oil indicates freedom from the likelihood of waxy
deposits which could otherwise interfere with the satisfactory operation of the
expansion valve and lower the rate of heat transfer.

Steam Cylinder Oils

Steam engines, pumps, forging hammers, and pile drivers are among the
equipment using steam cylinders. The performance of this type of machinery is
affected directly by the efficiency of the lubrication of the valves, piston rings,
cylinder walls, and rods. The selection of the lubricating oil is influenced by the
steam temperatures encountered, the moisture content of the steam, the
cleanliness of the steam (that is, possible contamination by solids), and the
necessity for the oil to separate from the exhaust steam or condensate. Excessive
oxidation of the oil in service could cause a buildup of deposits in the stem and
rod packings and result in shutdown of the equipment for cleaning.

Machine Tool Tableway Lubricating Oils

Satisfactory lubrication of the ways and slides of machine tools is important in

maintaining the precision of equipment designed to work to close tolerances.
The movement of worktables, workheads, tool holders, and carriages should be
facilitated by the lubricant so that the control is smooth and precise. The
characteristics required for these oils include a suitable viscosity to enable ready
distribution of the oil to the sliding surface, while ensuring that the necessary oil
films are formed at traverse speeds under high-load conditions. Static friction
must be minimized, and the oil should prevent the alternate sticking and slipping
of moving parts, particularly at very low speeds. Especially when the position of
these surfaces is in the vertical plane, good adhesive properties are required to
maintain an adequate film on intermittently lubricated surfaces.

ApplicableASTM/IPStandards
ASTM IP Title

19 Demulsification Number-Lubricating Oil

35 Flash Point (Open) and Fire Point by Means of the
Pensky-Martens Closed Tester
D 92 36 Flash and Fire Points by Cleveland Open Cup
D 93 34 Flash Point by Pensky.Martens Closed Tester
D 95 74 Water in Petroleum Products and Bituminous
Materials by Distillation
D 97 15 Pour Point of Petroleum Oils
110 Barium in Lubricating Oil
111 Calcium in Lubricating Oil
114 Oxidation Test for Turbine Oils
117 Zinc in Lubricating Oil
120 Lead, Copper and Zinc in Lubricating Oils
D 129 61 Sulfur in Petroleum Products by the Bomb Method
148 Phosphorus in Lubricating Oil, Additives, and
Concentrates
D 130 154 Detection of Copper Corrosion from Petroleum
Products by the Copper Strip Tarnish Test
166 Load-Carrying Capacity Test for Oils-IAE Gear
Machine
175 Engine Cleanliness-Pette r W1 Spark-Ignition Test
176 Oil Oxidation and Bearing Corrosion-Petter W1
Spark-Ignition
D 322 23 Dilution of Gasoline-Engine Crankcase Oils
D 341 Viscosity-Temperature Charts for Liquid
Petroleum Products
D 445 71 Kinematic Viscosity of Transparent and
Opaque Liquids (and the Calculation of
Dynamic Viscosity)
D 665 135 Rust-Preventing Characteristics of Steam-Turbine
Oil in the Presence of Water
D 808 Chlorine in New and Used Petroleum Products
(Bomb Method)
D811 Chemical Analysis for Metals in New and Used
Lubricating Oils
D 874 163 Sulfated Ash from Lubricating Oils and Additives
D 892 146 Foaming Characteristics of Lubricating Oils
D 893 Insolubles in Used Lubricating Oils
D 943 157 Oxidation Characteristics of Inhibited
Steam-Turbine Oils
D 974 139 Neutralization Number by Color-Indicator Titration

Applicable ASTMflP Standards (Continued.)

ASTM IP Title
D 1091 Phosphorus in Lubricating Oils and Additives
D 1317 118 Chlorine in New and Used Lubricants
(Sodium Alcoholate Method)
D 1401 Emulsion Characteristics of Petroleum Oils and
Synthetic Fluids
D 1500 ASTM Color of Petroleum Products
(ASTM Color Scale)
D 1947 Load-Carrying Capacity of Fluid Gear Lubricants
(Erdco, Ryder, WAAO Machines)
D 2270 226 Calculating Viscosity Index from Kinematic
Viscosity at 40 and 100~
D 2271 Preliminary Examination of Hydraulic Fluids
(Wear Test)
D 2272 Continuity of Steam-Turbine Oil Oxidation Stability
by Rotating Bomb
D 2422 Recommended Practice for Viscosity System for
Industrial Fluid Lubricants
D 2500 219 Cloud Point of Petroleum Oils
D 2602 Apparent Viscosity of Motor Oils at Low
Temperatures Using the Cold-Cranking Simulator
D 2619 Hydrolytic Stability of Hydraulic Fluids
(Beverage Bottle Test Method)
D 2670 Measuring Wear Properties of Fluid Lubricants
(Falex Method)
D 2711 Demulsibility Characteristics of Lubricating Oils
D 2782 Measurement of Extreme-Pressure Properties of
Lubricating Fluids (Timken Method)
D 2783 Measurement of Extreme-Pressure Properties of
Lubricating Fluids (Four-Ball Method)
D 2877 283 Measuring Frictional Properties of
Slideway Lubricants
D 2882 Vane Pump Testing of Petroleum Hydraulic Oils
D 2893 Oxidation Characteristics of Extreme-Pressure Oils
D 2896 276 Total Base Number of Petroleum Products by
Potentiometric Perchloric Acid Titration
D 2982 Detecting Glycol-Base Antifreeze in
Used Lubricating Oils
D 2983 Apparent Viscosity of Gear Oils at Low
Temperatures Using the Brookfield Viscometer
D 3119 Mist Spray Flammability of Hydraulic Fluids

Bibliography
Boner, C. J. and Gruse, W. A., Motor Oils-Performance and Evaluation, Reinhold, New
York, 1967.
Boner, C. J., Gear and Transmission Lubricants, Reinhold, New York, 1967.
O'Connor and Boyd, Standard Handbook of Lubrication Engineering, McGraw Hill, New
York, 1963.
Geurgi, C. W., Motor Oils and Lubrication, Reinhold, New York, 1950.

Chapter 9--Lubricating Greases

Introduction
The primary function of lubricants is to increase the efficiency of machinery
by reducing friction and wear. Secondary functions include the dissipation of
heat and removal of contaminants. Fluid lubricants are difficult to retain at the
point of application and must be replenished frequently. If, however, a fluid
lubricant is thickened, its retention is improved. A lubricating grease is simply a
lubricating fluid which has been gelled by means of a thickening agent so that it
may be retained more readily in the required area.
Lubricating greases have a number of advantages over lubricating fluids. Some
of these are: (1) dripping and spattering are nearly eliminated; (2)less frequent
applications are required; (3) greases are easier to handle; (4) less expensive seals
are needed; (5) greases form a seal in many cases and keep out contaminants; (6)
they adhere better to surfaces; (7) they reduce noise and vibration; (8) some
grease remains even when relubrication is neglected; and (9) greases are
economical.
Many ways have been devised to thicken lubricating oils. Soaps were the first
thickeners used and still have wide application. Other thickeners that have been
employed include polymers, clays, silica gel, etc.
The lubricating fluids which have been thickened to form greases vary widely.
By far the largest volume of greases in use today are those made with mineral
oils thickened with soaps. Many types of mineral oils are used, for example,
naphthenic, paraffinic, blended, hydrocracked, hydrogenated, solvent refined,
highly refined, etc. In addition to mineral oils, many other fluids, such as esters,
diesters, silicones, polyethers, and synthetic hydrocarbons, can be used.
When selecting a grease, one should first determine the type and viscosity of
the lubricating fluid required. The fluid provides the lubrication; however, grease
properties are based dominantly on the characteristics of the thickener system.
Each thickener system has its own unique characteristics. Properties of the
various soap-type greases will be discussed in later paragraphs.

Composition
Grease has been defined as a gelled lubricating fluid. The basic steps which are
required to make a grease include dissolving the thickener system in the fluid,
thoroughly mixing, cooling the mixture to permit proper crystallization of the
thickener, blending in the desired additives and inhibitors, and then final
finishing and processing. The inhibitors enhance the performance of the grease.
Included in the finishing and process steps are homogenization or deaerating or
both where needed.

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CHAPTER 9 ON LUBRICATING GREASES 165

The fatty materials used for soap formation may be of animal or vegetable
origin. The type of fatty materials used affects the properties of the soap and the
grease. Improved or special properties or both may be obtained by the use of
mixtures or blends of fatty materials.
Soaps are formed by the simple saponification of an acid and base to form a
salt and water. If the acid is a fatty acid, its salt is called a soap. If the metallic
moiety of the base is monovalent a simple soap is made, for example, lithium
stearate. If the metal is polyvalent, a complex soap having unique properties is
formed. For example, if two dissimilar acids are attached to the same metallic
element, calcium stearate acetate can be formed. Mixed base greases consist of a
mixture of two different thickener systems.
Salts of fatty acids (soaps) are present in greases in the form of fibers. The
structure and size of these fibers, that is thickness and length, depends upon the
metallic moiety and the conditions under which they are formed. In general,
fibers may vary from about 1 to 100 ~m in length with a length/diameter ratio
of about 10 to 100 ~ n . Large, coarse fibers do not absorb fluids as well as fine,
closely knit fibers. Thus, higher percentages of coarse fibered soaps are required
to make greases having the same consistency as those made with fine fibered
soaps.

Properties

Calcium Soap Greases

The earliest known greases were made with calcium soaps. Calcium soaps are
water resistant, mechanically stable, and inexpensive. The greatest shortcoming
of calcium soap greases is the low-melting points (dropping points) which are
usually about 200~

Sodium Soap Greases

Sodium soap greases have higher dropping points (about 400OF) than calcium
greases. However, they are not water resistant and emulsify in the presence of
water. They are not normally compatible with other greases. Sodium soap
greases do have an inherent ability to provide rust protection.

Lithium Soap Greases

Lithium greases were the first so-called multipurpose greases that offered both
the water resistance of calcium soap greases and the high-temperature properties
of sodium soap greases. Lithium soap greases have dropping points of about
3500F. They also have good mechanical stability; that is, they soften very little
upon working.

Complex Soap Greases

Complex soap greases are noted for their high-dropping points (500OF and
higher). They have good resistance to water and usually have good mechanical
stability properties.

Clay Greases
Clay thickened greases have been referred to as nonmelting greases since they
tend to decompose (at temperatures above 550~ before reaching their
dropping point. They usually have poorer mechanical stability and water
resistant properties than soap greases. They also are more difficult to inhibit
with extreme pressure additives.

Evaluation of Properties and Significance

A number of tests have been developed and standardized by American Society
for Testing and Materials (ASTM) and the Institute of Petroleum (IP) which
describe the properties of performance characteristics of lubricating greases.
Since these tests are conducted in laboratories under well-defined conditions,
they are used primarily as screening tests. Some of the grease tests do give an
indication of what a grease might do in service, but direct correlation between
laboratory and field performance is rarely possible, since the tests never exactly
duplicate service conditions.

Consistency
Consistency has been defined as the degree to which a plastic material, such as
a lubricating grease, resists deformation under the application of force. The
standard method for measuring grease consistency is the penetration test.
Consistency is reported in terms of ASTM cone penetration, National Lubricat-
ing Grease Institute (NLGI) number, or apparent viscosity. Cone penetrations
and NLGI number are discussed in the following paragraphs. Apparent viscosity
is included in the section on Shear Stability.
Cone Penetration-The standard method for the determination of the
penetration of a normal grease sample is ASTM Test for Cone Penetration of
Lubricating Grease (D 217/IP 50). In this method, a double-tapered cone of
prescribed geometry sinks under its own weight into a sample of grease at 25~
for 5 s. The depth of penetration is measured in tenths of a millimeter, and it is
the penetration value. Stiff greases will have very low-penetration values,
whereas a soft grease will have a high-penetration number.
The penetration number for small samples of grease may be determined by
using ASTM Test for Cone Penetration of Lubrication Grease Using One-Quarter
and One-Half Scale Cone Equipment (D 1403/IP 310). An equation is used to
convert the penetrations obtained in this test to equivalent penetrations for the
full scale test.
The following paragraphs describe four procedures used to obtain penetra-
tions.
Undisturbed penetration-The penetration is measured in the container as
received without any disturbance. This value is significant in determining the
extent to which a grease may harden or soften in the container in shipment or
storage or both.

Unworked penetration-This value is obtained where the grease is transferred

from the container, with only a minimum amount of disturbance, to the cup of
the grease worker. This result is not always reliable, since the amount of
disturbance cannot be controlled nor repeated exactly. It may be significant to
indicate consistency variances in transferring a grease from the container to the
equipment.
Worked penetration-Worked penetration is the standard penetration value for
a grease. It is measured after a grease has been worked for 60 double strokes in
the grease worker. This method is more reliable, since disturbing the grease is
more nearly standardized by the working process.
Prolonged worked penetrations-This value is obtained after a sample has been
worked for a prolonged period in the grease worker, that is, 10 000, 50 000,
100 000, etc. double strokes. After prolonged working in the grease worker, the
sample and worker are brought back to penetration test temperature (25~ in
1.5 h. It is then worked for 60 double strokes and the penetration is measured.
This test is significant, since it can indicate the degree of mechanical or shear
stability of a grease. It will be described later.
NLGI Grades-On the basis of worked penetrations, the NLGI has standard-
ized a numerical scale as a means of classifying greases in accordance with their
consistency. This scale is shown beiow in order of increasing hardness.
ASTM NLGI
Worked Penetrations Grade

445 to 475 000

400 to 430 00
355 to 385 0
310 to 340 1
265 to 295 2
220 to 250 3
175 to 205 4
130 to 160 5
85 to 115 6

Shear Stability
The ability of a grease to resist changes in consistency during mechanical
working is referred to as shear or mechanical stability. Two methods have been
standardized to evaluate the stability of a grease to working.
Prolonged Worked Penetration-ASTM D 217/IP 50, described previously, is
used before and after prolonged working in a grease worker to determine the
change in grease consistency.
Roll Stability-Roll stability is determined by ASTM Test for Roll Stability of
Lubricating Grease (D 1831) in conjunction with ASTM D 1403/IP 310.
After a worked penetration has been measured on a grease sample by ASTM D
1403, 50 g of the worked grease are placed into a horizontally-mounted cylinder

containing an 11-1b steel roller. The cylinder is rotated at 165 rpm for 2 h. The
inner roller rolls over the grease, working it during the test. After the test, the
penetration of the grease is once again measured by D 1403, and the difference
between the before and after penetrations is noted.
In both of these tests, the change in consistency is reported as either the
absolute change in penetration values or the percent change as outlined in ASTM
D 1831.
Roll stability tests are significant because they may show a directional change
that may occur in the consistency of a grease during service. No accurate
correlations have been determined.
Apparent Viscosity-Grease is by nature a nonNewtonian material. It is
characterized by the fact that flow is not initiated until stress is applied.
Increases in shear stress or pressure produce disproportionate increases in flow.
The term "apparent viscosity" is used to describe the observed viscosity of these
materials and is measured in poises. Since this observed viscosity varies with both
temperature and shear rate, it must be reported at a specific temperature and
shear rate. Apparent viscosity is determined by ASTM Test for Apparent
Viscosity of Lubricating Greases (D 1092).
In this test, a sample of grease is forced through a series of eight capillary
tubes by a floating piston actuated by a hydraulic system using a two-speed gear
pump. Poseutille's equation is used to calculate the apparent viscosity. The
results are expressed as a logarithmic graph of apparent viscosity versus shear
rate at a constant temperature, or apparent viscosity versus temperature at a
constant shear rate. This equipment also has been used to measure the
pumpability of greases at low temperature.
The apparent viscosity test is significant because it provides an indication of
ease of handling and dispensing at a specified temperature. It also is used as an
indication of the directional value of starting and running torques of grease
lubricated mechanisms. Specifications may include limiting values of apparent
viscosity for greases to be used at low temperature.

Dropping Point
The dropping point of a grease is the temperature at which it passes from a
semisolid to a liquid.
Two similar procedures are used to determine the dropping point of grease. In
both methods, a prescribed film of grease is coated on the inner surface of a
small cup whose sides slope toward a hole in the bottom. With ASTM Test for
Dropping Point of Lubricating Grease (D 566/IP 132), the sample is heated at a
prescribed rate until a liquid drop falls from the cup. In ASTM Test for
Dropping Point of Lubricating Grease of Wide Temperature Range (D 2265), the
sample is introduced into a preheated environment so that the heating rate is
controlled more uniformly. In both tests, the difference in temperature between
the grease in the cup and the environment are taken into account in calculating

the dropping point of the grease. Some greases containing thickeners other than
soaps may not separate oil nor melt.
The dropping point is useful (1) in identifying the type of thickener used in a
grease, (2) as an indication of the maximum temperature to which a grease can
be exposed without complete liquefaction or excessive oil separation, and (3)in
establishing bench marks for quality control.
Although greases normally do not perform satisfactorily at temperatures above
the dropping point, other factors are involved. High-temperature performance
can depend on the application method and frequency and whether or not a
softened grease is retained at the point of application by proper seals. Whether
the high temperature is continuous or intermittent, etc. also depends upon the
stability and evaporation properties of the grease.
Dropping point is useful, but it has no direct bearing on service performance
unless such a correlation has been established.

Oxidation Stability
ASTM Test for Oxidation Stability of Lubricating Greases by the Oxygen
Bomb Method (D 942/IP 142) was designed to predict shelf storage life of
greases in prepacked bearings. In this test, 5 glass dishes are filled with 4 g of
grease, each for a total of 20 g. These dishes are then sealed in a bomb on a rack,
and the bomb is pressurized to 110 psi (7.7 KPa/cm 2) with oxygen. The bomb is
heated in a bath at 210~ (99~ to accelerate oxidation. The amount of oxygen
absorbed by the grease is recorded in terms of pressure drop over a period of 100
h and, in some cases, 500 h. The pressure drop is a net result of absorbed oxygen
and any gases or by-products released from the grease.
Care must be exercised in the interpretation of data derived from the
oxidation bomb test. Additives incorporated into the grease can produce
misleading results because they may also react with oxygen. As an example,
sodium nitrite is sometimes added to grease to serve as a rust inhibitor. In the
oxidation bomb test, this material reacts with oxygen to form sodium nitrate. In
this instance, the drop in pressure is not indicative of the amount of oxidation of
the grease alone.
The oxidation bomb test is significant because it provides an indication of the
shelf life of a thin film of grease, as on machine parts or prelubricated bearings,
stored for long periods of time. It is a static test and not intended for predicting
the performance of grease under dynamic conditions. Nor is this test intended
for predicting the stability of grease stored in sealed commercial packages.

Effect of Copper on Oxidation Rate

ASTM Test for Effect of Copper on Oxidation Rate of Grease (D 1402) is
used to determine the effect of copper on oxidation rate. The procedure is the
same as the oxidation bomb test (ASTM D 942/IP 142) discussed in the
preceding paragraphs, except that clean, freshly prepared copper strips are

placed on edge in each of the five dishes of grease. The test is discontinued when
the pressure has dropped to 55 psi (3.85 KPa/cm 2) or at some predetermined
time period.
The results from this procedure indicate the catalytic effect of copper and its
alloys on the acceleration of grease oxidation under static conditions for long
periods of time. Such conditions occur when thin coatings of grease on metal
parts or bearings, in the presence of copper or copper alloys, are stored under
shelf conditions for extended time periods.
The method should not be used to predict the stability of grease on contact
with copper under dynamic conditions or when stored in sealed commercial
packages.

Effect of Grease on Copper

The procedure for the ASTM Test for Effect of Grease on Copper (D 1261) is
similar to ASTM Method D 942[IP 142, except only the two bottom dishes are
filled with 4 g of grease. A clean, freshly prepared copper strip is inserted on
edge into each of the dishes. The bomb is sealed and pressurized as in ASTM D
942, but it is kept in the bath at 210~ (99~ for only 24 h. The copper strips
are washed and examined for discoloration, etching, or corrosion.
The significance of ASTM D 1261 is that it provides a means for predicting the
staining or corrosion of copper-containing materials in contact with grease in
storage. Although the test is not designed to predict the stability of grease in
contact with copper, an indication of stability may be found at the end of the
test by examining the grease adjacent to the copper strips for color change.
The test is not intended to predict the effect of grease on copper or copper
alloys under dynamic service conditions.

Oil Separation
Greases differ markedly in their tendency to liberate oil. Although opinions
differ on whether or not lubrication is dependent on oil bleeding, excessive
liberation of free oil during storage is to be avoided.
The fluid can be squeezed out of a grease at varying rates depending on the gel
structure, the nature and viscosity of the lubricating fluid, and the applied
pressure and temperature.
ASTM Test for Oil Separation from Lubricating Greases During Storage (D
1742) is used to determine the tendency of lubricating greases to separate oil
during storage at 77"F (25~ It is not suitable for use with greases softer than
NLGI No. 1 consistency because of a tendency for the grease to seep through
the screen.
The test is useful because the results correlate with the oil separation which
occurs in containers of grease during storage under corresponding ambient
temperatures. It should not be used to predict the oil separation of grease under
dynamic service conditions.

Evaporation Loss
Exposure of a grease to high temperatures may cause evaporation of some of
the liquid lubricant causing the remaining grease to become drier and stiffer or
leading to other undesirable changes in the grease structure. Greases containing
some light viscosity oils for good low-temperature performance may show
evaporation losses at the higher temperatures. Evaporation also may cause
problems where vapors may be hazardous or combustible or interfere with
operations as in gas-cooled reactors.
Evaporation loss is determined by ASTM Test for Evaporation Loss of
Lubricating Greases over Wide-Temperature Range (D 2595). The test is useful
for the determination of loss of volatile materials from a grease at temperatures
between 200 and 600~ (93 and 316~ It also is used to compare the
evaporation losses of greases intended for similar service. (The grease which
shows the least loss to evaporation, all other factors being equal, will probably
perform longer in service.)
Results of ASTM D 2595 may not be representative of volatilization which
may occur in service.

Rust Prevention
Greases must not be corrosive to metals they contact and should not develop
corrosion tendencies with aging or oxidation. A method for assessing rust
prevention by greases is ASTM Test for Rust Preventive Properties of
Lubricating Greases (D 1743).
In the ASTM D 1743 method, a tapered roller bearing is packed with grease
and, following a short run-in period, dipped into distilled water and stored above
the water in 100 percent relative humidity at 125~ (52~ for 48 h. The beating
is then cleaned and examined for corrosion.
The significance of this test is that it indicates those greases capable of
preventing rust and corrosion in static or storage conditions. The correlation
with service conditions, particularly under static conditions, is considered to be
quite good.

Lead in Greases
ASTM Test for Lead in New and Used Greases (D 1262) is used to determine
the lead content of new and used greases containing 0.1 percent or more lead. It
is also applicable for the determination of lead in fractions separated from a
grease by means of appropriate solvents. Other metallic elements-sulfur,
chlorine, phosphorus-in amounts commonly found in greases do not interfere in
this method.
Lead content may be indicative of the amount of soaps or lead containing
additives in a grease. ASTM D 1262 can be used to monitor the level of these
components.

Water Washout
The ability of a grease to resist washout under conditions where water may
splash or impinge directly on a bearing is an important property in the
maintenance of a satisfactory lubricating film. ASTM Test for Water Washout
Characteristics of Lubricating Greases (D 1264) evaluates the resistance of a
lubricating grease to washout by water from a bearing at IO0~ (38~ 175~
(790C).
This test method uses a 204 K Conrad type 8-ball bearing equipped with front
and rear shields that have a specified clearance. It is packed with 4 g of the test
grease and then rotated at 600 rpm for 1 h while a jet of water at either 100~
(38~ or 175~ (79~ impinges on the bearing housing. The bearing is dried,
and the percent loss by weight of grease is determined.
The test serves only as a measure of the resistance of a grease to water
washout. It should not be considered the equivalent of a service evaluation
unless such correlation has been established. Even comparative results between
different greases may not predict the relative performance of the two greases in
actual field use.

Extreme Pressure Timken Method

The ASTM Test for Measurement of Extreme Pressure Properties of
Lubricating Grease (Timken Method) (ASTM D 2509) may be used to determine
the load carrying capacity of a grease.
In this test, a tapered roller bearing cup is rotated against a stationary,
hardened steel block. Fixed weights force the block into line contact with the
rotating cup through a lever system with a mechanical advantage of ten. The
"OK Value" is the maximum load the lubricant film will withstand without
rupturing and causing scoring in the contact zone after a 10-rain run.
The test is a rapid method which may be used to differentiate between greases
having low, medium, or high levels of extreme pressure properties. The results of
this test do not necessarily correlate with results from field service.

Extreme Pressure Four-Ball Test

ASTM Measurement of Extreme Pressure Properties of Lubricating Grease
(Four-Ball Method) (D 2596) is also used to determine the load-carrying
properties of lubricating greases. With this procedure two evaluations may be
made: (1) the Load-Wear Index (formerly called Heitz-Mean Load), and (2) the
Weld Point.
The test was developed to evaluate the extreme pressure, antiwear, and
antiweld properties of a lubricant. The tester is operated with one steel ball
under load rotating against three steel balls held stationary to form a cradle. The
grease under test covers the area of contact of the four balls. Unit pressures as
high as 1 000 000 lb/in. 2 can be attained.
The procedure involves the running of a series of 10-s tests over a range of

increasing loads until welding occurs. During a test, scars are formed in the
surfaces of the three stationary balls. The diameter of the scar depends upon the
load, speed, test duration, and lubricant. The scars are measured under a
microscope having a calibrated grid. From the scar measurements the Load-Wear
Index is calculated.
The significance of this test is that it is a rapid method which may be used to
differentiate between greases having low, medium, or high levels of extreme
pressure properties.
Lubricating greases with a fluid component that contains a silicone or a
halogenated silicone oil can not be evaluated with D 2596. In addition, the
results of this test do not necessarily correlate with results from field service.

WearPreventive Characteristics of Grease

The determination of wear preventive characteristics of greases in sliding
steel-on-steel applications is made with ASTM Test for Wear Preventive
Characteristics of Lubricating Grease (Four-Ball Method) (D 2266). With this
test a steel ball is rotated under load against three stationary steel balls with
grease lubricated surfaces. The diameters of the wear scars that occur on the
stationary balls are measured after completion of the test.
The test is significant because it can be used to determine the relative
wear-preventing properties under the test conditions.
ASTM Test D 2266 is limited in the following respects.
1. If test conditions are changed, the relative ratings may change.
2. Wear characteristics are not predicted for metal combinations other than
steel.
3. No differentiation can be made between extreme pressure and nonextreme
pressure greases.
4. No correlation can be inferred between the results of the test and field
service unless such correlation has been established.

Leakage Tendencies of WheelBearing Greases

ASTM Test for Leakage Tendencies of Automotive Wheel Bearing Greases (D
1263) is used to evaluate the leakage tendencies of wheel bearing greases during
testing under prescribed laboratory conditions.
The test employs a modified automotive front hub assembly that is operated
at 660 rpm for 6 h at 220~ (104~ The smaller bearing is packed with 2 g of
grease and the larger bearing with 3 g. Eighty-five grams of grease are put into
the hub. After the test, the leakage in the hubcap and leakage collector is
determined. The bearings are washed and examined for varnish, gum, and
lacquer-like material.
ASTM Test D 1263 provides a means to differentiate among grease products
with distinctly different leakage characteristics. In addition, skilled operators can
observe significant changes in other grease characteristics that may have occurred

during the test. However, these observations are subject to differences in

personal judgment and cannot be used for quantitative rating.
The test does not distinguish between wheel bearing greases having similar or
borderline leakage.

Functional Life of Ball Bearing Greases

Two procedures for evaluating the functional life of ball bearing greases are
contained in ASTM Test for Functional Life of Ball Bearing Greases (D 1741).
One procedure simulates the type of grease-packing commonly encountered in
the field when the grease is pumped into the bearing housing with a grease gun.
In the other procedure, one third of the free space in each bearing is filled with
grease, while no grease is placed in the housing. This type of grease packing is
typical of many applications including factory-packed bearings.
The tester used in D 1741 employs a pair of 30-mm (Type 306) deep-grooved
radial ball bearings installed on a shaft. The bearings are run at 3500 rpm with a
radial load of 25 lb (11.2 kg) and an axial load of 40 lb (18.1 kg) at
temperatures up to 125~ (257~ In both procedures, the bearings are run for
20 h, and then stopped and cooled for 4 h. This cycle is repeated until failure
occurs or for a specified number of hours.
The test has significance because it may be used as a screening device to assist
in the selection of greases which show promise as ball or roller bearing lubricants
or both for use under the temperature limitations of the test. Close
discrimination between lubricants is not possible with these procedures, and the
method is limited to greases whose operating temperatures are not above 125~
(257"F). In addition, the method is not an equivalent to long service field tests.

Low-Temperature Torque
Greases harden and become more viscous as the temperature is lowered. In
extreme cases the grease can become so rigid that excessive torque occurs within
the bearing. Greases designed for extremely low temperatures must not stiffen
nor offer excessive resistance to rotation.
ASTM Test for Low-Temperature Torque for Ball Bearing Greases (D 1478)
measures the starting and running torques of lubricating greases packed in small
beatings down to temperatures o f - 6 5 ~ (-54~ In this procedure, fully
packed bearings are installed on a spindle that can be rotated at 1 rpm. The
assembly is inserted in a cold box. The outer race is connected by a string
assembly to a spring scale where the restraining force is measured. When the
motor is started, the initial peak restraining force is recorded. After running for
10 min, the restraining force is recorded again. These two values are multiplied
by the length of the lever arm, and the products are reported as the starting and
running torques in gram-centimeters (g-cm).
The test is significant because it is a means to compare the low-temperature
torques of widely different greases. Since the method was developed using

greases with extremely low-torque characteristics at -65~ (-54~ it may not

be applicable to other greases, speeds, or temperatures. Also, test conditions are
substarttiaUy different from those found in the field so test results will not
necessarily correlate with results from field tests.

Torque Stability, Wear,and Brine Sensitivity of Ball Joint Greases

ASTM Test for Torque Stability Wear and Brine Sensitivity Evaluation of Ball
Joint Greases (D 3428) provides two procedures for evaluating the suitability of
lubricating greases for use in automotive chassis ball joints.
The torque stability procedure provides a measure of the frictional and
antiwear properties of lubricating greases when subjected to load and prolonged
working under oscillating motions in ball joints.
The brine sensitivity test determines the ability of a lubricating grease to
prevent noise from an oscillating ball joint when exposed to brine contamina-
tion.
In these tests, a grease lubricated automotive ball joint stud and bearing,
confined in a fixed housing, is rocked through an arc under prescribed
conditions of rocking frequency, rocking amplitude, load, and time. The noise,
wear, and torque are observed or recorded or both.
The tests are used as a means to screen lubricating greases to be used in
automotive chassis ball joints. Since both the test components and procedures
approximate those typical of current equipment and operation, test results are
considered to provide some measure of grease suitability. Neither test is intended
to measure the service life of an automotive chassis ball joint lubricating grease
under actual service conditions.

Greases in Ball Bearings at Elevated Temperatures

ASTM Test for Performance Characteristics of Lubricating Greases in Ball
Bearings at Elevated Temperatures (D 3336) is used to evaluate the performance
characteristics of lubricating greases in ball bearings operating under light loads
at high speeds and elevated temperatures.
With this test, the lubricating grease is evaluated in a 20-mm (Society of
Automotive Engineers (SAE) No. 204) heat resistant steel ball bearing as it is
rotated at 10 000 rpm under light load at a specified elevated temperature up to
700~ (371~ The procedure provides for two cycle periods. One test cycle
calls for 2189 h of operation on temperature and 2% of shutdown without heat.
The other test cycle calls for 20 h of operation on temperature and 4 h of
shutdown without heat.
No correlation with actual field service can be assumed for this test.

Greases in Small Bearings

The computer and aircraft industries have used small bearings for many years.
As the trend toward miniaturization mounted in other industries, a suitable test

was needed to evaluate lubricating greases in small bearings. ASTM Evaluation of

Greases in Small Beatings (D 3337) was developed to serve this purpose.
ASTM D 3337 may be used to determine grease life and torque in a small R-4
ball bearing. In this test the bearing is run at 12 000 rpm with a ~A-lbradial and
5-1b axial load. If high-temperature bearings are used, the equipment is capable
of testing up to 600~ (316~
The test has significance because it can be used as a means to differentiate
between expected lives of greases used in small bearings at high speeds and
temperatures. Grease torque also can be measured at both low and high speeds
using this procedure.
The method will not differentiate between greases of closely related
characteristics, and it should not be considered the equivalent of long-time, field
service tests.

Grease Flow Properties at High Temperatures

The consistency of a grease is a critical parameter which defines the ability of
a grease to perform in a fixed operating environment. The dropping point and oil
separation tests define the temperature at which the thickener melts or if oil
separates from the grease under high-temperature conditions. Neither of these
evaluations indicate less dramatic, yet significant, changes in consistency as the
grease approaches a fixed temperature.
ASTM Measurement of Flow Properties of Lubricating Greases at High
Temperatures (D 3232) can be used to measure the flow properties of
lubricating greases under high-temperature, low-shear conditions. Using this
method, a grease sample is packed in an aluminum block. The packed block is
placed on a hot plate capable of attaining temperatures in excess of 600~
(316~ at a heating rate of 10 -+ 2~ (5 -+ l~ A special trident probe
spindle, attached to a Brookfield viscometer, is lowered into the grease sample,
and the hot plate is turned on. Simultaneously, the spindle is caused to rotate at
a constant speed of 20 rpm. Torque measurements are read from the viscometer
every minute. Readings are continued until the reading drops below 0.5 on the
viscometer scale or until the maximum sample temperature of interest is
attained. With this data and an appropriate conversion table, a plot of apparent
viscosity versus temperature is prepared.
The results of this test provide a direct indication of the flow properties of a
grease between room and elevated temperatures. Although the test does not give
actual flow rates as in a pipeline, it is a means for obtaining some indication of
this property.

Deleterious Particles in Lubricating Grease

ASTM Estimation of Deleterious Particles in Lubricating Grease (D 1404)
defines a deleterious particle as one which will scratch a polished plastic surface.

The test is applicable regardless of grease color or fillers and also may be used for
testing other semisolid or heavy liquid substances.
With this method, the lubricating grease being tested is placed between two
clean, highly polished acrylate plastic plates held rigidly and parallel to each
other in metal holders. The assembly is pressed together squeezing the grease
between the plastic plates to a thin layer. Any solid particles in the grease larger
than the distance of separation of the plates and harder than the plastic will
become imbedded in the opposing plastic surfaces. The apparatus is so
constructed that one of the plates may be rotated about 30 deg with respect to
the other while the whole assembly is under pressure. This will cause the
imbedded particles to form characteristic arc-shaped scratches in one or both
plates.
The relative number of such solid particles may be estimated by counting the
total number of arc-shaped scratches on the two plates.
The test has significance because it is a rapid means for estimating the number
of deleterious particles in a lubricating grease. However, a particle that is abrasive
to plastic may not be abrasive to steel or other bearing materials. Therefore, the
results of this test do not imply performance in field service.

Applicable ASTM/IP Standards

ASTM IP Title

D 217 50 Cone Penetration of Lubricating Grease

D 566 132 Dropping Point of Lubricating Grease
D 942 142 Oxidation Stability of Lubricating Greases by
the Oxygen Bomb Method
D 1092 Apparent Viscosity of Lubricating Greases
D 1261 Effect of Grease on Copper
D 1262 Lead in New and Used Greases
D 1263 Leakage Tendencies of Automotive Wheel
Bearing Greases
D 1264 Water Washout Characteristics of
Lubricating Greases
D 1402 Effect of Copper on Oxidation Rate of Grease
D 1403 310 Cone Penetration of Lubrication Grease Using
One-Quarter and One-Half Scale Cone Equipment
D 1404 Estimation of Deleterious Particles in
Lubricating Grease
D 1478 Low-Temperature Torque of Ball Bearing Greases
D 1741 Functional Life of Ball Bearing Greases
D 1742 Oil Separation from Lubricating Grease
During Storage
D 1743 Rust Preventive Properties of Lubricating Greases
D 1831 Roll Stability of Lubricating Grease

Applicable ASTM/IP Standards (Continued.)

ASTM IP Title

D 2265 Dropping Point of Lubricating Grease of Wide

Temperature Range
D 2266 Wear Preventive Characteristics of Lubricating
Grease (Four-BaU Method)
D 2509 Measurement of Extreme Pressure Properties of
Lubricating Grease (Timken Method)
D 2595 Evaporation Loss of Lubricating Greases over
Wide-Temperature Range
D 2596 Measurement of Extreme-Pressure Properties of
Lubricating Grease (Four-Ball Method)
D 3232 Flow Properties of Lubricating Greases at
High Temperatures
D 3336 Performance Characteristics of Lubricating Greases
in Ball Bearings at Elevated Temperatures
D 3337 Evaluation of Greases in Small Bearings
D 3428 Torque Stability Wear and Brine Sensitivity
Evaluation of Ball Joint Greases

Bibliography
Bollo, F. G. and Woods, A. A.,"Modem Grease Technology," Advances in Petroleum
Chemistry and Refining, Vol. VI, Intersciencr New York, 1962.
Boner, C. J., "Lubricating Grease," Petroleum Products Handbook, V. B. Guthrie, Ed.,
McGraw-Hill, New York, 1960, Section 9, Part 3.
Boner, C. J., Manufacture and Application of Lubricating Greases, Reinhold, New York,
1954.
Dawtrey, S., "Grease," Modern Petroleum Technology, 4th ed., Applied Science, London,
England, 1973.
Harris, J. H., The Lubrication of Rolling Bearings, Shell-Mex and British Petroleum,
London, England, 1967.
Hotten, B. W., "Formation and Structure of Lubricating Grease," Advances in Petroleum
Chemistry and Refining, Vol. IX, Interscience, New York, 1964.

Chapter 10 Petroleum Waxes,

Including Petrolatums

Introduction
In the early years of petroleum processing, the waxy materials that were
separated were regarded as waste with no commercial value. Ultimately,
however, wax products were recovered from the waste streams and, with the
benefit of additional refining, were found to be useful replacements for natural
waxes in many applications. A variety of grades of petroleum wax evolved that
covered a broad range of physical properties. Now the petroleum wax product
lines are in demand for a wide variety of uses. (It is of some interest to note that
the end uses of wax are probably more diverse than the uses of any other
petroleum product.)
Modem refining methods have made available select grades of wax of
controllable and reproducible quality, and some have unique properties for
specialized applications. Refined paraffin waxes, in grades varying by melting
point and other qualities, represent the predominant segment of the total
petroleum wax demand. The demand for tacky or ductile waxes and
high-melting point waxes is met by the microcrystaUine waxes selectively
separated from the heavier fractions and residua of petroleum. In addition,
complex blends of waxes have become increasingly important to the packaging
industry, especially the hot melt blends containing petroleum wax base admixed
with polymers, resins, or other additives.

Occurrence and Refining of Waxes

Wax is found in varying amounts in most crude oils. Paraffin base crudes
(those rich in paraffin hydrocarbons) and mixed base crudes (containing both
paraffins and naphthenes) usually have greater wax contents than aromatic base
crudes. The type of wax recovered is dependent on the source and type of crude.
In the distillation of waxy crude oils, low-boiling cuts are removed first,
followed by the intermediate and higher-boiling fractions which are suitable for
making lubricating oils. To improve the low-temperature, pour-point property of
lubricating oils, the lube cut is dewaxed. The by-product from dewaxing is
refined to produce finished wax. Paraffin waxes are obtained from the
intermediate boiling range lubricating oil fractions. Microcrystalline waxes are
derived from the high-boiling lubricating oil fractions or residua.
Lube oil dewaxing in modern operations involves filtering a chilled solution of
waxy lubricating oil in a specific solvent. The waxy material thus removed is
179
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180 SIGNIFICANCE OF TESTS

designated as "slack wax." Slack wax contains a significant amount of oil that
must be removed before the wax is suitable for most applications.
A solvent crystallization process generally is used for deoiling slack waxes. The
raw wax is dissolved in solvent (for example, a methyl ethyl ketone-toluene
mixture); the solution is chilled; and the crystallized wax is filtered out. Various
grades of wax may be obtained by repeating the deoiling step at successively
lower temperatures. The crystallized paraffin wax obtained from deoiling usually
contains less than 0.5 percent oil. Some deoiled slack wax which is sold as crude
scale wax contains about 2 percent oil.
The final stages of making refined wax are for purposes of improving the
color, odor, and purity. Color and odor bodies and trace impurities of olefinic
and aromatic hydrocarbons are removed by either hydrogenation or sulfuric acid
treatment. In an alternative process the wax may be decolorized and deodorized
by clay filtration. Following either procedure, the final product is termed a
refined paraffin wax or a refined microcrystalline wax.
Petrolatums are oil-bearing products which are made from the heavy
lubricating oil fraction in residua. Various processes are used to remove excessive
oil, color, and odor bodies including combinations of such methods as solvent
dilution and settling or centrifugation, fractional solvent crystallization, and
percolation through clay or other adsorbent. The degree of refining varies-
industrial grades of petrolatum require minimal processing, while pharmaceutical
grades (the so-called petroleum jelly) require very selective treatment.

Definitions
ASTM Definition of Terms Relating to Petroleum (D 288) defines wax as: "A
product separated from petroleum which is solid or semisolid at 25~ (770F) and
consists essentially of a mixture of saturated hydrocarbons."
Closer classification of waxes is difficult because of the wide variety of waxes
that have become available through the expansion of refining technology and the
apparent overlapping among the types. However, refined petroleum waxes often
are identified as paraffin wax, microcrystalline wax, or petrolatum.
Paraffin wax is petroleum wax consisting mainly of normal alkanes, varying
amounts of condensed cycloalkanes, isoalkanes, and occasionally a very low
percentage of aromatic material. Molecular weights are usually less than 450, and
the viscosity at 210~ normally will be less than 6 cSt. Either needle or plate
type crystal structures are common. Paraffin waxes also exhibit pronounced
latent heats of crystallization, and some have transition points (temperatures at
which crystal structure modification occurs below the apparent solidification
point of the wax).
Microcrystalline waxes contain substantial portions of hydrocarbons other
than normal alkanes, and the components usually have higher molecular weights
than paraffin wax components. Microcrystalline waxes also have smaller crystal
structures and greater affinity for oil than paraffin waxes. Microcrystalline waxes
usually melt between 150 and 220~ and have viscosities between 10 and 20 cSt
at 2100F.
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CHAPTER 10 ON PETROLEUM WAXES, INCLUDING PETROLATUMS 181

By broad definition (ASTM D 288) petrolatum is: "A petroleum wax of

unctuous structure containing substantial amounts of oil." The definition
embraces the unrefined industrial grades as well as the refined pharmaceutical
grades. The semisolid nature of petrolatum is due to the gel-like dispersion of a
relatively high proportion of oil (usually above 10 percent) in the microcrystal-
line wax base. Petrolatums resemble microcrystaUine waxes in composition, but
contain lower proportions of normal paraffins. Melting points range from about
100 to 175~ and viscosities range from 10 to 25 cSt at 210~ Petrolatum
colors range from the almost black crude form to the highly refined white
pharmaceutical grade.
Petroleum wax is also an ingredient in certain so-called hot melts, and some
test procedures may be applicable to hot melts. Hot melts have been defined as:
"Those coatings, adhesives, or impregnants normally solid at ambient tempera-
tures and liquid at elevated temperatures which are applied to substrates as hot
liquids without the addition of volatile diluents." Wax-based hot melts are
blends of wax, polymers, resins, or other additives. Hot melt products vary
widely in total additive content depending on the end use. Many contain more
than 25 percent additives. The additives serve to improve such properties as wax
coating flexibility, barrier properties, gloss, scuff resistance, and viscosity.

Applications for Wax

Wax is one of the most versatile products of the oil industry. As a coating for a
variety of paper, film, and foil substrates in the packaging industry, wax provides
improved appearance, strength, moisture proofing, food oil resistance, sealing
strength, and other desirable effects. The packaging industry consumes the major
share of refined petroleum waxes either in the form of straight waxes or as
hot-melt blends.
Wax has long served as a source of light and heat in such applications as
candles, matches, and flares. In other uses, the high-gloss characteristic of some
petroleum waxes makes them suitable ingredients for polishes. The highly
refined waxes have excellent electrical properties for application in the
insulation of small transformers, coils, capacitors, and certain cables. Waxes are
used for the coating of fruit and cheese and the lining of cans and barrels. Blends
of waxes are used by dentists for making dentures and engineers for
mass-producing precision castings. Waxy petroleum streams also are used as
feedstock for the production of numerous petrochemicals.

Quality Criteria
Criteria for judging the quality of a wax must be specific for the type of wax
and its intended application.
Three general categories of properties are useful for assessing the quality of
waxes: (a) physical properties (characterizations used for quality control); (b)
chemical properties and composition (used for basic characterizations); (c)
functional properties (empirical evaluations under simulated consumer con-
ditions).
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182 SIGNIFICANCE OF TESTS

Criteria for Judging Physical Properties

Melting Point-The melting point is one of the most widely used tests to
determine the quality and type of wax. Petroleum waxes usually do not melt at
sharply defined temperatures because they are mixtures of hydrocarbons with
different melting points. Paraffin waxes, as relatively simple mixtures, usually
have narrower melting ranges than do microcrystalline waxes and petrolatums
which are more complex in composition and melting behavior.
The melting point of a wax has direct and indirect significance in most
applications. Paraffin waxes are usually marketed on the basis of melting point
determined from the plateau in the cooling curve which is also termed the
English melting point (EMP). (Waxes are also sometimes marketed on the basis
of so-called American melting point (AMP) which by definition is 3~ above the
EMP.) Melting point of a wax grade generally is expressed as a range, that is,
130/135 MP.
Some waxes (especially narrow-cut, highly paraffinic types) undergo a phase
change or transition point in the solid state which is usually about 25 to 40~
below the melting point. Accompanying this change of crystalline form there
may be significant changes in properties such as refractive index, density,
flexibility, hardness, coefficients of expansion and friction, tensile strength,
sealing strength, and gloss. For applications requiring consistency of properties
over a specific temperature range, waxes are selected which do not exhibit a
transition point in the critical range.
Viscosity-The fluidity of molten wax is important in applications involving
coating or dipping processes, since it influences the amount of wax that is
deposited on the substrate as well as the performance effectiveness of the
coating obtained. Examples of such applications are in paper converting, hot-dip
anti-corrosion coatings, and taper manufacturing.
Paraffin waxes do not differ widely in viscosity, typically falling in the range
of 3 to 6 cSt at 210~ (98.9~ although some grades have viscosities as high as
10 cSt. Microcrystalline waxes are considerably more viscous and vary over a
wide range-about 10 to 20 cSt at 2tO~F (98.9~
The hot-melt blends of petroleum waxes with various additive modifiers cover
a wide spectrum of viscosity. With additives of relatively low-molecular weight,
only minor thickening effects occur. (Some of the resinous group of additives
are prime examples.) On the other hand, additives that are high polymers, such
as the polyethylenes or various copolymers, may have very high-thickening
power. Thus, the components in a hot-melt formulation will be selected to give
the proper viscosity consistent with the expected application conditions in the
designated waxing equipment. Optimum viscosities usually exist for the various
dipping operations, roll coaters, curtain coaters, or high-shear coaters. Viscosities
of hot melts for coatings may range as high as 20 000 cP at 350~ (176.7~
although 100 to 2000 cP is the more common range.
Hardness-Hardness is a measure of resistance to deformation abrasion or
damage; hence, it is an important criterion for many wax applications.

Narrow-cut paraffin waxes generally have greater hardness than broad-cut waxes
of the same melting point, and waxes with higher proportions of normal
paraffins have greater hardness than highly branched hydrocarbons. Hardness is
indirectly related to blocking tendency and gloss. Hard waxes usually have
higher blocking points and better gloss than waxes of the same average molecular
weight but wider molecular weight range.
Hardness is determined by measuring the depth of penetration of a needle or
cone into a wax specimen. Techniques for measuring hardness (cone penetration
for softer waxes and needle penetration for the harder waxes) have been
standardized by American Society for Testing and Materials (ASTM) and
Institute of Petroleum (IP) and will be described in later paragraphs.
Strength of Wax-Another quality test for wax is tensile strength. Some
manufacturers and consumers find this to be a useful guide in monitoring the
quality of the wax, although the tensile strength of a wax is extremely sensitive
to the conditions of preparation of the wax specimen and the conditions of
applying the tensile load.
The modulus of rupture is also an indication of strength or toughness of wax.
Modulus of rupture is believed to correlate with the sealing strength and
flexibility of waxes for paper coating.

Criteriafor Judging Chemical Properties

Chemical properties and the composition of wax give a good indication of its
degree of refinement. The properties of greatest significance are color, odor, oil
content, amounts of solvent extractables, boiling point distribution, molecular
weight, ultraviolet absorptivity, peroxide content, and amounts of carbonizable
substances. In addition, there are specific chemical properties criteria for food
grade wax.
Color-Paraffin waxes are generally of a translucent white color, whereas
microcrystalline waxes and petrolatums range from white to almost black. A
fully refined wax should be virtually colorless ("water-white") when examined
in the molten state; typical scale wax usually exhibits a slight yellow or "straw"
tint. Absence of color is of particular importance in waxes used for
pharmaceutical purposes or the manufacture of food wrappings.
The acceptability of the color of microcrystalline waxes and petrolatums
depends on the use for which they are intended. In some applications (for
example, the manufacture of corrosion preventives), color may be of little
importance, but in others it may be critical. For pharmaceutical purposes, the
color of petrolatum is recognized in the grade specifications with colors ranging
from white to yellow.
Colors in the solid state normally are expressed in descriptive terms such as
white, off-white, yellow, amber, brown, etc. However, there is no standard test
method for measuring this characteristic.
Odor-Freedom from odor and taste is particularly important in applications
where the wax is likely to contact foodstuffs. When poor wax odor is detected,

it may be due to inadequate refining, contamination during transport, storage or

waxing operations, or deterioration in use. Odors due to inadequate refining are
usually associated with a high-oil content or, less frequently, with residual
solvent. Odor may be acquired during storage by absorption of odorous material
from the container in which the wax slabs are packed. Wax also readily absorbs
the odors of products such as cheese or soap if stored in proximity. Wax that has
been overheated in use tends to oxidize and develop an odor similar to rancid
coconut oil.
Subjective evaluations, such as odor, are difficult to standardize. There is,
however, a technique which ensures reasonable concordance within a group
whose members have agreed about odor level. Difficulties arise when there is a
difference of opinion as to what constitutes an acceptable odor.
Oil Content-Because petroleum waxes are mixtures of hydrocarbons, which
cover a range of molecular type and molecular weight, some components of a
given wax may be of lower melting point and show more solubility or
extractability than other fractions of the wax. These components are identified
as the oil content of wax when they are determined as the soluble fraction in the
methyl ethyl ketone crystallization of the oil content method (ASTM Oil
Content of Petroleum Waxes (D 721/IP 158)). It should be recognized that there
is no clear-cut division between oil and wax with regard to particular chemical
species.
It is necessary to distinguish between paraffin wax, microcrystalline wax, and
petrolatums when considering the significance of oil content because of the
different degree of affinity that each of these wax types has for oil.
Fully refined paraffin wax usually has an oil content of less than 0.5 percent.
Waxes containing somewhat more than this amount of oil (that is, 0.5 to about
2.0 percent) are referred to as "scale wax." An intermediate grade known as
"semirefined wax" is sometimes recognized for waxes having an oil content of
about 1 percent. Excess oil tends to exude from paraffin wax giving it a dull
appearance and a greasy feel. A high-oil content tends to have an adverse effect
on sealing strength, tensile strength, hardness, odor, taste, color, and color
stability. High-oil content also tends to plasticize wax and increase its flexibility.
Microcrystalline waxes have a greater affinity for oil than paraffin waxes
because of their smaller crystal structure. The permissible amount depends on
the type of wax and its intended use. The oil content of microcrystalline wax is,
in general, much greater than that of paraffin wax and could be as high as 10
percent. Waxes containing more than 10 percent oil would usually be classed as
petrolatums, but the demarcation is by no means precise.
Solvent Extractables-For waxes containing no more than 15 percent oil,
ASTM method D 721/IP 158 is used to define oil content. For waxy streams
that contain more than 15 percent oil and various "soft" or soluble fractions
(for example, petrolatum and slack waxes), a new procedure has been developed
(ASTM Test for Solvent Extractables in Petroleum Waxes (D 3235)).
(It should be remembered that the solvent separations are empirical, and the

distinction between "oil content" and "extractables" is associated with the

different solvent compositions. The terminology should not be used interchange-
ably. Thus, it is erroneous to indicate an oil content as being determined by
ASTM D 3235.)
Boiling Point Distribution-Boiling point distribution is useful because it
provides an estimate of hydrocarbon molecular weight distribution that
hafluences many of the physical and functional properties of petroleum wax. (To
a lesser extent, distillation characteristics also are influenced by the distribution
of various molecular types; that is, normal paraffins, branched, or cyclic
structures. In the case of the paraffin waxes which are predominantly straight
chain, the distillation curve reflects the molecular size distribution.)
In the most common distillation test, ASTM Test for Distillation of Petroleum
Products at Reduced Pressure (D 1160), cuts are obtained under reduced
pressure, such as at 10 mm for paraffin waxes or at 1 mm for higher molecular
weight waxes. The cuts are taken at intervals across the full distillable range, and
the complete results may be reported. In some cases, and for brevity, the
distillation results are reported as the temperature difference observed between
the 5 percent off and 95 percent off cut points. This would represent a "width
of cut" statement, expressed in degrees, at the reduced pressure. Waxes having
very narrow width of cut will tend to be more crystalline, have higher melting
points, higher hardness and tensile strength properties, and less flexibility.
Molecular Weight-The molecular weight of various waxes may differ
according to: (1) the source of the wax (whether it originated in the lighter or
heavier grade lubricating oils), and (2) the processing of the wax (the closeness
of the distillation cut or the fractionation by crystallization). Thus, the average
molecular weight of a wax may represent an average of a narrow or a wide band
of distribution.
As a generalization, for any series of similar waxes, an increase in molecular
weight increases viscosity and melting point. Howeverl many of the other
physical and functional properties are more related to the hydrocarbon types
and distribution than to the average molecular weight.
The procedure for determination of number average molecular weight is
described in later paragraphs.
Criteria for Food Grade Wax-Federal regulation CFR 121.1156 contains a
specification that describes food grade wax as a "mixture of solid hydrocarbon,
paraffinic in nature, derived from petroleum and refined to meet specifications."
Besides normal guidelines, the U.S. specification and its counterpart in the
United Kingdom impose stringent controls on the polynuclear aromatic
hydrocarbon content qf food grade waxes for direct use in foods or indirect
contact with foods in packaging materials. The controls are to ensure the
essential absence of polynuclear hydrocarbons, especially those that may be
carcinogenic. The rigorous procedure for estimating polynuclear aromatic
content of petroleum waxes is described in the section of this chapter on tests
for chemical properties.

Ultraviolet Absorptivity-For some process control purposes or for research

purposes, it may be desirable to monitor the total aromatic content of a
petroleum wax. ASTM Test for Ultraviolet Absorbance and Absorptivity of
Petroleum Products (D 2008) provides this capability.
Although this procedure shows good operator precision, the interpretation of
results requires some caution. Since the test does not include any selective
fractionation of the sample, it does not distinguish any particular aromatic. It is
also subject to the errors arising from interferences or differences in strong or
weak absorptivities shown by different aromatics. Therefore, the test is good for
characterization, but cannot be used for quantitative determination of aromatic
content or other absorptive component.
Carbonizable Substance-The so-called "Readily Carbonizable Substance" test
is no longer in wide use, although it is still a requirement for paraffin wax in the
monograph in the U.S. National Formulary, Volume 13. The test has some
utility as a check on the degree of removal of trace reactive materials in the
finishing of the wax products, but it is subject to errors and misleading
interpretation. In addition, it does not correlate with specific impurities of
interest, nor is it a good quantitative measure.
Peroxide Content-The presence of peroxides or oxidized products such as
aldehydes or fatty acids are found in wax as a result of oxidation and
deterioration of wax either in use or storage. Suitable antioxidants, such as 2,6
di-tertiary butyl-p-cresol and butylated hydroxyanisole, may be used to retard
oxidation. ASTM Test for Peroxide Number of Petroleum Wax (D 1832) is used
to measure the peroxide content of wax.

Criteria for Judging Functional Properties

Testing methods for evaluating functional properties are often empirical in
nature and based on the simulated conditions of use. The results of such tests
are intended to correlate with practice and used to determine the suitability of a
wax for a particular application.
The properties of waxed paper or board depend not only on the individual
characteristics of the wax and paper components, but also on the manner in
which they interact when they are combined in the waxing process. For this
reason, it is necessary to conduct certain functional tests on the finished paper.
According to the method of application, the wax may be coated on one or
both surfaces of the paper, or it may be impregnated into the pores and fibers of
the paper.
Wax Content of Substrates-Many of the functional properties of coated board
or waxed paper are dependent on the amounts of wax present either on the
surface or internally.
Surface wax on each or both sides of a weighed specimen can be determined
by scraping each side and weighing the specimen after each operation. Internal
wax is the difference between total wax content and total surface wax. Total
wax content can be determined by solvent extraction or by finding the

difference between average weight per unit area of waxed and unwaxed
specimens.
Blocking Properties-Blocking tendency is an important quality criterion for
waxes, especially those used in various paper and paperboard coating applica-
tions. Blocking occurs at moderately warm temperatures when waxed surfaces
stick together or block. If the surfaces of waxed paper block, the surface
appearance, gloss, and barrier properties are destroyed when the papers are
separated. The blocking and picking points indicate the temperature range at
which waxed film surfaces become damaged if contact is made.
In general, a low resistance to blocking is ~ssociated with the presence of
low-molecular weight and nonnormal fractions in the wax, such as oil or soft
waxes. Likewise, broad-cut waxes generally show somewhat lower blocking
points than shown by narrow-cut waxes of the same average molecular weight or
viscosity. In addition, the blocking point of a given wax may also be dependent
on the conditions under which the particular wax coating is prepared. For
example, subtle changes in the crystalline nature of the coating can occur with
variations in paper substrate quality, coating application temperature, chilling
conditions to set the coating, and particulars of conditioning or aging of the
coating. Standard testing procedures are designed to control these factors.
Testing for blocking tendency is done usually with a moderate load (0.3 psi)
applied to two adjacent waxed paper surfaces which are exposed to the range of
temperature across a gradient heating plate. The test serves to simulate normal
packaging quality needs. A more severe blocking tendency test in which the
adjacent waxed surfaces are under a greater pressure load (for example, 100 psi)
and which may serve to simulate a condition where a large tightly wound roll of
waxed paper is stored in a warm warehouse is also available.
Gloss-Waxed coatings not only provide protection for packaged goods, but
they also provide an attractive appearance because of their high-gloss character-
istics. The amount of gloss obtained is determined primarily by the nature of the
wax and coating and the smoothness of the substrate. Storage of coated paper at
elevated temperature tends to be injurious to gloss. Measurement of gloss
properties and gloss retention are described in later paragraphs.
Slip Properties-Friction tests provide an indication of the resistance to sliding
exhibited by two waxed surfaces in contact with one another. The intended
application determines the degree of slip that is desired. Coatings for packages
that require stacking should have a high coefficient of friction to prevent
slippage in the stacks. Folding box coatings should have a low coefficient of
friction to allow the boxes to slide easily from a stack of blanks being fed to the
forming and filling equipment.
Abrasion Resistance-The attractive appearance of a clear, glossy wax coating
is an important functional feature in many packaging applications such as the
multicolored food wraps, folding cartons, and decorated, corrugated cartons.
However, the surface appearance may be vulnerable to damage if its handling in
manufacture or use subjects it to any severe abrading action. A standard

procedure has been set up to evaluate the abrasion resistance of a wax coating
under impact of a stream of sand and using gloss change as the criterion for
evaluating abrasion.
Adhesion-The thermoplastic properties of wax are used to good effect in the
heat sealing of waxed paper packages. The strength of the seal is a function not
only of the physical properties but also of the chemical properties and
composition of the wax.
In some applications, such as for bread wraps, candy wraps, cereal, and cookie
inner bags, it is desirable to have only a moderately strong seal that can be
parted easily when the package is opened without any tearing action of the
paper itself. For these uses, predominantly paraffinic wax blends are used, and
seal testing shows a cohesive failure of the wax. In other applications, such as for
various heat-sealed folding cartons, frozen food cartons, and flexible packaging
bags, extremely strong and durable seals may be desired. In these cases, the wax
formulation contains a major proportion of tacky, adhesive, and high-tensile
components such as the resins and polymers compounded in hot melts. During
seal testing the wax cohesive and adhesive strength may be so great that the
failure occurs in the paper substrate rather than in the wax.
Moisture Barrier Properties-The ability of wax to prevent the transfer of
moisture vapor is a primary concern to the food packaging industry. Moisture
must be kept out to maintain the freshness of dry foods, and moisture must be
kept in to maintain the quality of frozen foods and baked goods. Both require
different procedures for measuring barrier properties. For example, for dry food
packaging, transmission rate is measured at elevated temperatures and high-
relative humidity, and, for frozen food, the transmission rate is measured at low
temperatures and low-relative humidity.
To have good barrier properties, a wax must be applied in a smooth,
continuous film and be somewhat flexible to prevent cracking and peeling.
Testing in the "flat" condition provides an assessment of the fundamental
barrier capability of the wax coating; for example, the resistance of the
microstructure to passage of water vapor. Testing in the "creased" condition
gives an evaluation of the strength of the thin wax fdm in maintaining its
integrity even when folded to a sharp crease through 180 deg and reflattened for
test. A strong, flexible, adherent Film will survive the creasing with minimal
damage, while inferior coatings will lose integrity, crack, or flake off at the
crease.

Test Methods

Quality criteria for wax are a product of the type wax and its intended
application. Three categories of tests-physical, chemical, and functional-are
used to assess the quality of waxes. The following paragraphs describe the most
common tests applied to waxes and petrolatums.

Physical Properties of Petroleum Wax

ASTM Test for Melting Point of Petroleum Wax (Cooling Curve} (19 87/IP
55)-In this procedure, a sample of molten paraffin wax in a test tube, with a
thermometer, is placed in an air bath which is inserted into a room temperature
water bath. As the wax cools, wax temperature versus time is recorded and
plotted. Since the latent heat of crystallization released during solidification of
the wax is sufficient to temporarily arrest the rate of cooling, a plateau occurs in
the time/temperature curve. The temperature at which the plateau occurs is the
melting point. This procedure is not suitable for microcrystalline wax,
petrolatums, or waxes containing large amounts of nonnormal hydrocarbons
because the plateau rarely occurs in cooling curves of such waxes.
ASTM Test for Drop Melting Point of Petroleum Wax, Including Petrolatum
(1) 127flP 133)-This method can be used for most petroleum waxes and
wax-based hot-melt blends. A chilled thermometer bulb is coated with the
molten wax (which is allowed to solidify), placed in a test tube, and heated at a
specified rate in a water bath. The melting point is the temperature at which the
first drop of liquid falls from the thermometer.
ASTM Test for Congealing Point of Petroleum Wax, Including Petrolatum (19
938/IP 76)-This procedure can be used for almost all types of petroleum waxes
and hot-melt blends. A thermometer bulb is dipped in the melted wax and
placed in a heated flask, serving as a jacket. The thermometer is held
horizontally and slowly rotated on its axis. As long as the wax remains liquid, it
will hang from the bulb as a pendant drop. The temperature at which the drop
rotates with the thermometer is the congealing point. The congealing point of a
microcrystalline wax or petrolatum is invariably lower than its drop melting
point.
ASTM Test for Kinematic Viscosity of Transparent and Opaque Liquids (and
the Calculation of Dynamic Viscosity) (D 445/IP 71)-Kinematic viscosity is
measured by timing the flow of a fixed volume of material through a calibrated
capillary at a selected temperature. The unit of kinematic viscosity is the stoke,
and kinematic viscosities of waxes are usually reported in centistokes.
Centistokes can be converted to Saybolt Universal seconds by using ASTM
Conversion of Kinematic Viscosity to Saybolt Universal Viscosity or to Saybolt
Furol Viscosity (D 2161).
ASTM Test for Apparent Viscosity of Petroleum lCaxes with Additives (Hot
Melts) (D 2669)-This method is suitable for blends of wax and additives having
apparent viscosities up to 20 000 cP at 350"F. Apparent viscosity is the
measurement of drag produced on a rotating spindle immersed in the test liquid.
A suitable viscometer is equipped to use interchangeable spindles and adjustable
rates of rotation. The wax blend is brought to test temperature in a simple
arrangement using an 800-ml beaker in a heating mantle. Viscosities over a range
of temperatures may be recorded and plotted on semilog paper to determine the
apparent viscosity at any temperature in the particular region of interest.

ASTM Test for Apparent Viscosity of Hot Melt Adhesives and Coating
Materials (D 3236)-This procedure is similar to ASTM D 2669 since it measures
the ratio of shear stress to shear rate through the use of a rotating spindle.
However, ASTM D 3236 is applicable to hot melts of a broader range of
viscosity. Through the use of a special thermally controlled sample chamber, hot
melts may be tested at temperatures of 3500F or more and at viscosities of
200 000 cP or more.
ASTM Test for Needle Penetration of Petroleum Waxes (D 1321)-The
hardness or consistency of wax is measured with a penetrometer applying a load
of 100 g for 5 s to a standard needle having a truncated cone tip. To prepare a
wax for testing, the sample is heated to 30~ above its congealing point, poured
into a small brass cylinde r, cooled, and placed in a water bath at the test
temperature for 1 h. The sample is then positioned under the penetrometer
needle which when released penetrates into the sample. The depth of
penetration in tenths of a millimeter is reported as the test value. This method is
not applicable to oily materials or petrolatums which have penetrations greater
than 250.
ASTM Test for Cone Penetration of Petrolatums {D 937/IP 179)-The Cone
Penetration test is used for soft waxes and petrolatums. It is similar to D 1321
except that a much larger sample mold is used and a cone weighing 102.5 g
replaces the needle. The method requires that a 150 g load be applied for 5 s at
the desired temperature.
ASTM Test for Tensile Strength of Paraffin Wax (D 1320J-This test is an
empirical evaluation of the tensile strength of waxes which do not elongate more
than 1/8 in. under the test conditions. Six dumbbell-shaped specimens, each
with a cross sectional area of 1/4 in. 2 at the neck of the dumbbell, are cast. The
specimens are broken on a testing machine under a load which increases at the
rate of 20 lb/s along the longitudinal axis of the sample. Values are reported as
pounds per square inch.
ASTM Test for Modulus of Rupture of Petroleum Wax (D 2004)-A wax slab,
8 by 4 by 0.15 in. is cast over hot water. Small strips, about 3 by 1/2 in. are cut
from the center of the slab. The strips are placed lengthwise on the support
beams of the apparatus, and a breaking beam is placed across the specimen
parallel to the support beams. A steadily increasing load is applied by water
delivered to a bucket suspended from the breaking beam. The modulus of
rupture (breaking force in pounds per square inch) is calculated from an
equation relating thickness and width of a test specimen with total weight
required to break it.

Chemical Properties of Petroleum Wax

ASTM Test for Saybolt Color of Petroleum Products (Saybolt Chromometer
Method) (D 156)-Saybolt color is determined on nearly colorless waxes by
putting the melted sample in a heated vertical tube mounted alongside a second
tube containing standard color discs. An optical viewer allows simultaneous

viewing of both tubes. Light is reflected by a mirror up into the tubes and to the
viewer. The level of the sample in the column is decreased until its color is
lighter than that of the standard. The color number above this level is reported.
ASTM Color of Petroleum Products (ASTM Color Scale} (D 1500/IP
196)-This procedure is used for waxes and petrolatums which are too dark for
the Saybolt colorimeter. Using a standard light source, a liquid sample is placed
in the test container and compared with colored glass discs ranging in value from
0.5 to 8.0. If an exact match is not found and the sample color fails between
two standard colors, the higher of the two colors is reported.
ASTM Test for Odor of Petroleum Wax (D 1833/IP 185)-The odor of
petroleum wax is determined by a preselected panel. Ten grams of wax are
shaved and placed in an odor-free glass bottle and capped. After 15 min, the
sample is evaluated in an odor-free room by removing the cap and sniffing
lightly. A rating of 0 (no odor) to 4 (very strong odor) is given by each member
of the panel. The reported value is the average of the individual ratings.
ASTM Test for Oil Content of Petroleum Waxes (D 721/IP 158)-The fact that
oil is much more soluble than wax in methyl ethyl ketone at low temperatures is
utilized in this procedure. A weighed sample of wax is dissolved in warm methyl
ethyl ketone in a test tube and chilled to -25~ to precipitate the wax. The
solvent-oil solution is separated from the wax by pressure filtration through a
sintered glass filter stick. The solvent is evaporated, and the oil residue is
weighed. The method is applicable to waxes containing not more than 15
percent oil.
ASTM Test for Solvent Extractables in Petroleum Wax {D 3235J-This method
is very similar to ASTM D 721/IP 158 except that the solvent used is a 1:1
mixture of methyl ethyl ketone and toluene. The method may be used on waxes
having high levels of extractables, for example, 15 to 50 percent extractables.
ASTM Test for Distillation of Petroleum Products at Reduced Pressure (19
1160)-In this standard test the sample is distiUed at an accurately controlled,
reduced pressure (usually 10 mm or 1 mm) in a distillation flask and column
which provides approximately one theoretical plate fractionation. The apparatus
includes a condenser and a receiver for collection and measurement of the
volume of cuts obtained. The data are reported as the series of vapor
temperatures observed (at the reduced pressure) for the specified intervals of
volumetric percentage distilled.
ASTM Test for Boiling Range Distribution of Petroleum Fractions by Gas
Chromatography (D 2887)-A sample of the test wax is dissolved in xylene and
introduced into a gas chromatographic column which is programmed to separate
the hydrocarbons in boiling point order by raising the temperature of the
column at a reproducible, calibrated rate. When wax samples are used, the
thermal conductivity detector is used to measure the amount of eluted fraction.
Data obtained in this procedure are reported in terms of percent recovered at
certain fixed temperature intervals. A full description of the carbon number
distribution cannot be obtained with this method because the relatively short

column used does not provide sufficient resolution to distinguish individual

peaks. In addition, the method is not applicable to higher chain length paraffin
waxes or to microcrystalline waxes.
ASTM Test for Molecular Weight of Hydrocarbons by Thermoelectric
Measurement of Vapor Pressures (D 2503)-In this method, a small sample of
wax is dissolved in a suitable solvent, and a droplet of the wax solution is placed
on a thermistor in a closed chamber in close proximity to a suspended drop of
the pure solvent on a second thermistor. -The difference in vapor pressure
between the two positions results in solvent transport and condensation onto the
wax solution with a resultant change in temperature. Through suitable
calibration, the observed effect can be expressed in terms of molecular weight of
the wax specimen as a number average (l~n).
Regulatory Test for Food Grade Petroleum Wax: 21 Code of Federal
Regulations 121.1156 and U.K. Mineral Hydrocarbons in Food Regulations
1966 ($1 1966 No. 1073)-The polynuclear aromatic content of waxes can be
estimated by the ultraviolet absorbance of an extract of the sample when
scanned in the 280 to 400 nm range. The sample is first dissolved in isooctane
and extracted using a dimethylsulfoxide-phosphoric acid solution to concentrate
the aromatic material and remove it from the saturated hydrocarbons. The
extract portion is tested for ultraviolet absorbance against specified maximum
limits. These limits were established as being indicative of the maximum
absorption peak areas associated with polynuclear aromatic hydrocarbons. If the
wax sample under test falls within these limits, the sample is considered to pass,
and no further continuation of the analysis is necessary.
If, however, the results in this first phase of testing exceed any of the limits,
there is a possibility that the high result may be an interference due to single ring
aromatic derivatives (these are highly absorptive, especially at lower wavelengths
and would normally occur along with the polynuclear aromatics). The benzenoid
structures are considered noncarcinogenic, and their interference in the test must
be eliminated. This is done by continuing the sample extract into a second phase
of analysis using a chromatographic separation procedure. The resulting
concentrate of polynuclear aromatics is tested against the same specified limits
for ultraviolet absorbance.
ASTM Test for Ultraviolet Absorbance and Absorptivity of Petroleum
Products (D 2008)-ASTM D 2008 is a standard method for testing a variety of
petroleum products of liquid or solid form. The procedure tests the product as a
whole, without including any separation or fractionation steps to concentrate
the absorptive fractions. When wax or petrolatum are tested in this procedure,
the specimen is dissolved in isooctane, and the ultraviolet absorbance is
measured at a specified wavelength such as 290 nm. The absorptivity is then
calculated. This procedure, as such, is not a part of the federal specification.
ASTM Test for Carbonizable Substances in Paraffin Wax (D 612)-Five
miUilitres of concentrated sulfuric acid are placed in a graduated test tube, and 5
ml of the melted wax are added. The sample is heated for 10 min at 158~

During the last 5 min, the tube is shaken periodically. The color of the acid layer
is compared with the color of a standard reference solution. The wax sample
passes if the color is not darker than the standard.
ASTM Test for Peroxide Number of Petroleum Wax (1) 1832)-In this test, a
sample is dissolved in carbon tetrachloride, acidified with acetic acid, and a
solution of potassium iodide is added. Any peroxides present will react with the
potassium iodide to liberate iodine which is then titrated with sodium
thiosulphate.

FunctionaI Properties of Petroleum Wax

In the manufacture of wax-treated paper packaging, a variety of substrates are
treated, and a variety of waxing methods and equipment are used. In some cases,
commercial specimens of waxed packaging materials may be submitted to
functional tests. Such testing serves to evaluate the total system, that is, the wax,
paper, and coating condition.
When it is desired, to test the functional property of the wax itself, or to
compare it with other waxes apart from the variables of substrate and waxing
process, a standard waxed specimen must be prepared under predetermined and
controlled conditions. Several of the functional test methods include instruc-
tions for specimen waxing which usually employ a standard paper substrate and
standard coating conditions.
ASTM Test for Weight of Surface Wax on Waxed Paper (D 2423)-This
method determines the amount of wax present as a surface film on a substrate
but not the absorbed wax. A waxed paper sample is cut to size and weighed; wax
is carefully scraped from one surface with a razor blade, then the sample is
reweighed to determine the amount of wax removed. The process is repeated on
the reverse side if total surface wax is desired.
ASTM Test for Total Wax Loading of Corrugated Paperboard (D 3344)-In
this method, taking together all wax that may be present as impregnating or
saturating or coating wax, the total wax loading of corrugated board is
measured. The determination is made by extracting the waxed board specimen
with warm solvent (1,1,1 trichlorethane) and evaporating to dryness to obtain
extracted wax. The resulting residue will include any soluble additive materials
associated with the wax, such as the polymeric additives normally used in the
wax-based hot-melt coatings.
ASTM Test for Blocla'ng Point of Petroleum Wax (D 1465)-Two strips of wax
coated paper, 1-in. wide, are placed face to face between two uncoated strips of
paper on a calibrated temperature-gradient heating plate. The specimens are
covered with foam rubber strips and steel bars to provide a moderate pressure
loading and then subjected to the gradient heat of the blocking plate for 17 h.
The specimens are removed, cooled, and peeled apart. The picking point is the
lowest temperature at which the surface film shows disruption. The blocking
point is the lowest temperature causing disruption of surface film over an area of
50 percent of the strip width.

ASTM Test for Pressure Blocking Point of Petroleum Wax and Wax Blends (D
2618)-This test is essentially the same as ASTM D 1465 except the specimen is
subjected to pressures of 20 to I00 psi (138 to 689 kN/m 2).
ASTM Test for 20-Deg Specular Gloss of Waxed Paper (1) 1834)-Specular
gloss is the capacity of a surface to simulate a mirror in its ability to reflect an
incident light beam. The glossimeter used to measure gloss consists of a lamp and
lens set to focus an incident light beam 20 deg from perpendicular to the
specimen. A receptor lens and photocell are centered on the angle of reflectance,
also at 20 deg from the perpendicular. A black, polished glass surface is used for
instrument standardization at 100 gloss units. The wax coated paper specimen is
held by a vacuum plate over the sample opening. The light beam is reflected
from the sample surface into the photocell, the gloss being reported on a
percentage basis.
ASTM Test for Gloss Retention of Waxed Paper and Paperboard after Storage
at 104~ (40~ (D 2895)-The gloss is measured by ASTM Method D 1834
before and after aging the sample for 1 and 7 days in an oven at 104~ (40*(2).
Gloss retention is the percent of original gloss retained by the specimen after
aging under specified conditions. The aging conditions are intended to correlate
with the conditions likely to occur in the handling and storage of waxed paper
and paperboard.
ASTM Test for Coefficient of Kinetic Friction for Wax Coatings (D 2534)-A
wax coated paper is fastened to a horizontal plate attached to the lower,
movable cross arm of an electronic load-cell-type tension tester. A second paper
is taped to a 180-g sled which is placed on the first sample. The sled is attached
to the load cell through a pulley. The kinetic coefficient of friction is calculated
from the average force required to move the sled at 35 in./min divided by the
sled weight.
ASTM Test for Abrasion Resistance of Wax Coatings (D 3234)-The abrasion
resistance of a smooth wax coating on paper or paperboard is measured by
determining how much change in gloss of the surface occurs under the abrading
action of sand particles. A measured quantity of sand is allowed to impinge
under specified conditions on the waxed surface, and the change in gloss is noted
using ASTM Method D 1834.
ASTM Test for Sealing Strength of Petroleum Wax (ASTM D 2005)-Two
wax-coated paper specimens, 5 by 10 in. are cut and sealed together by passing
them over a heated bar. The sealed papers are conditioned at 73~ and 50
percent relative humidity for 17 to 24 h. Test specimens 10 by 15 cm are cut
from the sealed paper and then delaminated using a power driven testing
machine at the rate of 5 in./min. During testing, the open ends of the seal being
delaminated are in the same plane with a 180-deg angle between the ends. The
unseparated portion is perpendicular to this plane. Sealing strength is the force
measured in grams/centimetre required to separate the sealed strips.
Water Vapor Permeability of Paper and Paperboard (TAPPI T 448)-The
method is used for determining the water vapor permeability of wax treated

Wax grade 127/129 156/158 150 175 USP

AMP paraffin AMP paraff'm micxocrystalline mictocrystalline petrolatum C)
Appearance translucent translucent opaque yellow solid white I
white solid white solid white solid semi-solid "u
Gravity, ~ calculated 43.4 38.7 36.8 34.5 32.4
Melting point, ASTM D 87/IP 55, OF 125.2 154.0 . . . . . .
m
Melting point, ASTM D 127/IP 133, OF 128 156 149 176 125" "
Congealing point, ASTM D 938/IP 76, OF 125 152 145 166 117
Penetration, ASTM D 1321 o
Z
77OF, 100 g, 5 s 14 15 29 17
Penetration, ASTM D 937/IP 179 m
77OF, 150 g, 5 s . . . . . . . 155 -4
Color, Saybolt, ASTM D 156 30+' ' 30+" 14 8 0
Color, ASTM D 1500/IP 196 ... L i.0" L 1.0 r-
10.53 m
Viscosity, ASTM D 445/IP 71; cSt at 210OF 3.18 7136 10156 16.64 C
Refractive index, ASTM D 1747 1.432 1.444 1.450 1.456 1.45
Odor, ASTM D 1833/IP 185 1.0 1.0 1.5 2.0 1.5
Caxbonizable substance, ASTM D 612 pass pass
Off content, ASTM D 721/IP 158 weight, % 0.2 {)ii 21'~ bli 50a X
m
Specular gloss, ASTM D 1834 35 39 44 38
Blocking point, ASTM D 1465, ~ 95 117 120 127
Water vapor permeability, TAPPI 464
Grams water/24 h/m 2 4.2 P
C
Flat, 25 g/ft2 deposition 6.S 8.{3 ...
Creased, 3 g/ft 2 deposition 9.7 36 ... 12 ,,~
Z
Seating strength, ASTM D 2005, g/cm
(2.5 g/ft 2 deposition) 15 7 16 16
Coefficient of friction, ASTM D 2534 0.26 1.0 0.92 0.64 .,~ m
.-I
Tensile strength, ASTM D 1320, psi 290 360 385 385 -11
Chemical analysis: volume, % o
r
Alkanes 95 55 47 42
Noncondensed cycloalkanes 5 40 45 48 .-I
Condensed cycloalkanes ... 3 6 8 C
Benzenes ... 2 2 1
Naphthalenes ... .. .. . . . . . 1 .~

aMethyl isobutylketone used in place of methyl ethyl ketone for determination of oil content. O~

substrates at normal atmospheric conditions: namely, 73~ and 50 percent

relative humidity. A dessicant is placed in a shallow test dish, and the specimens
of wax coated paper are sealed to the shoulder of the dish above the dessicant to
completely seal the dessicant in the dish. The assembly is weighed at the start
and placed in the controlled testing room or cabinet at the conditions required.
The dish assembly is reweighed at periodic intervals such as 24, 48, or 72 h
intervals until successive weighings show that a constant rate of gain has been
attained. The water vapor transmission rate 0/r is reported as the grams of
water transmitted per square metre of test specimen per 24 h. The report
includes notation as to whether the specimen was flat or creased before testing.
Water Vapor Permeability of Sheet Materials at High Temperature and
Humidity (TAPPI T 464)-This method is similar to the T 464 method
previously described, but evaluates the barrier properties of a waxed substrate
under more severe conditions; namely, in an environment of 100~ and 90
percent relative humidity.

Inspections of Typical Petroleum Waxes

Table 1 lists a number of inspection data on examples of petroleum waxes.
These data are simply illustrative and presented for general information only.
They are not to be regarded as specifications or limiting guidelines. Data for
other wax samples of the same nominal grades may differ significantly from
those quoted in Table 1.

Applicable ASTM/IP Standards

ASTM IP Title

D 87 55 Melting Point of Petroleum Wax (Cooling Curve)

D 127 133 Drop Melting Point of Petroleum Wax,
Including Petrolatum
D 156 Saybolt Color of Petroleum Products
(Saybolt Chromometer Method)
D 445 71 Kinematic Viscosity of Transparent and
Opaque Liquids (and the Calculation of
Dynamic Viscosity)
D 612 Carbonizable Substances in Paraffin Wax
D 721 158 Oil Content of Petroleum Waxes
D 937 179 Cone Penetration of Petrolatum
D 938 76 Congealing Point of Petroleum Waxes,
Including Petrolatum
D 1160 Distillation of Petroleum Products at
Reduced Pressure
D 1320 Tensile Strength of Paraffin Wax
D 1321 Needle Penetration of Petroleum Waxes
Copyright by ASTM Int'l (all rights reserved); Tue Dec 29 16:07:05 EST 2015
Downloaded/printed by
University of Washington (University of Washington) pursuant to License Agreement. No further reproductions authorized.
CHAPTER 10 ON PETROLEUM WAXES, INCLUDING PETROLATUMS 197

D 1465 Blocking Point of Petroleum Wax

D 1500 196 ASTM Color of Petroleum Products
(ASTM Color Scale)
D 1832 Peroxide Number of Petroleum Wax
D 1833 185 Odor of Petroleum Wax
D 1834 20-Degree Specular Gloss of Waxed Paper
D 2004 Modulus of Rupture of Petroleum Wax
D 2005 Sealing Strength of Petroleum Wax
D 2008 Ultraviolet Absorbance and Absorptivity of
Petroleum Products
D 2423 Weight of Surface Wax on Waxed Paper
D 2534 Coefficient of Kinetic Friction for Wax Coatings
D 2618 Pressure Blocking Point of Petroleum Wax and
Wax Blends
D 2669 Apparent Viscosity of Petroleum Waxes
Compounded with Additives (Hot Melts)
D 2887 Boiling Range Distribution of Petroleum
Fractions by Gas Chromatography
D 2895 Gloss Retention of Waxed Paper and Paperboard
After Storage at 104*F (40"C)
D 3234 Abrasion Resistance of Wax Coatings
D 3235 Solvent Extractables in Petroleum Waxes
D 3236 Apparent Viscosity of Hot Melt Adhesives and
Coating Materials
D 3344 Total Wax Loading of Corrugated Paperboard

Bibliegraphy
Bennet, H., Industrial Waxes, Vol. I & II, ChemicalPublishingCompany,Inc., New York,
1963.
Petroleum Waxes: Characterization, Performance, and Additives, TechnicalAssociation of
the Pulp and Paper Industry, SpecialTechnicalAssociationPublicationNo. 2, 1963.
Technical Evaluation of Petroleum Waxes, Technical Association of Pulp and Paper
Industry, SpecialTechnicalAssociationPublication No. 6, 1969.
Warth, A. H., Chemistry and Technology of Waxes, ReinholdPublishingCorp., New York,
1956.

Chapter 11 White Mineral Oils

Introduction
"Russian Oil," originally made from the straw colored crude oil produced in
the Surakhany district of Russia and first introduced abroad in 1913 for its
therapeutic value in the treatment of constipation, was the grandfather of the
white oils of today. Within the subsequent time span, many new processes and
process improvements have been made to produce these unique and valuable
petroleum products. At the same time, there has been an increasing demand by
both government and industry for more stringent purity requirements and
special properties for use in new applications.
Usage has expanded and, with it, the scope of products that may be classified
as white mineral oils. In the context employed in this chapter, white mineral oils
are considered to be those petroleum fractions, from kerosine to viscous
lubricating oil, that have been drastically treated to remove all reactable
hydrocarbons to give pure, colorless, odorless, and nonreactable petroleum
products. It is the combination of these four properties, unique to these refined
natural petroleum fractions, that has expanded the applications of white oils
from a simple medicinal to their widespread use in such diverse fields as
cosmetics, pharmaceuticals, plastics, agricultural and animal sprays, food
processing and protection, animal feed~ refrigeration and electrical equipment,
chemical reagent and reaction media, and precision instrument lubricants.

Manufacture
White oils are made from selected petroleum fractions distilled to provide
finished products with the viscosity desired by the white oil refiner. For
example, a manufacturer may have in his base white oil line, oils with viscosities
of 32, 40, 50, 70, 100, and 370 SUS (all at IO0~ From these base oils, he is
able to blend and supply white oils covering the viscosity range 32 to 370 SUS.
In addition to viscosity, properties considered during feedstock selection include
pour point, cloud point, distillation range, smoke point, specific gravity, etc.
Typically, a white oil feedstock is distilled to specification from the required
crude oil cuts, pretreated by solvent extraction or hydrotreating, and dewaxed if
necessary. The order of the feedstock preparation is dependent on the refiner's
operations. The type pretreatment used is determined by the nature of the white
off manufacturer's process and the type base white oils that best fit his market.
With the advent of hydrotreating, white oils can be produced without acid
treatment. However, in traditional manufacture, white oils are made by
exhaustively treating the selected feedstock with 20 percent fuming sulfuric acid

198
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CHAPTER 11 ON WHITE MINERAL OILS 199

to remove the aromatic, unsaturated hydrocarbons and other impurities present

in the natural petroleum oil. Gaseous sulfur trioxide treatment also may be used
to remove reactable hydrocarbons. Petroleum sulfuric acids, produced as
by-products during acid treatment, are removed by extraction and neutraliza-
tion. The oil is then further refined to its ultimate degree of purity by
adsorption.

Purity Guardianship
Since white oil was introduced initially as a medicine.it followed logically that
national pharmacopoeias assumed responsibility for establishing quality and
purity criteria for white oils. In the United States, this responsibility was taken
by the U.S. Pharmacopoeia, whose legal status is based on the adoption of its
definitions and standards in the Food, Drug, and Cosmetic Act, and by the
National Formulary which is published by the American Pharmaceutical
Association. In the United Kingdom, the British Pharmacopoeia became
responsible for establishing, maintaining, and strengthening the rigid standards
for white mineral oil purity. The requirements of the two pharmacopoeias are
substantially the same. The prime objective of specifications for pharmaceutical
oils is to ensure the product is as inert as possible and free of toxic materials.
Differences in the key specifications for white oils among the two pharmaco-
poeias and the National Formulary are shown in Table 1.
The U.S. Pharmacopoeia specification includes an ultraviolet light absorbance
test as a requirement for mineral oil which is essentially the same as ASTM
Evaluation of White Mineral Oils by Ultraviolet Absorption (D 2269). The
procedure measures the absorbance of a dimethyl sulfoxide extract.
Since, during manufacture, natural inhibitors in petroleum oils are removed,
the resultant white oils are not stable to oxidation. Both the U.S. Pharmacopoeia
and the National Formulary permit the addition of a suitable stabilizer. The
British Pharmacopoeia permits the addition of tocopherol or butylated
hydroxytoluene in a proportion not greater than 10 ppm.
Besides pharmaceutical uses, the nonreactivity of a white oil makes it suitable:
(1) as a carrier for alkali dispersions for use in organic chemical reactions; (2) in
textile and precision instrument lubricants where nongumming is desired; (3) as
a tobacco desuckering oil; and (4) in many human, plant, and animal
preparations where nontoxicity and freedom from irritation are desired. Each of
these uses may require unique qualities.

Assessment of Quality
Many test methods are available to determine whether the quality for white
oils exists as prescribed by the pharmacopoeias, the National Formulary, and
other consumers. The following paragraphs will outline the significance of the
most important of thest tests.

Mineral Oil Light Mineral Oil Liquid Paraffin

Z
USP XVIII 1970 NF XIII 1970 BP 1968

]>
Description colorless, transparent, oily, nearly free from fluorescence: odorless and transparent, colorless, oily liquid z
tasteless when cold: faint odor on heating free from fluorescence in day- m
light: almost odorless and 0
tasteless "11

m
Specific gravity, 25~ 0.845 to 0.905 0.818 to 0.880 0.868 to 0.888 a tJ)

Viscosity, cSt at 37.8~ 38.1 min 37 max 64 min

Solid paraffins A maximum opalescence at 0~

Acidity/alkalinity Nil

Sulfur compounds negative to sodium plumbite test

Carbonizable substances maximum color of acid layer stipulated

Polynuclear compound
limit 1%

E 1 cm 240 to 280 nm 0.08 max

Absorbance
260 to 350 nm b 0.1 max

aSpecified as density 20~ 0.870 to 0.890.

bOn dimethyl sulfoxide extract.

Acid Test (Readily Carbonizable Substances)

The acid test, ASTM Test for Carbonizable Substances in White Mineral Oil
(Liquid Petrolatum) (D 565), is a measure of the purity of a white oil and its
freedom from aromatic, unsaturated, and other materials reactable with sulfuric
acid.
In the test, equal portions of oil and 94.7 +- 0.2 percent sulfuric acid are
shaken in a prescribed manner at 212~ for 10 min, and the color of the acid
layer is compared with that of a standard color solution. The more fully refined
the oil, the lighter the color of the acid layer.
Most white oils manufacturers, for their own information, protection, and
process control, have gone beyond this pharmacopoeia requirement and
developed rating systems to measure the degree of color of the acid layer and
thus assure the highest levels of oil purity.

Aniline Point
The ASTM Test for Aniline Point and Mixed Aniline Point of Petroleum
Products and Hydrocarbon Solvents (D 611/IP 2) provides a measure of the
aromaticity and naphthenicity of an oil. In the test, equal volumes of aniline and
oil are mixed and heated until a miscible mixture is formed. On cooling at a
prescribed rate, the temperature at which the mixture becomes cloudy is
recorded and identified as the aniline point. While not typically applicable to
pharmaceutical grade white oils, it is employed in technical oil specifications as a
measure of degree of refinement and type base oil stock. For any particular oil
fraction, a higher degree of refinement is reflected by an increase in aniline
point. Aniline point also increases with the average molecular weight of the oil as
well as with increasing proportions of paraffinic hydrocarbons to naphthenic
hydrocarbons. Aniline point specifications also can be used to advantage for
light technical grade white oils used in agricultural sprays where the presence of
aromatic hydrocarbons might cause foliage damage.

Cloud Point
ASTM Test for Cloud Point of Petroleum Oils (D 2500/IP 219) provides the
temperature at which wax appears in an oil. This information is significant for
oils to be used at low temperatures where precipitation of wax might affect the
performance of the oil. Examples include refrigerator and hydraulic oils.
The cloud point test is considered to be more meaningful than the "Solid
Paraffins" test called for by the pharmacopoeias which determines whether or
not wax precipitates out at 32~

Color and Transparency

By definition, a pharmaceutical grade white oil must be colorless and
transparent. On the Saybolt scale, water has a value of +25 while typical white

otis have color ratings of +30. In other words, pharmaceutical grade white oils
have less color than water.
Freedom from color and transparency are the unique properties of white oils
that make them useful in their many cosmetic, pharmaceutical, agricultural,
food, and industrial applications. Among the latter are textiles, plastics,
precision instruments, leather, household specialties, and printing ink.
White oil color is determined by means of ASTM Test for Saybolt Color of
Petroleum Products (Saybolt Chromometer Method) (D 156). In this instru-
ment, the height of a column of the oil is decreased by levels corresponding to
color numbers until the color of the sample is clearly lighter than that of the
standard. The color number immediately above this level is recorded as the
Saybolt color of the oil.

Dielectric Breakdown Voltage

Dielectric breakdown voltage is the measure of the ability of an oil to
withstand electrical stress. White oils used in the electrical or electronics
industries as a coolant, insulating fluid, lubricant, or cleaner must have a
high-dielectric strength. Dielectric breakdown voltage "is determined by ASTM
Test for Dielectric Breakdown Voltage of Insulating Liquids Using Disk
Electrodes (D 877).

Distillation Range
The distillation range for very white light oils provides information on
volatility, evaporation rates, and residue remaining after evaporation. Such data
is' important for agricultural and household sprays, agricultural product
processing, and printing inks. The baking and plastic industries often include
initial boiling point temperature or the minimum allowable temperature at
which the first several percent of the oil comes overhead during distillation or
both as part of their specifications for white oils.
The distillation range on low-viscosity grades of mineral oils is determined by
ASTM Test for Distillation of Petroleum Products (D 86/IP 123). Distillation
range for higher boiling grades is measured by ASTM Test for Distillation of
Petroleum Products at a Reduced Pressure (D 1160).

Flash and Fire Point

Flash and fire points of white oils are a measure of their fire hazard. High-flash
and fire points are particularly important in many industrial applications where
the oils are used at high temperatures.
Flash and fire points are determined by ASTM Test for Flash Point
by Pensky-Martens Closed Tester (D 93/IP 34) or by ASTM Test for Flash and
Fire Points by Cleveland Open Cup Tester (D 92/IP 36). The Cleveland open cup
method is also used to determine fire point.
Both methods measure flash point at the minimum temperature to which the

oil must be heated to provide a sufficient amount of vapor to ignite. Since the
Pensky-Martens tester is a closed system, flash point values are lower with it than
those determined by the Cleveland method.
The fire point is the temperature at which the oil ignites and burns for 5 s.

Fluorescence
Both pharmacopoeias have statements on fluorescence. The U.S. Pharmaco-
poeia describes a white oil as free or nearly free from fluorescence, while the
British Pharmacopoeia states that the oil shall be free from fluorescence by
daylight. Fluorescence is a measure of purity and indicates the presence of
aromatic hydrocarbons.
Examination of a sample bottle of oil under ultraviolet light is an even more
sensitive test which many manufacturers employ as a rapid means of detecting
incompleteness of refining or the presence of petroleum contamination. While it
is possible to obtain fluorescent oils that are free of polynuclear aromatic
compounds, oils that do not fluoresce are virtually certain to be free of such
compounds.

Neutrality
In the U.S. Pharmacopoeia, the test for neutrality is 10 ml of oil boiled with
10 ml of ethyl alcohol, and the alcohol is tested by litmus paper. The British
Pharmacopoeia employs 20 ml of alcohol.
This is an extremely sensitive test in that the presence of as little as 0.01 mg
potassium hydroxide/g is sufficient to turn red litmus paper blue. The test is
largely a relic of earlier times when it was thought that detectable amounts of
chemicals used in processing could remain in the finished product.

Odor and Taste

The absence of odor and taste when cold and the development of not more
than a faint odor of petroleum when heated is specified by the U.S.
Pharmacopoeia. The British Pharmacopoeia requires that white oil be almost
odorless and almost tasteless. Both tests are highly subjective, but, with practice,
many inspectors can detect the slightest trace of an off odor or taste.

Peroxide Value
The peroxide value is an accelerated test to measure the oxidation stability of
an oil. Although stability is not an expressed requirement of the pharmaco-
poeias, sufficient stability is needed to ensure adequate shelf life without the
development of rancidity, acidity, or color degradation.
Many consumers of white oils in the pharmaceutical, cosmetic, textile, and
coatings industries prescribe oxidation stability tests in their purchase specifica-
tions. When white oils are used as heating fluid baths or for othe~ uses at

elevated temperatures where medicinal purity is not prescribed, more stabilizer

may be used to increase stability.

Pour Point
Pour point provides a means of determining the type petroleum feedstock
from which the white oil was manufactured or its previous processing history. It
also reflects the presence of wax or paraffinic hydrocarbons. Clearly, in any
application where the white oil is used at low temperatures or the oil is subjected
during handling or storage to low temperatures, the pour point is important and,
in many industrial applications, critical.
In the ASTM Test for Pour Point of Petroleum Oils (D 97/IP 15), the oil is
heated to a specified temperature which is dependent on the anticipated
pour-point range, cooled at a specified rate, and examined at 5~ (3~ intervals
for flow. The lowest temperature at which no movement of the oil is detected is
recorded. The 5~ (3~ temperature value immediately preceding the recorded
temperature is defined as the pour point.

Refractive Index
The refractive index is the ratio of the velocity of light in air to its velocity in
the substance under examination. It is used, together with density and viscosity
measurements, in calculating the paraffin-naphthene ratio in white oils. Because
refractive index is a measure of aromaticity and unsaturation on a given stock,
manufacturers also use it as a means of process control.
Refractive index is measured using ASTM Test for Refractive Index and
Refractive Dispersion of Hydrocarbon Liquids (D 1218).

Smoke Point
Smoke point is of particular interest to industries, such as the baking industry,
whose processes expose or use the oil at extremely high temperatures.
The smoke-point test is conducted in a black box suitably vented and
illuminated to permit detection of white vapors. The oil is carefully heated
under specified conditions until the first consistent appearance of vapors is
detected. The temperature of the oil at that time is recorded as the smoke point.

Gravity, Density and API Gravity

Density, specific gravity, or American Petroleum Institute (API) gravity may
be determined by ASTM Test for Density, Specific Gravity, or API Gravity of
Crude Petroleum and Liquid Petroleum Products by Hydrometer Method (D
1298/IP 160). The terms are defined as follows:
Specific Gravity-The ratio of the mass of a given volume of liquid at 60~ to
the mass of an equal volume of pure water at the same temperature.
Density-The mass (weight in vacuo) of liquid per unit volume at 15~ as
stated for the specified hydrometer.
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CHAPTER 11 ON WHITE MINERAL OILS 205

API gravity is a special function of specific gravity that was arbitrarily

established to permit gravity calculations in whole numbers. It is related to
specific gravity by the following formula:

API gravity, deg = 141.5 - 131.5

sp gr at 60/60~
Density, specific gravity, and API gravity values permit conversion of volumes
at the measured temperature to volumes at the standard petroleum temperatures
of 15~ and 60~ Calculation to weight is possible where compositions are
fomulated on a weight basis. At a given viscosity density, specific gravity and
API gravity provide a means for determining whether a white oil is derived from
a paraffinic or naphthenic stock.

Sulfur Compounds
The total sulfur content of white oils normally is well below 100 ppm
because of the severe refining to which the oil has been subjected. Therefore,
sulfur is not a limiting factor in the specifications of the U.S. Pharmacopoeia or
the U.S. Formulary.
Both the U.S. Pharmacopoeia and the U.S. Formulary carry a sulfur
compounds test which is similar to the ASTM doctor test, although less sensitive.
This test is required by the Food and Drug Administration on all food grade
white mineral oil.

Unsulfonated Residue
ASTM Test for Unsulfonated Residue of Petroleum Plant Spray Oilg (D 483)
provides a crude measure of the reactable hydrocarbons present in an oil. It is
often included in specifications for oils intended for use as foliage sprays where
aromatic and unsaturated hydrocarbons would cause foliage damage. For
high-quality white oils the readily carbonizable substance test is used because it
is a much more sensitive measure for such impurities.

Ultraviolet Absorption Tests

Considerable concern has been generated in recent years over the possible
presence of carcinogenic polynuclear aromatic hydrocarbons in white oils.
Because of this concern much effort has been expended to develop tests to
detect the smallest traces of these carcinogens.
ASTM Test D 2269 measures the absorbance over the wavelength range of
260 to 350 nm in a 10 mm cell of a dimethyl sulfonide extract of the oil. The
polynuclear aromatic hydrocarbons present in the white oils are concentrated.
The Food and Drug Administration has recognized that there is little likelihood
of carcinogenic hydrocarbons being present if the absorbance of the extract in
the wavelength range is no greater than 0.1. This level of absorbance is roughly
equivalent to 5 ppm polynuclear hydrocarbons with a test sensitivity of 0.3
ppm.
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206 SIGNIFICANCE OF TESTS

Wax Precipitation Point

The wax precipitation point test is unique to the refrigerator and freezer
industries where oil is added to the Freon refrigerant to provide lubrication
during the expansion and compression cycles. Just prior to expansion the
refrigerant bearing the oil passes through a length of capillary copper tubing. It is
critical to the process that no wax precipitates and clogs the capillary tubing.

Applicable ASTM/IP Standards

ASTM IP Title

D 86 123 Distillation of Petroleum Products

D 92 36 Flash and Fire Points by Cleveland Open Cup
D 93 34 Flash Point by Pensky-Martens Closed Tester
D 97 15 Pour Point of Petroleum Oils
D 156 Saybolt Color of Petroleum Products
D 287 API Gravity of Crude Petroleum and Petroleum
Products (Hydrometer Method)
D447 Distillation of Plant Spray Oils
D 483 Unsulfonated Residue of Petroleum Plant Spray Oils
D 565 Carbonizable Substances in White Mineral Oil
(Liquid Petrolatum)
D 611 2 Aniline Point and Mixed Aniline Point of
Petroleum Products and Hydrocarbon Solvents
D 877 Dielectric Breakdown Voltage of Insulating Liquids
using Disk Electrodes
D 1160 Distillation of Petroleum Products at
Reduced Pressure
D 1218 Refractive Index and Refractive Dispersion of
Hydrocarbon Liquids
D 1298 160 Density, Specific Gravity, or API Gravity of
Crude Petroleum and Liquid Petroleum Products
by Hydrometer Method
D 2269 Evaluation of White Mineral Oils
by Ultraviolet Absorption
D 2500 219 Cloud Point of Petroleum Oils

Bibliography
British Pharmacopoeia, 1968.
Dunstan, A. E., Nash, A. W., et al, The Science of Petroleum, Vol. IV, Oxford University
Press, London, England, 1938.
Franks, A. J., "New Technology of White Mineral Oils," American Perfumer, Vol. 76, No.
2, 1961.
Meyer, E., White Mineral Oil, Petrolatum and Related Products, Chemical Publishing
Company, New York, 1968.
"Mineral Oil," Congressional Federal Register, 4 Mar. 1966, 31 FR 3394 121. 2589.

"Odorless Light Petroleum Hydrocarbons," Congressional FederalRegister, 21 July 1967,

32 FR 10735 121. 1182.
"Petroleum Wax," Congressional Federal Register, 8 July 1964, 29 FR 9326 121. 1156.
The National Formulary XIII, 1970.
United States Formulary XVIII, 1970.
"White Mineral Oil," Congressional Federal Register, 17 Oct. 1968, 33 FR 15415 121.
1146.

Chapter 12mPetroleum Oils for

Rubber

Introduction

Historical Background
Petroleum products covering a molecular weight range that includes light
solvents, lubricating oils, waxes, and residual materials have been used with
rubber for at least 150 years. Today, these same products are still used, and,
since the advent of synthetic rubber, their use has reached greater proportions
than ever before. This chapter, however, will be limited to petroleum oils.
Why are such products usable when one normally thinks of oils as the enemy
of rubber? The explanation is that the degrading effect of oils on vulcanized
rubber is put to use as a softener for unvulcanized rubber. Rubber, both natural
and synthetic, is elastic in the raw state. It must be broken down by mechanical
means to a more plastic state prior to adding the necessary compounding
ingredients. Oils are added to accelerate the masticating effect which makes the
rubber more workable and pliable. Materials that cause this softening effect are
called softeners. They also are called processing aids or plasticizers, although the
latter term is usually reserved for plastics.
Natural Rubber-In the early days of the rubber industry, natural rubber was
the only rubber polymer used. It is characteristic of natural rubber to break
down fairly easily when milled, and, as a consequence, little softener is required.
While petroleum oils are usable for this purpose, it was found that naval stores
derivatives, such as pine tar, not only aided breakdown but also facilitated the
development of tack in the mixture. Tack is the ability to cohere, and it is a
highly desirable property for certain rubber applications. For this reason, pine
tar became a preferred softener in all natural rubber compounds, and it is used
to some extent today. In current practice, however, natural rubber is used
frequently in blends with synthetic rubber. Because petroleum oils are less
expensive and work well with this combination, they now are used generally for
plasticization.
Synthetic Rubber-The preparation of a synthetic rubber equivalent to natural
rubber has long been a research laboratory goal. This has been particularly true
in countries vulnerable to having their rubber supply shut off in time of war.
With this motivation, both Germany and the United States devoted much effort
to the problem prior to World War II. This culminated in the development of
synthetic rubber in both countries, with some of the German technology
licensed in the United States.
208
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CHAPTER 12 ON PETROLEUM OILS FOR RUBBER 209

Synthetic rubber reached large-scale production during World War II.

Although it was a reasonable substitute, it was not a duplicate for natural
rubber. One place where the lack of similarity between natural and synthetic
rubber showed up was in factory processing. Synthetic rubber proved to be
much more difficult to process. This problem offered a real technical challenge
to the rubber compounder when synthetic rubber was first commercialized.
While many different schemes to overcome this deficiency were tried, the use of
softeners, plus better quality control in the polymer plants, proved to be a
reasonably satisfactory solution.
Early efforts focused on the hunt for the best softener to use with the
butadiene-styrene polymer (SBR) which was chosen for commercialization in
this country. Based on performance, cost, and availability, petroleum oils proved
to be the best of several alternatives.
During the investigations on the use of oils, it was found that more oil was
required for synthetic rubber than for natural rubber. Thus, oils and their
properties became more important to the compounder both from the processing
standpoint and the effect on physical properties of the final rubber product.
From the standpoint of the supplier, the increased demand for rubber oils made
them an important specialty product.
Oil-Extended Rubber-At the close of World War II, the synthetic rubber
plants in production were adequate to supply United States' needs. With the
advent of the Korean War, a shortage was foreseen-particularly since a "guns
and butter" economy existed. An ingenious technical innovation averted any
shortage and resulted in a modified synthetic rubber with properties which were
highly satisfactory for many applications.
This innovation carried the degree of monomer polymerization to a higher
level than was done normally, which was then cut back or extended with
substantial quantities of oil. The cut back was necessary to get the rubber back
to a workable level since the higher degree of polymerization produced a
polymer that was impossible to process by itself. This technique stretched the
SBR supply of the country without a corresponding need to expand styrene and
butadiene monomers production. Today, both extended and nonextended
synthetic rubbers are produced. In the case of SBR, production of extended
exceeds nonextended.
In terms of quantities of oil used, about 5 to 10 percent oil is added to
nonextended rubber. In the oil extended polymers the amount of oil may
represent 35 percent or more of the overall polymer.

Composition of Rubber Oils

Petroleum oils for use in rubber are generally in the lubricating oil viscosity
range, although residual materials are sometimes employed. The importance of
composition of these oils lies in the effect composition has on their
compatibility with rubber.
Rubber-plasticizer systems may be thought of as solutions in which plasti-

cizing oils are not used in sufficient quantity to form a liquid external phase. As
with all such systems, solubility is dictated by the nature of the constituents. In
the case of rubber-oil mixtures, insolubility is manifested by "sweatout" or
exudation of oil to the surface of a rubber article-usually most pronounced
after vulcanization. To avoid the sweatout problem and benefit the rubber
compound in a variety of ways, good compatibility is desirable to the rubber
compounder. Benefits include lowered volatility of oil from polymer, faster
incorporation of compounding ingredients during mixing, better dispersion of
reinforcing pigments which correspondingly aids physical properties, reduction
of oil takeup time and heat generation, and numerous other effects.
As the interest in processing oils and their usage grew, composition assumed
more importance. Two basic methods for obtaining compositional information
about rubber oils came into use-molecular and carbon type analysis.

Molecu lar Type Analysis

Molecular type analysis separates an oil into different molecular species. The
extensive work of Rostler [1] 1 and co-workers produced a method of this type
which is useful for characterizing oils for the rubber compounder. The method
has been standardized as ASTM Test for Characteristic Groups in Rubber
Extender and Processing Oils by the Precipitation Method (D 2006). By using
pentane and sulfuric acid of different strengths the procedure separates an oil
into the following groups: asphaltenes, polar compounds, Group 1 unsaturates,
Group 2 unsaturates, and saturates. Rostler [2,3] demonstrated that the
individual groups have characteristic effects when compounded in rubber.
Another molecular type analysis which gives similar information to that of
ASTM D 2006 is the so-called "clay-gel analysis." In this method, group
separation is achieved by adsorption in a percolation column with selected
grades of clay and silica gel as the adsorption media. This procedure is now
standardized as ASTM Test for Characteristic Groups in Rubber Extender and
Processing Oils by the Clay-Gel Adsorption Chromatographic Method (D 2007).

Carbon Type Analysis

Although informative, molecular type analytical methods are cumbersome and
time consuming. For these reasons, there has been great interest in the
correlation of composition with physical properties. Among the most definitive
of these efforts was the refractive index-density-molecular weight (n-d-M)
method reported by Van Nes and Van Westen. [4] Van Nes and Van Westen
demonstrated the n-d-M method is a reliable procedure for determining carbon
type composition of oil fractions. The method has been standardized as ASTM
Test for Carbon Distribution and Structural Group Analysis of Petroleum Oils
by the n-d-M Method (D 3238). Carbon type composition gives the breakdown
of total carbon atoms between various structures.
1 The italic n u m b e r s in brackets refer to the list of references appended to this chapter.

Kurtz [5] and associates developed a correlative method for determining

carbon type distribution from viscosity-gravity constant (VGC) and refractivity
intercept (ri). Both these functions are independent of molecular weight which
makes them well suited for characterizing oils of widely different viscosities.
These workers showed that it is possible to superimpose lines of constant VGC
and r i on a triangular graph of carbon type composition. Then, if VGC and r i are
calculated for an oil whose composition is desired from viscosity, gravity, and
refractive index, a point is fixed on the graph which uniquely establishes the
percentage of aromatic ring structures (CA), naphthene ring structures (CN), and
diolefin structure (CD) for the oil. This method has been standardized as ASTM
Test for Carbon-Type Composition of Insulating Oils of Petroleum Origin (D
2140).
Sweely [6] and co-workers were also the first to apply physical property
methods for composition to rubber process oils. Since the physical properties
required are easily obtainable, they present a convenient way for the rubber
technologist whose laboratory is not set up for analysis of petroleum oils to
obtain compositional information on process oils. Usually physical property
methods are applied to the analysis of the whole oil; however, if more detailed
information is required, the oil can be given a molecular type separation into an
aromatics and a saturates fraction and the carbon type composition of each
determined.
As a summary for this section on composition, analysis based on molecular or
carbon type distribution provides the rubber compounder with sound informa-
tion. For research work, instrumental methods such as high-resolution mass
spectrometry, nuclear magnetic resonance, and infrared spectroscopy are being
used more frequently. In addition, new analytical techniques for polar
compounds are much faster than conventional methods.

Importance of Composition to Compounders

What does the determination of oil composition mean to the rubber
compounder? First of all, both molecular and carbon type compositions give a
measure of aromaticity of oils. The aromatic content of an oil determines its
compatibility with many rubbers. Thus, aromatic content dictates whether an oil
is acceptable for use in a given rubber compound or not.
The degree of aromaticity affects performance of an oil in elastomers,
particularly with the more polar types such as butadiene-acrylonitrile rubbers
and polyvinyl chloride. In this case, carbon type analysis can be more
informative than molecular type.
Asphaltenes present in an oil are determined by pentane precipitation. They
indicate the presence of resinous oxidation products or residual material which
may be undesirable to the rubber compounder since such products often lack
batch-to-batch uniformity.
All petroleum oils contain oxygen, nitrogen, and sulfur compounds to some
degree. If these nonhydrocarbons or polar compounds are reactive, as would be

the case with acidic or basic compounds, they could impart an adverse effect on
the vulcanization characteristics of the rubber with which they are used. They
may also cause discoloration and staining of light colored rubber goods under
exposure to sunlight or ultraviolet light. For these reasons, oils containing high
contents of polar compounds usually are checked for any adverse effects before
acceptance for general usage.

Classification of Rubber Oils

To aid the user of rubber process oils, a classification system has been
developed based on some of the properties just discussed. This classification,
which is given in ASTM Recommended Practice for Description of Types of
Petroleum Extender Oils (D 2226) is shown in Table 1.
Table 1 does not list aromatics; however, an indirect measure of aromaticity is
given by the saturates limits. Saturates are used instead of aromatics for
classification purposes because aromatics must be desorbed from adsorbent in
the clay-gel method, whereas the saturates are determined directly after removal
of solvent.
TABLE 1- Classification o f o i l types.

Asphaltenes, Polar Compounds, Saturated

Types max % max % Hydrocarbons, %

101 0.75 25 20 max

102 0.5 12 20.1 to 35
103 0.3 6 35.1 to 65
104a 0.1 1 65 rain

aType 104 oils are further classified into two subtypes: 104A and 104B for SBR polymers
only. Type 104B oils have a viscosity-gravity constant of 0.820 max; type 104A have a
viscosity-gravity constant greater than 0.820.

Observe also in Table 1 that VGC is used to differentiate between Type 104A
and 104B oils. In this case, VGC is being used as an estimator of aromaticity. In
addition to its use for determining carbon type composition in the viscosity-
gravity constant/refractivity intercept method, VGC by itself has long been used
to indicate aromaticity of rubber oils. VGC is a function independent of
molecular weight and quite useful for comparing different oils. Viscosity-gravity
constant has been standardized as ASTM Calculation of Viscosity-Gravity
Constant (VGC) of Petroleum Oils (D 2501).
One other measure of aromaticity that has received a considerable degree of
acceptance in the rubber industry is ASTM Test for Aniline Point and Mixed
Aniline Point of Petroleum Products and Hydrocarbon Solvents (D 611).
Unfortunately, aniline point is not molecular weight independent. This results in
oils with the same aromatic contents, but different viscosities that have different

aniline points. Other methods should be used if a more precise measure of

aromaticity is required.

Physical Properties of Rubber Oils

In general, rubber compounders use tests to control uniform quality of rubber
oils and predict how the oils will affect the rubber compound or oil-extended
rubber. Standard physical property tests used by the petroleum industry satisfy
these requirements.
The following paragraphs describe the significance of physical property tests
that normally are used for rubber oils. Details on individual tests can be found in
the appropriate Annual Book of ASTM Standards.

Specific Gravity
Specific gravity provides a means to convert volumes to weights and vice versa.
Since rubber compounding is done on a weight basis, a considerable volume
effect in rubber can be obtained with oils of different gravities. Knowledge of
specific gravity permits the calculation of the magnitude of the difference.
For oils of similar viscosity, specific gravity can be used as a rough measure of
aromaticity (the higher the specific gravity, the greater the aromaticity).
As described in earlier paragraphs, specific gravity also is needed to calculate
VGC and refractivity intercept in the determination of carbon type composition.
ASTM Test for Density, Specific Gravity, or API Gravity of Crude Petroleum
and Liquid Petroleum Products by Hydrometer Method (D 1298) is used to
determine specific gravity.

Viscosity
Viscosity gives a measure of the flow properties of the oil which, in turn,
determines the ease of handling at various temperatures. Viscosities of oils at low
temperature have been shown to correlate with low-temperature properties of
rubber containing these oils. Because viscosity is a measure of molecular weight,
it can be used to estimate the compatibility of oils in polymers. Polymers with a
critical tolerance for oil will not hold large volumes of oil of high-molecular
weight. Viscosity for rubber oils is measured by ASTM Test for Kinematic
Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic
Viscosity) (D 445).

Co/or
Oil color is an indicator of rubber oil suitability for use in light color rubber
compounds. It also influences polymer color in oil-extended polymers. Initial oil
color cannot be used as a measure of color stability of an oil itself or of a rubber
compound containing it. Color is determined by ASTM Color of Petroleum
Products (ASTM Color Scale) (D 1500).

Ultraviolet Absorptivity
For oils of a similar type, ultraviolet (UV) absorptivity is a good indicator of
the resistance of an oil to discoloration under exposure to artificial or natural
light. Oils with low absorptivities at 260 nm have been found to impart good
color stability to light-colored rubber compounds. ASTM Test for Ultraviolet
Absorbance and Absorptivity of Petroleum Products (D 2008) is used to
measure UV absorptivity.

Refractive Index
ASTM Test for Refractive Index and Refractive Dispersion of Hydrocarbon
Liquids (D 1218) is a convenient test for establishing batch-to-batch continuity
in rubber oil shipments. Refractive index is needed also to calculate the
refractivity intercept in the determination o f carbon type composition.

Aniline Point
ASTM D 611 gives a rough measure of aromaticity of an oil which is useful in
the prediction of swelling characteristics of rubbers exposed to the oil. This test
should be used with caution since aniline point is molecular weight dependent.

Flash Point
Rubber compounders often use flash point as a measure of oil volatility.
Volatility is important because rubber products are exposed to elevated
temperatures during mixing operations and, oftentimes, in service. Although
flash point has a certain utility for this purpose, it gives no indication of the
amount of low-boiling material present. Therefore, a distillation curve should be
used when volatility is a critical factor.
Flash point also is used to determine fire hazard aspects, particularly when use
of oils with low-flash points is being considered. Flash point is determined by
ASTM Test for Flash and Fire Points by Cleveland Open Cup (D 92/IP 36) or by
ASTM Test for Flash Point by Pensky-Martens Closed Tester (D 93[IP 34).

Evaporation Loss
ASTM Test for Evaporation Loss of Lubricating Grease and Oils (D 972) gives
a measure of oil volatility under controlled conditions and is used frequently for
specification purposes. However, because volatility of oil from a rubber
compound may be influenced by its compatibility with the rubber, a volatility
test of the compound often is made under laboratory test conditions pertinent
to the intended service.

Pour and Cloud Point

Pour and cloud point tests are useful in establishing low-temperature
characteristics of an oil. Pour point is mainly of concern in connection with
Copyright by ASTM Int'l (all rights reserved); Tue Dec 29 16:07:05 EST 2015
Downloaded/printed by
University of Washington (University of Washington) pursuant to License Agreement. No further reproductions aut
CHAPTER 12 ON PETROLEUM OILS FOR RUBBER 215

handling oils at low temperatures. Cloud point is useful in showing whether any
wax is present in an oil. ASTM Test for Pour Point of Petroleum Oils (D 97)
normally is used to determine pour point of rubber oils.

Specialty Applications of Process Oils

While rubber affords a substantial outlet for processing oils, it is by no means
the only outlet for materials of this type. Other areas (confined to polymeric
materials) where mineral oils can be used include caulks and sealants, textile
specialties, resin extenders, polyvinyl chloride, and other polymer plasticizers
and adhesives.
In these product areas, a wide variety of specialized oils are used.
Requirements range from high-priced oils that satisfy Food and Drug Adminis-
tration regulations to the cheapest oil available where product cost is the only
consideration. Process oil producers are sufficiently versatile to meet any
reasonable requirements. ASTM test methods and specifications simplify the
task.

Applicable ASTM/IP Standards

ASTM IP Title

D 92 36 Flash and Fire Points by Cleveland Open Cup

D 97 15 Pour Point of Petroleum Oils
D 445 71 Kinematic Viscosity of Transparent and
Opaque Liquids (and the Calculation of
Dynamic Viscosity)
D 611 Aniline Point and Mixed Aniline Point of
Petroleum Products and Hydrocarbon Solvents
D 972 Evaporation Loss of Lubricating Greases and Oils
D 1218 Refractive Index and Refractive Dispersion of
Hydrocarbon Liquids
D 1298 160 Density, Specific Gravity, or API Gravity of
Crude Petroleum and Liquid Petroleum Products
by Hydrometer Method
D 1500 196 ASTM Color of Petroleum Products
(ASTM Color Scale)
D 2006 Characteristic Groups in Rubber Extender and
Processing Oils by the Precipitation Method
D 2007 Characteristic Groups in Rubber Extender and
Processing Oils by the Clay-Gel Adsorption
Chromatographic Method
D 2008 Ultraviolet Absorbance and Absorptivity of
Petroleum Products
D 2140 Carbon-Type Composition of Insulating Oils of
Petroleum Origin
Copyright by ASTM Int'l (all rights reserved); Tue Dec 29 16:07:05 EST 2015
Downloaded/printed by
University of Washington (University of Washington) pursuant to License Agreement. No further reproductions authorized.
216 SIGNIFICANCEOF TESTS

Applicable ASTM/IP Standards (Continued.)

ASTM IP Title

D 2226 Recommended Practice for Description of Types of

Petroleum Extender Oils
D 2501 Viscosity-Gravity Constant (VGC) of Petroleum Oils

References
[1 ] Rostler, F. S. and Sternberg, H. W., Industrial and Engineering Chemistry, Vol. 41,
1949, p. 5 98.
[2] Rostler, F. S. and White, R. M., Rubber Age, Vol. 70, 1952, p. 735.
[3] Rostler, F. S., Rubber Age, Vol. 70, 1952, p. 223.
[4] Van Nes, K. and Van Westen, H. A., Aspects of the Constitution of Mineral Oils,
Elsevier Publishing Company, Houston, Texas, 1951, p. 132.
[5] Kurtz, S. S., Jr., King, R. W., Stout, W. J., Partikian, D. G., and Skrabek, E. A.,
Analytical Chemistry, Vol. 28, 1956, p. 1928.
[6] Sweely, J. S., Ferris, S. W., Peterkin, M. E., and Kurtz, S. S., Jr., Revue Generale du
Caoutchoue, Vol. 34, 1957, p. 170.

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