SMC P A M P H L E T AMCP 7 0 6- 1 85

ENGINEERING DESIGN
HANDBOOK

MILITARY PYROTECHNICS SERIES

PART ONE

THEORY AND APPLICATION

H E A D Q U A R T E R S . U S. A R M Y M A T E R I E L C O M M A N D APRIL 1967
 ' HEADQUARTERS
UNITED STATES ARMY MATERIEL COMMAND k
WASHINGTON,|D. C. 20315

AMC PAMPHLET 28 April 1967

No. 706-185

ENGINEERING DESIGN HANDBOOK

MILITARY PYROTECHNICS SERIES

PART ONE--THEORY AND APPLICATION

This pamphlet is published fdr;the information,and guidance

of all concerned. j

(AMCRD-R) !|

FOR THE COMMANDER:

K. H. BAYER
M a jo r G e n e r a l^ USA
A c t in g C h ie f o f S t a f f

OFFICIAL:

Colonel,
Chief, Adn strative Office

DISTRIBUTION-:
Special
 AMCP 706-185

PRE FACE

The Engineering Design Handbook Series o f the Army Materiel Command

is a coordinated series o f handbooks containing basic information and funda­
mental data useful in the design and development o f A m y materiel and systems.
The handbooks are authoritative reference books of practical information and
quantitative facts helpful in the design and development of A m y materiel so
that it will meet the tactical and the technical needs o f the A m e d Forces. The
present handbook is one of a series intended to fill a longfclt need for an au­
thoritative and comprehensive source o f information on military pyrotechnics.
* It is a common misconception to regard military pyrotechnics as being
synonymous with fireworks. Military pyrotechnics is rapidly developing into a
science which exploits all applicable scientific and engineering principles and
practices.
This handbook, Military Pyrotechnics, Part One, Theory and Application,
includes a chapter on the history of the pyrotechnic art, a chapter giving a
general introduction to the application of pyrotechnic devices to military prob­
lems, and chapters on Physical-Chemical Relationships, Visibility, Production
of Heat, Production of Light, and Production o f Smoke.
. Material for this handbook, except for Chapter 1, was prepared by the
Denver Research Institute of the University of Denver, under the direction of
Dr. Robert W. Evans. Material for Chapter 1, History of Military Pyrotechnics,
was prepared by the McGraw-Hill Look Company Technical W riting Service.
A ll material was prepared for the Engineering Handbook Office o f Duke Uni­
versity, prime contractor to the Army Research Office-Durhain. The prepara­
tion o f this handbook was under the technical guidance of an interservice com-
mittee with representation from the Army Chemical Center, Ballistic Research
Laboratories, Frankford Arsenal, Hurry Diamond Laboratories and Pic&tinny
Arsenal o f the Army Materiel Command; the Naval Ammunition Depot (Crane),
Naval Ordnance Laboratory and the Naval Ordnance Test Station. The chair­
man o f this committee was Garry Weingarten of Picatinny Arsenal.
Elements o f the U. S. Arm y Materiel Command having need for handbooks
may submit requisitions or official requests directly to Publications and Repro­
duction Agency, Letterkenny Army bepot, Chambersburg, Pennsylvania 17201.
Contractors should submit such requisitions or requests to their contracting
Officers.' ■ ■ • | ' ' ' . '
Comments and suggestions on this handbook are welcome and should be ad­
dressed to Army Research Office-Durhain, Box CM, Duke Station, Durham,
North Carolina 27706.

i
 AMCP 706-185

TABLE OF CONTENTS

Paragraph Page
P R E F A C E ........ . i
LIST OF ILLUSTRATIONS xii
LIST OF TABLES .. xvi

CH APTER 1

H ISTORY OF M ILITA R Y PYROTECHNICS

1-1 In trod u ction ___ '..... 1-1

1-2 Early History . . . . . . 1-1
1- 2.1 Greek Fire ........ 1-1
1- 2.2 Chinese Pyrotechnics 1-2
1-2.3 G u n pow der............ 1-2
1-2.4
I Miscellaneous Uses 1-2
1-3 18th and 19th Centuries 1-2
1-4 Early 20th Century . . . 1-3
1-4.1 W orld War I . . . . 1-3
1-4.2 Between the Wars 1-4
1-4.3 W orld W ar II . 1-4
1-5 Post W orld War II Period 1-5
REFEREN CES . . . . 1-6

CH APTER 2

INTRODUCTION TO M ILITARY PYROTECHNICS

2-1 In trod u ction ............ 2-1

2-1.1 Pyrotechnic Device^ and Uses .......... ......... 2-1
21.2 Characteristics o f Pyrotechnic Compositions 2-3
2- 1. 2.1 Performance Characteristics ...................... 2-3
2- 1. 2.2 Processing and Sensitivity Characteristics 2-3
2-1.2.3 General Funct ioning Characteristics........ 2-3
211.3 Constituents in Pyrotechnic Compositions . . . . 2-4
211.4 Comparison o f Pyrotechnic Mixtures and Explosives 2-5
REFEREN CES . . . 2-6

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AMCP 706-185 !
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TABLE OF iCOHTENTS (cont’ d)

j CH APTER 3
PH YSICAL-CHEM ICAL RELATIONSHIPS
• 1 1 '
Paragraph j ; Page
3-1 State of a System . . ; ................................ ............................... 3-1
3-1.1 The Gaseous State ............................................................... 3-1
3-1.1.1 Idfesil Gases; ................................................................... 3-1
3-1.1.2 The Universal Gas Constant and Standard Con-
| ditions i. : ................................................................ 3-2
3-1.1.3 Real Gases j . .................................................................. 3-2
3-1.1.4 Gas Mixtures ................. ................................ ............. 3-3
3-1.1.5 Sample Calculations .................................................... 3-4
3-1.2 The Liquid State ................................................................. 3-5
3-1.2.1 Vapor Pressure ........................................................... 3-5
3-1.2.2 Boiling Point ................................................................ 3-5
3-1.3 The Solid State |.. ............................................................... 3-5
3-2 Thermodynamics . . . j.. . . . . . ........................................................ 3-7
3-2.1 Thermcfdynamic Relationships .......................................... 3-7
3-2.1.1 First Law of Thermodynamics................................... 3-7
3-2.1.1.1 • |[ Heat Effects at Constant Volume and Constant
Pressure ........................................................ 3-7
3-2.1.1.2 Heat C a p a city ............................................... 3-8
3-2.1.1.2.1 I Hea't Capacity of G ases.............................. 3-9
3-2.1.1.2.2 j Heat Rapacity of Liquids and Solids . . . . 3-9
3-2.1.2 Second Law! of Thermodynamics . . . : ........................ 3-9
3-2.1.3 Third Law of Thermodynamics ............................. 3-10
3-2.2 Thermochemistry^ ................................................................. 3-11
3-2.2.1 Heats of R ea ction ................. 3-11
3-2.2.2 Effect of Temperature on theHeat of Reaction 3-12
3-2.2.3 Enthalpy Tables ........................................................... 3-13
3-2.2.4 Bond Energies ............................................................. 3-13
3-2.3 Free Energy andj Equilibrium ........................................... 3-13
3-2.3.1 Chjmical Equilibrium ................................................. 3-14
3-2.3.2 The? LeChatelier Principle ......................................... 3-16
3-2.3.3 Free Energy , and the Equilibrium C on stan t............ 3-16
3-2.3.4 Frele Energy! Calculations ........................................... 3-17
3-2.3.5 Tabulated Free Energj' Values ............................... 3-19
3-2.4 Adiabatic Flame1Temperature ..................... 3-19
3-2.5 Sample 'iThermodynamic Calculations ........... 3-20
3-2.6 Summary of Thermochemical Calculations...................... 3-23
3-3 Chemical Kinetics .................... 3-23
3-3.1 Molecularity of Reactions ................................................... 3-24
3-3.2 Order o f Reaction ............. 3-25
3-3.3 Influence of Temperature on Reaction R a te s .................. 3-26
3-3.4 Chain Reactions |........................ 3-27
3-3.5 Heterogeneous R eactions.............. .......... .. 1 ................ 3-27
3-3.6 Ignition amd Propagative Burning ------.^. ................. 3-27
■ ■ , i f • ■
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TABLE OF CONTENTS (coat’d)

f .
Paragraph Page
3-3.6.1 Ignition 3-28
3-:3.6.2 Burning of Metal P articles............ .................. ■— 3-29
3-3.6 3 Burning of Solid Propellants ................................... 3-29
3-3.6.4 Rate o f Propag itive B u rn in g .................... ......... .. 3-30
34 Thermoanalytical Techniques . . . . ...... ..................................... 3-32
REFEREN CES ................................................................ . 3-36

CH APTER 4

VISIB ILITY

4-1 Introduction .......... ................................................. 4-1

4-2 Vision ........ .................................... 4-1
42.1 Brightness Contrast ............................ 4-1
4-4.2 Overall Contrast 4-2
4-3 Attenuation Of C on tra st........ ............................... .................... 4-2
4-3.1 Attenuation of Contrast by the Atm osphere................ .. 4-3
4-3.2 Obscuration o f Vision by Artificial Smoke C lo u d s ........ 4-4
4-4 Visibility o f Targets and S ig n a ls .......................... .. 4-6
4-4.1 Visibility o f Targe ts Under Artificial Illumination . . . 4-6
4-4.2 Visibility of Signals ...................... ..................... .. 4-8
4-4.2.1 Visibility of Smoke Clouds .................................... 4-9
4-4.2.2 Visibility of lig h t S ou rces.............. ................... .. 4-9
4-4.3 Estimation o f Visibility ...... ............................................ 4-10
4-4.4 Illustrative Exam ples ........ ................................. .*------ -- 4-15
REFEREN CES . . . . J! ................................... ................. . 4-18

CH APTER 5

PRODUCTION OF H EAT

5-1 Historical Summary ............................. 5-1

5-2 Introduction . . . . . . . .............................. 5-5
,5-3 Theory ___ . . . ------ ...................................... 5-5
5-3.1 Amount of Energjjr R eleased............ ....................... 5-6
[5-3.2 Heat Transfer . 5-7
15-3.2.1 Conduction 5-9
:5-S.2.2 Convection and Radiation . . . . .......... ...................... 5-10
!5-3.3 Heat Effects .................................. ........................... 5-10
5-4 Incendiaries . . . . . .......... .................... ................., .......... 5-11
5-4.1 Small Arms Incendiary A m m unition........................ .. 5-11
15-4.1.1 Ignition and Combustion o f A ircraft F u e l s ........ .. 5-13
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AMCP 706-185 i -

TABL1 OF CONTENTS (cont’ d)

Paragraph Page
5-4.1.2 Nature of a Small Arms Incendiary Burst 5-14
N 5-4.1.3 Small Arms Incendiary Fillers . . . . . . . . . . 5-16
5-4.1.3.1 Fuels . . . . . . . . . . . . . . . ...... ........ ............. .. 5-17
5-4.1.3.2 ' O xid izers;.!___ ______ _. . . . _____ . . . . . . ____ _ 5-17
5 4.1.3.3 : ' Binders, Lubricants, and Other Incendiary
| Mixture Additives . . . . . . . . . . . . . . . . . . . . . 5-19
5-4.1.3.4 V 'typical Compositions ............................ 5-20
5-4.1.4 Typical Small; Arms Incendiary B u lle ts ...... ......... 5-20
5-4.2 Incendiaries for Ground Application . . . . . . . . . . . . . . . 5-21
5-4 2.1 Ignition and Combustion of Ground Targets . . . . . 5-21.
5-4.2.2 Incendiary Compositions . . . . . . . . . . . . . . . . . . . . . . 5-22
5-4 2.2.1 Metal-Based Ground Incendiaries .. 5-22
.. 5-4.2.2.2 .liquid Fuel-Based Incendiaries . . . . . . . . . . . . 5-24
5-42.2.2.1 : j- Liquid Incendiaries . ! ............................... 5-25
5-4.2.2.2.2 " 1 Solidified Liquid Incendiaries . . . . . . . . . . 5-25
5-4.2.2.2.2.1 Rubber Thickeners . . . . . . ; ......... 5-26
5-4.2.2.22.2 Napalm Thickeners ............................. 5-26
5-4.2.2.2.23 Methacrylate Thickeners . . . . . . . . . . . 5-27
‘ 5-4.2.2.3 Other Incendiaries ....................................... 5-28
5-4.2.3 Typical Incendiary Devices ................................... 5-28
5-5 Delay Compositions and Heat Powders ............................ .. 5-29
5-5.1 Pyrotechnic Delays ........................................... 5-29
55.1.1 Delay Elements ........ ..................... .................... . 5-29.
5-5.1.1.1 . Obturated1Delay Elements . .......... . ,5-30
5-51:1.2 Vented Delay Elements ........................................ 5-30
. ■ • it. •• i ■ ■ ■ ■ ■ ■ •
5-5.1.2 Delajr Compositions 5-30
5 5.1.2.1 Black Powder Delays ....................... 5-31
5-5.1.2.2 Typical Gasless Compositions ; . . . ................... 5-32
5-5.1.3 Factors Affecting Perform ance......... .................... 5-32
5-5.1.3.1 Composition .......................................... 5-33
5-5.1.3.2 External Pressure ........................ ........................ 5-34
5-5.1.3.3 External Tem perature----- ............................... 5-35
5-5.1.3.4 Terminal Charge, Anticipatory Effect .............. 5-36
5-5.1.3.5 Particle Size ' .................... 5-36
5-5.1.3.6 I[?nition Compositions . ...................... ............. . 5-87
5:5.1.3.7 Column Diameter ................................. 5-37
5-5.1.3.8 Loading Pressure ................................... 5-38
5-5.1.3 9 Blousing Material ................................. 5-39
5-5.1.3.10 . Acceleration .................. ............................. ... 5-43
5-5.1.3.11 Storage . . . . . . . . . ___ : . ................. 5-43
5-5.2 Heat Powders _________________________________________ 5-45
5-6 Initiators, First Fires, and Starters' . . . . . . . . . . . ■ . . . . . . . . . 5-45
5-6.1 Prime Ignition . . . .1 ........ ; ............. ................. ....... ....... 5-45
5-6.2 Characteristics o f Ideal Igniter, First Fire, and : '
Starter Compositions . . . . . ; . . . . . . . . . _________ 5-46

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TABLE OF CONTENTS (cont’d)

Paragraph Page
5-6.3 Typical Compositions 5-48
REFEREN CES . . . . . 5-48

CH A PTE R 6

PRODUCTION OF LIGHT

6-1 Historical Summary 6-1

6- 1.1 Consolidated Illuminants ..................................................... 6-1
6- 1. 1.1 Flares and S ig n a ls ...................................................... 6-1
6- 1. 1.2 Tracers .................................................................6-2
6- 1.2 Nonconsolidated Illuminants ...... ...................................... 6-5
61.2.1 Photoflash Devices ........................................................ 6-5
641.2.1.1 Photoflash B om bs........ .......................................... 6-5
6- 1. 2. 1. 1.1 Composition Type . ....................................... 6-5
6- 1. 2. 1. 1.2 Dust Type ........................ ............................. 6-6
6-1.2.11.3 Segregated Oxidant T y p e .......................... 6-7
6- 1. 2. 1.2 Photoflash Cartridges ........................................... 6-7
641.2.2 Spotting Charges ........................................................ 6-8
642 Theory o f Light and C o l o r .............. .......................................... 6-8
6- 2.1 Behavior o f L i g h t ............................... ................................ 6-8
6- 2.2 Spectral Distribution .................................. ........................ 6-9
6- 2. 2.1 Discrete S p e c tr a .......... ................................................ 6-9
6- 2. 2. 1.1 Line Spectra .......... .............................................. 6-9
6- 2. 2. 1.2 Band Spectra ...................................... ........i____ 6-10
6 2.2.2 Continuous Spectra .............................. ...................... 6-11
6-2.3 Radiation Sources 6-11
6-2.3.1 Thermal Radiation S ou rces................... 6-11
6-2.3.1.1 B la ck b od y ....................... 6-11
6-2.3.1.2 Graybody ........................ 6-12
6-2.3.1.3 Incandescent Sources . . . ........ 6-12
6- 2. S .2 Luminescence ........................ 6-18
6-2.3.2.1 Chemiluminescence .......... 6-14
6- 2. S . 2.2 Phosphor sscence and F luorescence.................. 6-14
6-2.S.3 Flame Sources_________ __; ...........................................6-14
6-2.4 Photometry . . . . 1 ........... 6-14
6-2.4.1 Instruments for Measuring Light Intensity . . . . . . 6-15
6-2.4.2 Measurement o f theLight Output o f F la r e s ........... 6-15
6-2.4.S Intensity . ................. ............................. 6-16
6-2.44 Brightness ................................................ . 6-16
6-2.4.5 Illumination .................. .......................................... 6-16
6-24.6 Photometric tJnits ............ ........................ '. ................ 6-16
6-2.5 Color 6-17
6-2.5.1 Additive Color ■*■....___ _____ _________________ __ 6-17

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 AMCP 706-185

TABLE OF CONTENTS (cont'd)

Paragraph Page
6-2.5.2 Subtractive Color .................................... 6-18
fi-2.5.3 Chro;maticity Coordinates ...................... 6-18
6-2.5.4 Munsiell Color ; System ............................ 6-20
6-2.5.5 Color; Value ...... ..................................... .. 6-20
6 2.6
- Atmospheric Effects ........................................ fr-20
6-3 , Consolidated Illuminating D e v ice s .................. .... 6-21
6-3.1 Illuminating Flares ...................... ................ 6-21
6-3.1.1 Aircraft F la r e s ...... ............. ................... 6-21
6-3.1.2 Surface Flares,........ ........................... . . . 6-23
6-3.2 Illumination S ig n als........ ............................... 6-23
6-3.2.1 Aircraft Illumination Signals ............ . 6-23
6-3.2.2 Ground Illumination S ig n a ls ................ 6-24
6-3.3 Tracers .].............. ........................... ................. 6-24
6-3.4 Typical Com positions.......... ..................... ..... 6-27
6-3.5 Factors Affecting Perform ance............ ......... 6-27
6-3.5.1 Heat jof Reaction .......................... .. 6-30
6-3.5.2 Composition . ; ............................ ........ ..... 6-33
6-3.5.S Emitters .............................................. ...... 6-33
6-3.5.4 Color |Intensifies ........................ ............ 6-37
6-3;5.5 Binders ........ .............................. ............. 6-38
6-3.5.6 Particle Size• .......................... 6-39
•;F ' : •
6-3.5.7 Consolidation . ................ ..... 6-41
6-S.5.8 Flare] Diameter* .............. .. 6-43
6-3.5.9 Case Materials' and Coating 6-43
6-3.5.10 Temperature and P ressu re...... .............. 6-45
6-3.5.11 Rotational Spin ........................................ 6-47
6-3.5.12 Moisture and Stability .......................... 6-49
6-4 Nonconsolidated Illuminant Charges ............ .... 6-52
6-4.1 Aerial Photographic Illum inants.................. 6-53
6-4.1.1 Photofiash Cartridges . . ...................... '.... 6-54
6-41.2 Photoflush Bombs .................................. .. 6-54
j ( , 1
6-4.1.3 Other, Photographic Illuminant Systems 6-54
6-4.2 Spotting Charges .................... ......................... 6-55
6-4.2.1 Small jArm Spotting R o u n d s ___ _____ 6-55
6-4.2.2 Tracking ........ ;....... ................................... . 6-55
6 4.2.3 Indication o f F u n ction in g.......... .. 6-56
6-4.3 Typical Compositions ................ ...................... 6-56
6-4.4 Light Production ............................................ . 6-56
6-4.4.1 Light Output Characteristics .................. 6-57
6-4.4.1.1 Tiime Intensity , .................. 6-57
6-4.4.1.2 Spectral D istribution........ 6-58
6-4.4.2 Nature; of the Photoflash Burst 6-58
6-4.5 Factors Affecting Performance 6-61
6-4.5.1 Charge Weight |. . . . . . — 6-61
6-4.S.2 Composi tion . . 1.......... ...... 6-62

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TABLE OF CONTENTS (coat’d)

Paragraph Page
6-45.3 Particle Size. 6-64
(J-4.5.4 Cloud Shape 6-65
6-4.5.5 Bursters and Igniters ................................................... 6-66
6-4.5.6 Confinement 6-67
6-4.5.7 Ambient P ressu re........................................................ 6-69
REFEREN CES 6-70

CH APTER 7

PRODUCT ION OF SMOKE

7-1 Historical Summary, General 7-1

7-1.1 , Screening Smokes 7-1
7-1.2 Signal Smokes 7-3
7-1.3 Tracking and Acquisition Smokes 7-4
7-2 Properties of Smoke .|.............. ................................................. 7-4
7-2.1 Properties of Particulate C lo u d s .................................... 7-5
7-2.1.1 Optical Properties of Particulate C lo u d s.............. 7-7
7-2.1.2 Properties o f Particulate Clouds Affecting Their
Stability .).................................... ........................... 7-7
7-2.1.2.1 Motion o f Smoke Particles 7-7
7-2.1.2.1.1 Sedimentation 7-7
7-2.1.2.1.2 Diffusion
jus: .... 7-8
7-2.1.2.2 Evaporation and Condensation . . . . 7-8
7-21.2.3 Coagulation and Agglomeration . . . 7-8
7-2.2 Travel and Persistence of Particulate Clouds 7-9
7*2.21 Meteorological F a c to r s .............. 7-9
7-2.211 W ind Speed and Direction 7-9
7-2.21.2 Turbulence ......................... 7-9
7-2.21.3 Thermal Gradient ............................... 7-10
7-2.2.2 Stability of lAerosol Clouds Under Various
Meteorological C on dition s...................... , 7-10
7-2.2.21 Stable Conditions 7-10
7-2.22.2 Unstable C onditions................ ............ 7-11
7-2.2.23 Estimation o f Atmospheric Diffusion 7-11
7-2.3 Specific Properties o f Military Smokes 7-12
7-2.31 Screening S m ok es...................... . 7-12
7-23.2 Signal Smojkes ...................... .. 7-13
7-2.33 Tracking and Acquisition Smokes . 7-13
7-23.4 Smoke for Dissemination o f Agents 7-13
7-3 Dissemination Techniques 7-14
7-3.1 Formation of the Dispersed Phase . 7-14
7-31.1 Vapor Condensation Processes 7-14
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TABLE OF pONTENTS (cont’ d)

Paragraph
7-3.1.2
I■
Dispersion Processes .................................... ..
Page
7-14
7-3.1.3 Combined Processes ....................... ................. ............ 7-15
7-3.2 J filitiijr Production o f S m ok e............ — .................... . 7-16
7-3.3 . White iSimokes . I ........................ ........ ................................. 7-16
7-3.3.1 Oil: Smoke ............ ..................... ........... ........................ 7-17
7-3.3.1.1 Venturi j Thermal G enerators........ ................... 7-17
7-3.3.1.1.1 Operation o f Venturi Thermal Generators 7-17
7-3.3.1.1.2 Fuel Blocks ............ ........................... ......... 7-18
7-3.3.1.1.3 , Typical Venturi Thermal Generators . . . . 7-20
7-3.3.1.2 Other Methods for Producing Oil Smoke . . . . . . . 7-20
7-3.3.2 Phosphorus Smokes .................... ............................... 7-21
7-3.3.2.1 White Phosphorus............ ................................... 7-21

1
7-S.3.2.2 Buraing-Type Mixtures Containing Red
7-22
7-3.S.2.3 7-22
7-3.3.2.4
7-22
7-3.3.2.S 7-23
7-S.3.3 7-23
Phosphorus.......................................................
7-3.3.3.1 7-23
Metal Phosphides .......... .............. ......................
7-3.3.3.1.1 7-23
Other Reactions for Producing Smokes
7-3.3.3.1.2 7-24
Containing Phosphorus..............................
7-3.3.3.1.3 7-25
Typical D e v ice s.................. . . . .............................
7-3.3.S.2 7-25
metal Chloride1Smokes .................... ............... ..........
7-3.3.3.2.1 ,7-25
Liquid Metal Chlorides ......................................
7-3.3.3.2.2 7-25
I !, FM 1Smokes ...... ........................... ...............
7-3.3.3.3 7-27
] Silicon Tetrachloride .................................
7-3.3.S.4
Stannic C h lorid e..........................................
[Solid Metal Chlorides ...................... ...........; . . 7-27
7-S.3.3.5 7-28
,j HC Smokes .................. .............. ...............
7-S.3.4 7-28
Chemistry of HC Smoke M ixtures............
7-3.3.4.1 7-29
'Modified jHC Smokes ............................ .............
7-3.S.4.2 7-29
Zinc Mexachlorobenzene-Potaasium Perchlorate
7-3.3.43 7-29
j| System|................................ ........... ...................
7-3.S.4.4 7-30
iTypical D e v ice s............................... ..................
7-3.S.4.5 7-30
Sulf uric Acidj S m ok es............................................
7-3.3.5
Sulfur Trioxide ................................... .............
7-80
Oleum J . i .......................... ................ .
7-3.3.5.1 7-30
Chlorosulfonic A d d ............................................
7-S.3.5.2 7-80
Sulfuryl C h lorid e .............. .............. ....... ........
7-3.3.5.2.1 7-30
FS Smoke ........ ............................. ..
7-3.3.S.2.2 7-80
Smoke-Producing Reactions Involving Ammonia
7-S.3.5.2.3
or Jikmines ............ .................... ........
.Ammonium and Amine Salts of Volatile A dds 7-31
7-S.3.5.3 7-81
Metal Chlorides and Am m onia..........................
| Hydrogen Chloride and Ammonia ..........
| Titanium Tetrachloride and Ammonia . . .
x
I Silicon Tetrachloride, Ammonia, and
; Waiter ............... .............. .........................
£:lsilfur Compounds
1. and A m m onia.......... ..
it i I
| i
 AM CP 706-185

TABLE OF CONTENTS (cont’ d)

Paragraph Page
7-3.3.5.8.1 Sulfur Trioxide and Ammonia or Amines 7-31
7-3.3.5.3.2 Chlo^osulfonic Acid and Ammonia or
t '
Amines ...................■. . . . . , .......................; 7-31
7-3.3.5.3.3 Sulfuryl Chloride and Ammonia or Amines 7-31
7-3.3.6 Sulfur Sm oked............................................................. 7-81
17-3.3.7 Organic Metallic Compounds ................................... 7-31
7-3.3.8 Comparison o f White Sm okes...... ........................ 7-82
7-3.4 Colored Smokes ............ ....................................................... 7-33
7-3.4.1 Dyes . . . . ............................. 7-33
j 7-3.4 2 Fuels , ___ ............................ . . . . . . . . . . . . . . . . . 7-39
7-34.3 Oxidants . ________ 7-39
17-3.4.4 Cooling Agents .......................... 7-40
] 7-3.4 5 Binders ........ ....................... 7-40
I 7-3.4 6 Evaluation o f Colored Smokes . . . . . . . . . . . . . . . . . . 7-40
17-3.4.7 Sensitivity o£ Colored Smoke Mixtures . . . . . . . . . . 7-40
17-34.8 Toxicity o f Colored Smoke Mixture . . . . . ______ ... 7-41
7-34.9 Typical D e v ice s___ . . . ____ . . . . . . ____ . . . . . . . . . . 7-41
7-3.4.10 Direct Volatilization o f Dye ....................................... 7-41
7-3.4.11 Colored Smoke from Solution o f Dyes . . . . . . . . . . . . 7*43
! 7-3.4.12 Black Smoke ; . . . . . . . . . . . . . _____ ___ . . . . . . . . . . . 7-44
7*3.4.13 Explosive-Type Colored Smoke Bursts . . . . . . . . . . . 7 45
7-3.4.13.1 Propellent Bursters .......... ................................. 7 4 6
7-3.4.13.2 High Explosive B u rsters.......... .......................... 7 46
7-3.4.14 Typical Mixtures . . . . . _________ ___; . . . . . . . . . . . 7 4 6
7-3.5 Agent Aerosols 746
REFEREN CES 749
AMCP 706-185
I
I

■■ ! 1 ■
' ■ ■
LIST OF ILLUSTRATIONS

Figure No. ' I I Title Page

3-1 Compressibility Factors as a Function of Reduced Pressure . . . . 3-3
3-2 Cubic Lattices . J................................................ ..................... ........... 3-6
3-3 Effect of Temperature on Enthalpy Change for a Chemical
Reaction .......... ............... ] ................................. ............................... 3-12
3-4 Enthalpy of Aluminum Oxide Versus Temperature ..................... 3-20
3-5 Enthalpy of Products of Magnesium-Air Reaction ....................... 3-21
3-6 Enthalpy of Products of Magnesium-Sodium Nitrate Flare
(Reaction 1) .. L ..............i................ ............................................... 3-23
3-7 Enthalpy o f Products of Magnesium-Sodium Nitrate Flare
(Reaction 2) .. I .............. .......................... .’ ....................... .......... 3-23
3-8 Enthalpy of IM -ll'llncendiaty; Mixture ............ .............................. 3-26
3-9 The Relationship Between Heat of Reaction and Heat of
. Activation ........ |.............: i .............................. ................... .......... 3-26
3-10 Ignition Time-Temperature plots for a Binary Pyrotechnic
Mixture ........ ... J.......... .... 1............................................................. 3-28
3-11 Model for Burning of Aluminum Particles ............................ 3-29
3-12 Model for Steady State Progressive Burning .................................. 3-30
3-13 Differential Thermal Analysis' Thermocouple Circuit . . . . . . . . . . . . 3-31
3-14.1 Thermogravimetric Curve for the Ingredient Sodium Nitrate . . . . 3-32
3-14.2 Thermogravimetric Curve for j t he Ingredient Magnesium . . . . . . . 3-32
3-14.3 Thermogravimetric Curve for jthe Ingredient Laminae 4 1 1 6 ........ 3-32
3-15.1 Differential Thermal^ Analysis iCurve for the Ingredient Sodium
Nitrate ................ ..................................................... ............. .. 3-33
3-15.2 Differential Thermal Analysis Curve for the Ingredient Magnesium 3-33
3-15.3 Differential Thermal Analysis Curve for the Ingredient Laminae
4 1 1 6 ........................ 1.. . . . . . . 1 . . . . . . . . . .......................................... 3-33
3-16.1 Differential Thermal Analysis Curve for the Magnesium-Sodium
Nitrate Mixture (Curve I ) ................................ ............................. 3-34
3-16.2 Differential Thermal Analysis Curve for the Sodium Nitrate-
Carbon Mixture .. i .............. l........................ ................................... 3-34
3-16.3 Differential Thermal Analysis Curve for the Magnesium-Sodium
Nitrate Mixture (Curve II) ' . ....................................... ........... ..... 3-34
3-16.4 Differential Thermal Analysis Curve for the Sodium Nitrate-
Laminae Mixture . I .............. ,........... ................................................. 3-34
3-16.5 Differential Thermal Analysis Curve for the Magnesium-Laminae
Mixture ................ ............... ............................... ........................... .. 3-35
3-17.1 Differential Thermal Analysis Curve for the Magnesium-Sodium
Nitrate-Carbon Composition ; . . . . . . ........................ ..................... 3-35
3-17.2 Differential Thermal Analysis Curve for the Magnesium-Sodium
Nitrate-Laminae Composition j..;....... ........................................ .. 3-35
 AMCP 706-185

LIST OF ILLUS RATIONS (cont’d)

Figure No. Title Page
4-1 Thresholds o f Brightness-Contrast for 80% Detection for Five
Angular Fields (Minutes of A rc) 4-2
4-2 Apparent Contrast as a Function of Distance .................................. 4-2
4-3 Optical Slant Range Diagram for the Optical Standard Atmosphere 4-5
4i4 Brightness Requirements as a! Function of Acuity and Contrast 4-6
4t5 Effect of Direction of Illumination on the Luminance of a
Smoke Column .................. J........................................... ............. - •• 4-9
4-6 Effect of Relative Direction oi Sun and Smoke on Time of
i
DiswrivAry . . . ........ 4-9
4-7 Visibility Nomograph . . . . . 4-12
4-8 Visibility Nomograph for Sig lal L ig h ts ............................................ 4-14
4-9 Visibility Nomograph Showii ig Calculation .................................... 4-16
4-10 Visibility Nomograph for Sigi lal Lights Showing Calculation . . . . 4- i7
5-1
Gasoline or Kerosene 5- 14
5-2 Maximum Temperature, T, as a Function of Heat of Reaction and
I Average Specific Heat, C 5-16
5-3 Cooling Time to 800°K as a Function of Temperature and Heat
i
Capacity, C .......... .. 5-16
5-4 Cooling Time to 800°K as a Function of Heat o f Reaction and
Specific Heat, C . . . . . . . . J............................ ............................... . 5-17
5-5 Time-Temperature Histories jfor IM-11, IM-23, and IM -1 0 3 ........ 5-18
5-6 Cooling Curves for Mixtures Containing Various Particle Sizes
I and Shapes of Magnesium-jAluminum 50/50 A l l o y .................... 5-19
5-7 Typical Caliber .50 Incendiary B u lle t ........ .................................... 5-21
‘5-8 Typical Caliber .50 Armor-Piercing Incendiary Bullet 5-22
5-9 Typical 20 mm Armor-Piercing Incendiary Bullet . . . . 5-23
5-10 Typical 20 mm High Explosive Incendiary Projectile 5-24
,5-11 Four-Pound Magnesium Alloy Incendiary B o m b ........ 5-29
15-12 Four-Pound Thermite ( Incendiary Bomb ...................... 5-30
.5-13 Typical Napalm Bomb .................................................... 5-31
! 5-14 Typical Incendiary Grenade .............. ............................ 5-32
•5:15 Obturated Delay Element j i . . . ...................................... 5-32
' 5-16 Sealing o f Vented Delay Element 5-33
■j 5-17 Time Delay Ring or Train, V e n te d ................................ . ............ 5-38
; 5-18 Total Heat Evolved Versus Burning Time of Binary Barium
Chromate-Boron Compositions Loaded to a Height of 0.79 Inch in
M112 Fuze Housing at 36,000 p s i ............ ....................................... 5-38
5-19 Burning Time of M112 Fuse Versus External Pressure ............... 5-39
5-20 Burning Time of M112 Fuze Containing 90% Barium Chromate-
10% Boron Composition Versus Logarithm of Absolute
Temperature .............................. ......................................................... 5-43
6-1 Emission Spectrum and Energy Levels of Hydrogen A t o m .......... 6- 10
6-2 Various Types of Spectra and Corresponding Electronic,
Vibrational and Rotational Motion ............................ ................... 6-11

xiii
 !

AMCP 706-185

1
LIST OF ILLUSTRATIONS (cont’d)
Figure No. | ; Title Page
6-3 Planck’s Law: Radiance as a Function of Wavelength for Various
Temperatures j|.............. 1................................. .................................. 6-12
6-4 Radiant Energy :in Different Wavelength Bands as a Function
o f Temperature .......... r .......... ......................... ....................... ....... 6-12
6-5 Isothermal Efficiencies: Fraction of Energy Emitted by an
Isothermal Radiator in Various Wavelength Bands as a Function
of Temperature ............................................ .............. .. 6-13
6-6 “ Optical” Temperatures of a Tungsten Filament ........................ 6-13
6-7 Dimensions of th e Psychological Color Solid .................................. 6-18
6-8 Additive Mixture of Primary Colors ............................................... 6-18
6-9 Tristimulus Values of the iSpectrum Colors According to the
1931 I.C.I. Standard O bserv er............ ...................................... 6-19
6-10 C.I.E. Chromaticity Diagram .................. ................... ..................... 6-19
6-11 Illumination Diagram fo r ; Parachute Suspended Flare .............. 6-23
6-12 Intensity Curves,for Various Parachute Flare H e ig h ts................ 6-24
6-13 Typical Aircraft'Parachute Flare .................................................... 6-25
6-14 Operation o f Typical Aircraft Parachute Flare ............................ 6-26
6-15 Typical Aircraft Tow Target F l a r e ........................ ; ....................... 6-27
6-16 Typical Surface Trip Flaije ................................ ............................... 6-31
6-17 Typical Hand-Held Illuminating Signal ............................ ............. 6-32
6-18 Small Arms T r a c e r .......... I ............................ ....................... ............ 6-32
6-19 Armor-Piercing Tracer ............................................................... 6-33
6-20 Artillery Tracer Element in P ro je ctile .............................................. 6-34
6-21 Artillery Tracer jj.............. I ......... ................................................. .. 6-35
6-22 Zones in Flame Propagation'.................... ....................... ................. 6-39
6-23 Temperature Distribution in a Pyrotechnic Flame .............. ........ 6-40
6-24 Luminous Intensity as a Function of Magnesium Content of
Binary Mixtures Containing Various Oxidizing Agents ____ _ 6-41
6-25 Bunting Rate as a. Function of Magnesium Content of Binary
Mixtures Containing Various Oxidizing Agents ......................... 642
6-26 Chromaticity Data! for Red,' Yellow, and Green F la r e s .......... . 6-44
6-27 Typical Spectra of Signal Flares .................. ................................... 645
6-28 Spectral Energy Distribution o f Green F l a r e ................................ 648
6-29 Magnesium Content Versus Excitation Purity for a Yellow Flare 649
6-30 Effect of Polyvinylchloride on the Candlepower of Mixtures
Containing Strontium Nitiate and Ground Magnesium, Grade A 649
6-31 Effect o f Polyvinylchloride On the Color Value of Mixtures
Containing Strontium Nitrate and Ground Magnesium, Grade A 6-50
6-32.1 Burning Rate vs Particle Size o f M agnesium ............ .................. 6-52
6-32.2 Candlepower vs Particle Size o f M agnesium .................................... 6-52
6-33 Effect o f Loading Pressure on Burning Rate of Pyrotechnic
Compositions . .|............. L ............................................................... 6-53
6-34 Effect o f Spin Upon Trace Duration of Various Standard Tracer
Compositions When Loaded into Caliber .50: M l Jacket ______ 6-53
6-35 Diagram of Bomb Burst and (Trail A n g le .......................................... 6-54
6-36 Typical Characteristics of Bijack and White Negative Material . . . 6-56

Xiv ! 1
 AM CP 706-185

LIST OF ILLUSTRATIONS (cont’d)

Figure No. Title Page
6 37 Typical Photoflash Cartridge 6-58
6-38 Typical Photoflash Bomb . . . . 6-61
(5-39 Typical 20 mm Spotting R otud 6-63
6-40 Photoflash “ Daisy” Cartridge 6-63
6-41 Typical Flash Charge for ndication o f Functioning” . 6-65
6-42 Typical Time-Intensity Curie 6-66
6-43 Synchronization o f Shutter 6-67
6-44 Time-Intensity Curves for M120A1 Flash Powder and M122 Dust
! Photoflash Bombs _____ ,L ........... . . ....... ....................... .................. 6-67
6-45 Spectral Energy Distribution Curve o f M120 Photoflash Bomb . . . 6-68
6-46 Effect o f Particle Size o f P itassium Perchlorate on Luminous
j Efficiency o f 60/40 Potast ium Perchlorate-Aluminum
Compositions .................. 6-68
6- 47 Size and Light Output o f F lash Cloud vs Time ............................... 6-68
7- 1 Approximate Size Range of
Airborne P a rticles................ .... 7-5
7-2 Scattering by Spherical Par tides With Indicated Refractive
•Indexes ............................. 7-6
7-3 Typical Venturi Thermal G en erator.................... .............................. 7-18
7-4 Typical Oil Smoke Pot (F bating) .............. .................................... 7-20
7-5 Typical Oil Smoke Pot (Tri lining) .................... ..................... 7-20
7-6 Typical W P-Filled Device ( 1115 W P Smoke Hand G re n a d e )___ 7-22
7-7 Typical Red Phosphorus-Fi lied Device .......................... ............... 7-23
7-8 AN-M8 HC Smoke Hand Gr e n a d e .......... ................................... 7-28
7-9 M5 HC Floating Smoke pJot .............. ............................................. 7-28
7-10 Differential Thermal 'Analysis and Thermogravimetric Analysis
Curve for 1,8-dihydroxyanthraquinone ...... ........... .................... 7-36
7-11 Differential Thermal Analysis and Thermogravimetric Analysis
Curve for 1,4-di-p-toluidinoanthraquinone ................ ................ 7-36
7-12 105 mm M84 Colored Smoke Projectile ........................................... 7-41
7-13 M18 Colored Smoke Hand G ren a d e ...................... .......................... 7-43
7-14 4.2-in. Colored Marker Projectile, Colored Smoke, E75 7 -4 4 '
7-15 105 mm M l Colored Marker Projectile 7-45'

xv
AMCP 706-185

LIST IOF TABLES

.1 ' ' ' . ' ' '
Table No. •! ■ Title Page
2-1 Tabulation o f Pyrotechnic D e v ice s........ ........... ............................... 2-2
2-2 Comparison o f Soine Properties of Pyrotechnic Compositions
With E xplosives............ . ................... ....... ........... . ........... ............ 2-5
3- 1 Criteria o f Spontaneity .. , 1. . . . . . . .......... 3-11
3-2 Thermodynamic Properties of Solid Magnesium Oxide .................. 3-14
3-3 Thermodynamic Properties of Solid Aluminum Oxide _______. . . . . 3-15
3-4 Thermodynamic Properties of Solid Sodium O x id e ................ 3-16
3-5 Thermodynamic Properties of Liquid Sodium Oxide ...................... 3-17
3-6 Thermodynamic Properties o f O x y g e n ......... ..................... 3-18
3-7 Example of Thermochemical Calculations: Lanthanum-
Potassium Perchlorate Reaction ........................................... . . . . 3-24
3-8 Example of Thermochemical Calculations: Zirconium-Oxygen
Reaction . . . . . I . .................. ......... ......... . . . . . . . . . ------ 3-25
4- 1 Meteorological Radge for Typical Weather C on dition s.......... . . . 4-4
4-2 Reflectance Values] (in percent) of Various Terrain Features
and Building Materials ' . .................. .................... .......... ........... 4-7
4-3 Maximum Angular ( Size of Light Source as a Function of
Adaptation Brightness ..!. . ....... ........................................... ......... 4-10
4-4 Visibility of Flashing Light Compared to Steady Light .............. 4-11
4-5 Absorption of Sunlight by Atmosphere ................ 4-11
4-6 Sky Brightness . J . . . . ____y . .......................................... ....... 4-13
4-7 Sky-Ground Ratio j_ ....:.!....................... .... 4-13
4- 8 Increase in Illumination Required for Positive Recognition _____ 4-15
5- 1 Heats Evolved from Reactions of Aluminum and Various
Oxidizing Agents . . . . . . ! . . ........................................................... 5-6
5-2 Oxygen Content o f ;[Various N itrates................. ........ 5-7
5-3 Oxygen Content of]Various Perchlorates.......................................... 5-8
5-4 Oxygen Content of [Various Oxides and Peroxides . . . . . ____ . . . 5-8
5-5 Heat of Reaction o f Reducing Agents With BariumPeroxide . . . . 5-9
5-6 Summary of Limits{o f Flammability of Various Gases and Vapors
in A ir and in Oxygen . . . ! . . . . ........... ..... 5-12
5-7 Typical Small Arms Incendiary Mixtures ................ 5-20
5-8 Heat of Reaction of Thermite-Type Mixtures Containing
Magnesium........ ,|...............j . ............................................................. 5-85
5-9 Modified Thermite Com positions.................................. .... 5-25
5-10 Heats o f Combustion and. Hydrogen-Carbon Ratios of
Selected Fuels . ] .............. ;.................... .■............. 5-26
5-11 Composition of IM-Type Incendiary Gels ........................................ 5-27
5-12 Composition o f PT,, Incendiary Mixtures .................. 5-28
5-13 Gasless Delay Compositions in Current Use . . . . . ......... 5-34

xvi

■it
 . AMCP 706-185
i • ' ' •

LIST OF TABLES (cont’d)

Table No. Title Page

5-14 Burning Rates of Gasless Delay Compositions ................................ 5-35
5-15 Heats o f Reaction of Inorganij Mixtures Considered for Delays .. 5-36
5-16 on Burning Time, Heat of
Reaction, and Impact Valu ;s of the Barium Chromate-Boron
System . ............ ............................................................. •.................... 5-37
stent of Anticipatory Effect as a Function of Burning Rate of
Various Barium Chromate-Boron Compositions .......................... 5-38
5-18 Extent of Anticipatory Effect as a Function of Column Length of
55/35/10 Tungsten-Barium Chromate-Potassium
| Chromate Composition . . . 5-39
5-19 Effect o f Specific Surface on Burning Time of Tungsten Delay
Compositions ...................... 5-40
5-20 Ignition Powders for Gasless Delay Elements ................................... 5-40
5-21 Effect o f Fuze Housing Mate rial and Dimensions on Burning Time
I of Barium Chromate-Borori Com positions................ ................... 5-41
5-22 Effect of Loading Pressure on Barium Chromate-Boron
i Compositions ............................................................................. 5-42
5-23 Effect of Storage on Fuzes Loaded With Barium Chromate-Borbn
l Compositions ..................................................... ,............ . 5-44
i5-24 Burning Times of Fuzes Loaded With 93/7 Barium Chromate-
I Boron Compositions Stored Loose Under Various Conditions . . . 5-44
•5-25 Commercial Safety Match Composition ........................ 5-46
5-26 Safety Match Striker Composition ............................ . 5-47
5-27 SA W (“ Strike-Any where” ) Match Composition .......... .. 5-47
5-28 Friction Primer Compositidns ......... ... ... .............. ............................ 5-48
i 5-29 Some First Fire, Starter, and Igniter Compositions ....................... 5-49
i 6-1 Conversion Factors for Photometric U n its .................. ...................... 6- 17
■6-2 Candlepower Requirements Versus Height of Illuminating Source 6-21
6-3 Characteristics of Various illuminating Flares ....................... • 6-22
6-4(A ) Characteristics of Various Aircraft Signal F la r e s ................ .......... 6-28
! 6-4(B ) Characteristics of Various Ground Signal Flares 6-30
6-5 Typical Illuminating, Signaling, and Tracer Compositions . . . . . . 6-36
i 6-6 Heats o f Reaction of Aluminum With Stoichiometric Quantities
of Various Oxidants .............................. ..................... ...................... 6-37
6-7 Heats o f Reaction of Magnesium With Stoichiometric Quantities
o f Various Oxidants ...................•------, ............................................. 6-38
6-8(A ) Physical Data and Burning Characteristics for Stoichiometric
Mixtures o f Various Oxidants With Atomized M agnesium ........ 6-43
6-8(B ) Characteristics o f Binary fix tu re s Containing Oxidizing
Agents and Atomized Magnesium, Grade A .......... ........................ 6-46
6-9 Characteristics of Pyrotechnic Compositions Containing
Various Polyester Resin) Binders .................... ................................ 6-47
6-10 Effect of Particle Size on Burning Rate and Candlepower for
Magnesium-Sodium Nitrate-Polyvinylchloride-Laminac Mixture 6-49
6-11 Effects o f Change in Specific Surface of Magnesium Particles . . . 6-50

X V II
 i

AMCP 706*185

LIST] OF TABLES (cont’d)

Table No. 1 Title Page

6-12 Effect of Loading: Pressure on Burning Characteristics of
Magnesium-Sodium Nitrate Flares ................................................ 6-50
6-13 Effect of Simulated Altitude and Temperature on Illumination
Characteristics of Yellow Signals .......................... ........................ 6-51
6-14 Effect of Simulated Altitude and Temperature on Illumination
Characteristics of Red Signals ........................................................ 6-51
6-15 Effect of Simulated Altitude and Temperature on Illumination
Characteristics of Green jSignals .................................................... 6-52
6-16 Designation and Descriptioh of Photoflash C artridges.................. 6-55
6-17 Characteristics of j|Type III! Photoflash C om position...................... 6-57
6-18 Designations and Descriptions of Flash Powder Photoflash Bombs 6-59
6-19 Characteristics of Dust Photoflash Bombs ........................................ 6-60
1 1:
6-20 Segregated Oxidant Photoflash Bombs ............................................ 6-61
6-21 Typical Compositions for Photoflash and Spotting C h arges.......... 6-62
6-22 Luminosity Characteristics at Sea Level o f Photoflash
Compositions Consisting of High-Energy Fuels in Stoichiometric
and Fuel-Rich Combinations With Potassium Perchlorate ___ 6-64
6-23 Thermodynamic Data for Stoichiometric Mixtures of
Oxidizing Agents and Atouiized A lu m in u m ................................ 6-65
6-24 Luminosity Values of Various Oxidants With Atomized
Aluminum and Atomized Magnesium Tested in M112 Photoflash
Cartridge ___ ---------------j-. ............................................................... 6-66
6-25 High Explosives Tried As Bursters in Flash B o m b s .................... 6-68
6-26 Luminosity Characteristics of Photoflash Compositions
Consisting of High-Energy] Fuels in Stoichiometric Combination
With Potassium Perchlorate .......................................... ................. 6- 69
7-1 Terminal Velocities^ and Diffusion Coefficients of Rigid Spheres
o f Unit Density in Air at 760 mm Hg Pressure and 2 0 ° C ........ 7-8
7-2 Characteristics of Typical Oil Smoke P o t s ...................................... 7-19
7-3 Characteristics of Typical Devices Using Phosphorus F illin g ___ 7-24
7-4 Variation o f Burning Time of Type-C HC Smoke Mixture With
Aluminum Content 'll
........ ................................................
' • ' ,
................. 7-26
7-5 Characteristics of Typical Devices Using HC M ix tu re ............ . 7-29
7-6 Total Obscuring Power of White Smokes ................ ................... . 7-32
7-7 Amount of Smoke Agents Required To Produce 1,000 Cubic Feet
of Standard Smoke .......... < .............................................................. 7-32
7-8 Amount of Smoke Produced Per Unit Weight o f Smoke Agent
at 75% Relative iHumidityj.................................... .................. 7-33
7-9 Some Dyes Which j'lave Been Used in Burning-Type Colored
Smoke Munitions!............... ................................................................. 7-34
7-10 Some Dyes Which Have Been Used in Explosive-Type Colored
Smoke Munitions! ............i......... ................. ................................... 7-35
7-11 Characteristics of Topical Ejection-Type Colored Smoke
Devices .............. J............... t .................... ......... ............................... 7-42
7-12 Basic Differences Between the Colored Marker and Base-
Ejection Smoke Projectiles for 105 mm G u n ................................ 7-45
7-18 Typical Smoke Compositions 1.............................................................. 7-47

xviii
\

[
 fr n ;y ~r.- 'V -

AMCP 706*185

CHAPTER 1

HISTORY OF M ILITAR Y PYROTECHNICS

1-1 INTRODUCTION in Europe mentions the Roman Circus during the

Pyrotechnics is an old craft that has continued reign of Augustus (27 B.C. to 14 A .D .). Roman
to assume greater military importance. In their use of pyrotechnics appears to have been largely
simplest form, pyrotechnic devices consist of an for display. Movable frameworks were fitted with
oxidizing agent and a fuel that produce an exo­ adjustable parts and designed to set in motion
thermic’ self-sustaining reaction when heated to various colored lights.
ignition temperature. Man’s earliest pyrotechnic A military use of pyrotechnics that began early
devicesjmay have been the result of an accidental and persisted for many centuries was the use of
mixing| o f saltpeter (K N O j) with charcoal; or fire ships in marine warfare. The earliest recorded
natural] tars and resins, animal fats, volcanic dusts, mention of fire ships is from the 4th century B.C.
salts, sulfur, or other flammable materials. when the Phoenician seamen of Tyra used them in
In modern warfare, some of the important uses battle against Alexander the Great. Later records
for pyrotechnic devices are: as incendiaries; as show that the Greeks used them against the Turks,
luminous sources for missile tracking; as acces­ the Crusaders used them at Acre, and the English,
sories in aircraft, missiles, and nuclear 4 evices; in the 16th century, used them with success against
to produce sound signals; and to produce visible the Spanish Armada.
luminous and smoke signals. Illuminating devices
are also used for photography.4 Recent adaptations 1-2.1 GREEK FIRE
include devices designed for actuation by radio
One of the earliest and most successful means of
signals1 directed to a missile thousands o!f miles
chemical warfare was the mixture known as Greek
from earth. '
fire, the use of which is first reported in the 7th
century, A.D. This mixture of sulfur, resin, cam­
1-2 EARLY HISTORY1235 07 phor, and other unknown combustible substances,
Incendiary and colored smoke mixtures were melted with saltpeter, was a powerful incendiary
used for war, religious celebrations, and er tertain- that also produced suffocating fumes. It was used
ment in Arabia, China, Egypt, Greece, and India in many different ways. Sometimes woolen cords
in very ancient times. As early as 2000 B.C., tales were soaked in the mixture, dried, and rolled into
of war in India mention incendiaries, smoke balls. The balls were then lighted and hurled by
screens, and noxious fumes. Later, against Alex­ large engines at enemy ships or tents. Defenders of
ander jthe Great (365-323 B.C.), defenders of an cities prepared it in liquid form ; poured it into
(ndiaii city were reported able to “ shoot thunder ja rs; then ignited the mixture and poured it upon
and lightning from the walls. ’ ’ To this day. natural those besieging the city walls. In open battles,
deposits of saltpeter are abundant in India, and it was squirted by hand pumps and bellows through
probably served as a source of this material for pipes into enemy ranks, or against wooden barri­
employment in the compositions making these dis­ cades. In 901 A.D. the Saracens were reported to
plays’possible. have blown it from pipes mounted on the decks of
Knowledge of pyrotechnics traveled from the their ships. Five centuries later, in Emperor Leo’s
East to Europe at the beginning of the (Christian attack on Constantinople in 1453 A.D., 2000 enemy
era. The earliest record of pyrotechnic exhibitions ships were reported destroyed by its use.

i
1-1

1
 AMCP 706-185

1-2,2 CHINESE PYROTECHNICS j the use of contact or short range incendiary de­
Records of Chinese pyrotechnic items go back vices.
to the 10th century. Rockets and Roman candles
are mentioned in 969 A.D. and, by the 13 th cen-
1-2.4 MISCELLANEOUS USES
. tury, colored smokes for signaling, incendiary­
The first recorded use of screening smoke in
carrying fire arrows, and rocket-propelled arrows
more recent times occurred in 1701, when Charles
were employed. The rocket-propelled arrows, fired
X II of Sweden burned damp straw to produce a
in clusters from metal containers, were sometimes
smoke screen to cover a river crossing. Elsewhere
fitted with poisoned razor-sharp heads for attacks
in Europe at this time pyrotechnic devices were
from ambush and the defense of defiles. ) Other
being developed for their military value. The
Chinese weapons of this time included “ flying fire
French kings encouraged experiments and tests,
spears” equipped with tubes that threw fire for­
saw that proper records were kept, of which many
ward for about 30 feet. Pyrotechnic devices were
are still available, and collected information from
also used in defending cities—the Kin Tarters
travelers returning from other countries. French
are known to have used fire powders and other priests returning from China brought detailed
pyrotechnic devices against a Mongol attack in knowledge of the state of the art in that country.9
1232 A.D.

1-3 18TH AND 19TH CE N TU R IE S-386

1-2.3 GUNPOWDER l
. i| Berthollet’s discovery of potassium chlorate in
The inventor of gunpowder is generally be­
1 1788 began the modern era in pyrotechnics. Po­
lieved to have been the English philosopher, |Friar
tassium chlorate made color effects in pyrotechnic
Roger Bacon. In 1242 A.D. he revealed the in­
flames possible and the introduction of magnesium
gredients for black powder in defending hlimself
in 1865 and aluminum in 1894 added greatly to the
against an accusation of witchcraft. Although
variety of effects attainable.
Bacon knew of the explosive power of gunpowder,
' In Europe there was also a great interest in
he apparently did not recognize the possibility of
ithe use of rockets. Several types were developed,
using it for projection of missiles. !l
the most successful being the Congreve rocket,
The earliest recorded useof firearms or o f gun­
which was 30 inches long, 3*4 inches in diameter,
powder as a propellant is in the beginning o f the and carried an incendiary charge. The British
14th century. Records of the University of Ghent used rockets with pyrotechnic compositions in a
in Belgium indicate that the first gun was invented number of campaigns. A rocket corps was part
by Berthold Schwarz in 1313, and commercial of the British Army during the Revolutionary War,
records indicate that guns and powder were ex­ and again during the War of 1812. The 1805 ex­
ported from Ghent to England in the following pedition of Sir Sidney Smith against Boulogne
year. Guns and gunpowder may have been Iused included boats fitted for salvo firing of rockets, and
in the English invasion of Scotland in 1327 but rockets were used successfully in the British attack
the earliest undisputed record of the use of gun­ on Copenhagen and by W ellington’s army.
powder in war is in France at the battle of C’recy , In the United States at this time, a number of
in 1346. Gunpowder was also used as an explosive pyrotechnic devices were items of general am­
to blast fortification walls, the first reported at­ munition issue. An 1849 Ordnance manual de­
tempts being at Pisa in 1403, and in land mines, scribes signals, lights, torches, tarred links, pitched
which were described in 1405. l| fascines, incendiary matches, and other illumina­
When gunpowder began to be used as a |;pro- tion devices. The manual also lists firestone,
pellant in the 14th to 15th century, the usefulness Valenciennes composition, and fireballs— incendi­
o f the incendiaries then available declined. ] Be­ aries, when projected from mortars, designed to
cause o f the use o f gunpowder, armies began to set fire to enemy property. Besides the Congreve
engage each other at such distances as to prohibit rocket, which came in 2*4- and S^-inch sizes. The

i ■
1-2 i
j
 AMCP 706-185

2^4-inch rocket had a maximum range of 1760 screens with success at the Battle of Jutland in
yards and, the 3x/4-inch rocket had a somewhat 1916.. As a result of this success, the Allies and
greater range. The rockets were made of sheet or the Germans developed pyrotechnic screening smoke
cast iron and fired from tubes mounted on portable for use on both land and sea during W orld War I.
stands or light carriages. An 1861 Ordnance
manual lists most of the 1849 devices with more
1-4.1 WORLD W AR I
detail and some improvements. Two new items
During World War I, opposing troops in
were also/listed: an incendiary projectile filling
trenches separated by short distances regularly
called rockfire, which burned slowly and was hard
employed pyrotechnic devices. Illuminating pro­
to extinguish. It was employed to set fire to build­
jectiles were used as protection against surprise at­
ings, ships, and flammable stores. Another new
tack, and signals were used to request, adjust, or
device was the petard, a powder-filled wooden box
stop artillery fire; to mark enemy and friendly
that was used to demolish doors, gates, barriers,
troop locations; and for emergencies on land, sea,
and other, obstacles.
and in the air.
A number of gunpowder improvements were
The advent of the airplane overcame the diffi­
made in the United States and Europe during the
culties of using incendiaries against distant armies.
latter half of the 19th century. After General
Forerunners of today’s incendiary bombs were
Thomas J. Rodman, U.S. Army, discovered the
first dropped on London in May 1915 from Ger­
principle o f the progressive burning of propellant
man Zeppelins, and a prototype of the portable
powder ih 1860, powder grains were made in sizes
flamethrower was used by the Germans against the
adapted to the caliber of gun, with larger and
French in April and June of that year, although
perforated grains used in larger weapons. The
with little success. Later in the war, bombs con­
Swedish inventor, Nobel, made many of his im­
taining white phosphorus, thermite, and thickened
portant discoveries at this time. In 1863 hej first
liquid fuels were dropped from airplanes.
manufactured nitroglycerin commercially, and dur­
Before and during W orld W ar I most pyro­
ing the next twenty years invented dynamite, the
technic development and manufacturing in the
fulminate blasting cap, blasting gelatin, gelatin
United States was carried out by private contrac­
dynamite, and ballistite. Another improvement
tors to the Army or Navy. The Star rifle light, the
came in 1886 when Vieille, a French chemisi;, dis­
Very pistol, position lights, and simple rockets
covered the means to colloid nitrocellulose and thus
were the main items used. As the war continued,
control the grain size of the propellant powder.
the armed services began to test and develop pyro­
technic devices for special purposes.
1-4 EARLY 20TH CENTURY *.3.w .»,M ° The use of chemical agents during the war re­
An important pyrotechnic development early sulted in the establishment of a Chemical Warfare
in this century was the tracer bullet. Tracers have Service in 1918. This organization became a
been used in all types of projectiles, but their de­ permanent branch of the U.S. Army in 1920,
velopment has been most closely connected with and in 1946 its name was changed to the U.S. Army
ammunition for automatic small arms, tracers Chemical Corps. This technical service pursued
were the best devices for directing automatic small the development of incendiaries, screening and sig­
arms fire against fast moving ground targets. In naling smokes, flame throwers, and toxic chemical
this country, research and development of small compounds.
arms tracers was carried out at Frankford Arsenal. Aberdeen Proving Ground in Maryland Was
The U.! S. Navy and Picatinny Arsenal also con­ activated in October 1917, and by December of
ducted tracer development for 20 mm, 40 mm, and that year was making acceptance tests of ammuni­
larger guns. tion and other Ordnance materiel. Aberdeen rec­
The German Navy conducted fleet maneuvers ords for 1918 list tests o f illuminating parachute
using chemically produced screening smoke for the projectiles for the 155mm gun.
first time in 1906, and later used such smoke Frankford Arsenal, during the early days of

1-3
AMCP 706-185

the war, adapted foreign pyrotechnic compositions! been little scientific testing of pyrotechnic de­
to small arms ammunition. Later, it developed! vices, the body of data that existed at Picatinny
tracer and igniter compositions and started a well- Arsenal at the outbreak of W W II was of: con­
integrated program for standardization. These siderable value in developing improved pyro­
early tracer compositions were made by a small1 technic items needed for the highly mobile forces
batch process, wet mixed, dried, and ground to, of that war.
produce a stable, uniform composition. These early' Aberdeen Proving Ground added development
compositions were only moderately satisfactory in i testing to its proof testing in the 1920’s. In 1921
that the calomel used as a flame brightener pro­ development tests were reported on green, yellow,
duced season cracking in brass, and also limited ■ and white smokes, and two years later tests of long
the life of the composition. | burning white parachute signals were conducted.
During the war the Navy developed and used 1 About 1933, Frankford Arsenal refined the
3-, 4-, 5-, and 6-inch illuminating projectiles with process of making tracer compositions so that only
a projection range up to 7 miles, a major advantage 1 the calcium resinate and the hygroscopic strontium
because the Star rifle light was projected to a maxi­ peroxide were wet mixed. Since then, streamlining
mum range of only 800 yards. The Navy:|also de- : of the process has continued and now all ingredi­
veloped water markers for use from submarines, as ! ents in the tracer mix are purchased ir. the required
well as for dropping from aircraft. These jlmarkers granulation, blended dry, and charged into bullet
consisted of surface burning smoke and flame-pro- ! cavities under high'pressures; In 1936 Frankford
ducing items, colored aerial stars, and i surface began developing delay action and dim igniters,
marking dyes. ' some of which are now standard compositions. Just
before the United States entered W orld W ar II,
Frankford greatly improved incendiary mixture
1-4.2 BETWEEN THE WARS
! IM-H. This standard incendiary mixture, which
During the period between W orld |W ar I was originally developed by Picatinny Arsenal,
and World W ar II, arsenals, such as Piieatinny was quickly adopted by the British and was used
and Frankford, and the Army Chemical Corps ,by American forces in all small arms incendiary
carried on limited research on military applications bullets,during World War II.
of pyrotechnics. Some universities also assisted The Navy pyrotechnic development between th e!
in this work. | ' wars was centered at the U.S. Navy Yard in
Picatinny Arsenal, which had been established Washington, D. C. Production was carried out at
by the Ordnance Corps in 1879 as a small powder ■ the Naval Ordnance Plant at Baldwin, New York.
depot to manufacture and load munitions1, began For a time its one product was illuminating pro­
loading propellant charges in 1896, projectiles in ' jectiles, but in 1930 production of aircraft para-
1902, and propellant manufacture in 1907. In j chute flares was also added. Also, by 1933 the
1919, it began to develop and manufacture pyro­ ! Experimental Ammunition Unit of the Naval Gun
technic Signals, and continued the pyrotechnic , Factory had developed a number of pyrotechnic
research and development effort in the period be­ items including emergency identification signals,
tween the wars. During this time, it made con­ ; aircraft signal cartridges, and ammunition tracers.
siderable progress in developing new smoke, flare,
tracer, and delay compositions, and beganjto ac­
cumulate evidence regarding the necessity for 1-4.3 WORLD W AR II
purer ingredients, more careful control of particle' In 1940, and later with the entry o f the United
size, and improved processing methods. Other in­ States into W orld W ar II, pyrotechnic items such
vestigations produced techniques to measure lu­ as flares, illuminating projectiles, smoke signals,
minosity and color of pyrotechnic flames, technical spotting charges, many types of ground and air­
requirements for specifying ingredients, and'recog­ craft signals,! and incendiaries were needed in
nition of the importance of avoiding moisture in enormous quantities. -
pyrotechnic compositions. Although there had Flares were widely used to illuminate landing

1-4
 AMCP 706-185

fields at night, in rain, and in fog. They Were tracers, and troop warning devices were developed
dropped from aircraft to illuminate enemy terri­ to meet the new tactical requirements. New in­
tory; to silhouette ships for observation; and to gredients such as atomized magnesium, resins, color
locate targets for bombing. Photofiash bombs il­ intensifies, and others were tested and adopted;
luminated large areas for night photographyj improved techniques to measure luminosity and
Smoke screens were used by land and sea forces color, such as the barrier-layer cell photometer,
for a variiety o f purposes: aircraft and smoke mats were introduced.
screened ships during air attacks and amphibious The Ballistic Research Laboratories had been
landings,; concealed underwater demolition teams established in 1938 to centralize research activities
and tactical maneuvers of ground troops. at Aberdeen Proving Ground and to undertake re­
B y the end of the war pyrotechnics provided search in fundamental Ordnance problems. With
visual communication both day and night between completion of a new laboratory in 1941, basic
planes and tanks, tanks and artillery, infantry studies were begun in areas pertinent to pyrotech­
and aircraft, and ships and the shore. nics such as flame propagation, burning rates, sen­
Incendiary bullets, bombs, projebtiles, and sitivity of pyrotechnic compounds, and the physical
grenades! were widely used in Europe. Allied tac­ chemistry of gases. ,
tics in bombing German cities employed equal Naval pyrotechnics development during World
quantities o f incendiaries and high explosives. On W ar II was centered at the Naval Ordnance
a weight basis, the incendiary bombs cause 1 five Laboratory, then located at the Naval Gun Factory,
times more damage than high explosive bombs. The Washington, D. C., and production was centered
central parts of more than 50 of Germany’s largest at the Naval Ammunition Depot, Crane, Indiana.
cities were leveled by fire. Before nuclear weapons The Navy improved existing items for greater re­
were used fifty percent o f 70 Japanese cities had liability and storage characteristics, and developed
been buraed. More than 99 percent of the total such items as chemical delay powders, self-releas­
bomb load dropped on Japanese cities was in­ ing buoyant submarine signals, rescue flares, depth
cendiary, with less than 1 percent high explosive. charge markers, aircraft signal cartridges, and
During the war, hundreds o f millions of incendiary parachute flares.
bombs, projectiles, and grenades were provided by
the Chemical Warfare Service— over 48 million
incendiary bombs alone were supplied to ti e U.S. 1-5 POST WORLD W A R II PERIO D 4 12
Army A ir Force. Funds for research and development of pyro­
Flame throwers, which had been developed technic items were limited in the period following
during W orld W ar I, were improved and used with World War I I ; however, significant advances were
success in the campaigns in the Pacific areas during accomplished which made available improved pyro­
W orld W ar II. technic devices, signals, smokes, incendiaries, and
Picatinny Arsenal developed many improved battlefield illuminants when the Korean Conflict
pyrotechnic items to meet the military change developed in the early 1950’s.
from trench warfare, which had existed in World Most pyrotechnic research' and development to­
W ar I 1 , to the highly specialised mobile forces day is carried out by the Government at Picatinny
o f W orld W ar II. Pyrotechnic ammunition for Arsenal, Aberdeen Proving Ground, Frankford
military maneuvers and means for providin g visual Arsenal, the Army Chemical R&D Laboratories,
communication among the various elements in­ the Naval Ordnance Laboratory, the Naval Ord­
volved'were essential. More efficient flares, flash nance Test Station, the Naval Ammunition Depot,
charges, and a variety o f spotting charges, signals, and by Government-sponsored agencies.

1-5
AMCP 706-185

REFERENCES
1. tt. T. L. Davis, “ Early Pyrotechnics. I. Fire : Dictionary of Applied Chemistry, Vol. X , p.
for the Wars of China; II. Evolution of the! 781, Logmans Green, London, 1950.
Gun; TIL Chemical Warfare inj Ancient1 8. History of Research and Development o f the
China,’ ’ Ordnance 33, 52, 180, 396 (1948-49). Chemical Warfare Service in World War II,
b. L. Katz, “ Pyrotechnics in Missile Design,” published for The Chemical Corps Association,
Ordnance 44, 334 (3959). I <■ Washington, D. C., Reinhold, N. Y*., 1948.
9. L. P. Broph?, D. M. Syndam, R. C. Cockrane,
c; H. Ellern, “ Military Pyrotechnics,” Ord-1
The Chemical Warfare Service from Labora­
nance 44, 662 (i960). I
tory to Field, Office of the Chief of Military
2. T. L. Davis, Chemistry of Powder and Ex- ,
History, Department of the Army, Washing­
plosives, John Wiley & Sons, Inc., New York, 1
ton, D. C., 1959.
1943. | !" 10.
C. H. Custard, G. Francis, W . Schnackenberg,
3. H. B. Faber, Vol. 1, The History and Develop- j
Small Arms Incendiary Ammunition, A Re­
mewl of Military Pyrotechnics, U. S'. 'Govern- j
view of the History and Development, Frank-
ment Printing Office, Washington, D. C., 1919. ;
ford Arsenal Report R-1407-3, December 1956
4. S. Sage and R. W. Evans, “ Pyrotechnic Re­ 11. L. Finkelstein, A. E. Gaul, Incendiaries, Vol.
search Comes of Age, ” Ordnance ||48, 262 j
' 18, History of Research and Development of
(1964).' ' ' . j /
Chemical Warfare Service in World War II,
Alan St. II. Brock, A History of Fireworks,
published for The Chemical Corps Association,
George C. Hanap and Co., Ltd., London. ’ Washington, D. C., Reinhold, N. Y., 1948.
6. A. M. Prentiss, Chemicals in War, McGraw- 12. D. Hart, Research and Development of Mili­
H ill Book Co., New York, 1937. tary Pyrotechnics. Picatinny Arsenal. Dover,
7. K. F. Sawyer, “ Screening Smokes,” Thorpe’s ! N. J., 1955. ' '

1-6

.. . -1
 AMCP 706485

CHAPTER 2

INTRODUCTION TO M ILITARY PYROTECHNICS

2 4 INTRODUCTION With the advent Of the space age, pyrotechnic-

Modern military pyrotechnics as an outgroWth devices have become increasingly important. They
of “ Greek F ire” and the “ art of making 1 ire- are used extensively for spotting and tracking
works” has progressed to the extent where pyro­ rockets and missiles, for recovery operations, and
technic devices and systems in both offensive and for special purpose countermeasures. To meet the
defensive military operations have become indis­ requirements for these applications, it has been
pensable. it has developed into a science requir­ necessary to investigate pyrotechnic reactions un­
ing extensive and intensive basic and applied re­ der conditions of low pressure, low temperature,
search to meet new conventional and unique nili- greatly reduced quantities of atmospheric oxygen,
tary and space requirements. varied degrees of confinement, and with different
The early modest state of progress was char ged types of initiating systems.
considerably, however, when military operations Basic studies have been undertaken to attain
became mechanized with the development of the a fundamental understanding of the preignition,
ignition, and self-propagative reactions of pyro­
tank, the bombing plane, the submarine, long-range
technic ingredients. Theories have been developed
artillery, the aircraft carrier, other vehicles, and
which are used as a guide for formulating flame
weapons; and the introduction of combined opera­
compositions burning cigarette-fashion, with spe­
tions. T o ’ coordinate all these forces and to pro­
cific burning rate requirements. Theoretical and
vide for Visual communications between plane and
empirical relationships have been developed to
tank, tank and artillery, infantry and air force,
predict the rates o f propagative burning o f slow-
both day and night, the development of pyrotechnic
burning pyrotechnics as a function o f particle size
ammunition for these purposes was absolutely
and composition. Instrumentation has been de­
essential. Increased use o f aircraft for bombing
veloped to evaluate luminous intensity and colors
and observation purposes required the use of flares
of pyrotechnic flames, luminous intensity and dura­
and photoflash bombs which could be released i'rom
tion of flashes, color of smoke clouds, and improved
rapidly moving planes to illuminate enemy terri­
output of pyrotechnic flares. Laboratory studies
tory for night photography and observation and to
include use of thermal analytical techniques, spec-
locate targets for bombing.
trophotometric and chromatographic analyses.
A variety o f smoke signals, spotting charges;
To continue to meet new challenges, principles
bombardment flares, illuminating shells, ground and
and theories of engineering and science must be ex­
aircraft signals had to be developed to satisfy new
ploited and put to practice. Only when this is done
tactical requirements. New demands for signaling
will it be possible to elucidate reaction mechanisms,
capability required the development of improved
performance of pyrotechnic devices and to de­
colored smokes and signals.
velop superior compositions and items.1'2'8’4'8-8
For submarine identification and air-sea r<scue
operations, sea water activated, battery-operated;
floating marking signals were developed with good 24.1 PYROTECHNIC DEVICES
life and stability. Many types o f simulator i for AND USES1-2'8'7'9'10
land and sea troop training were also developed The terminal effect of military pyrotechnic
and became an indispensable aid in these opera­ items such as light, heat, smoke or sound results
tions. from a n . exothermic oxidation— reduced chemical
AMCP 706-185

TABLE 2-1
TABULATION O F ! PYROTECHNIC DEVICES

1. Flares 1
a. Reconnaissance
b. Observation
c. Bombardment
d. Deplaning and emplaning ofj troops and materiel
e. Prevention of enemy infiltration or reconnaissance
f. Target identification |
g. Battlefield illumination i
h. Marking targets and bomb release lines
i. Emergency airstrip location |andidentification
j. Decoys
[
k. Missile tracking

Signals
a. Between various elements of j ground troops
b. Between ground troops and Iplanes, or vice versa
c. Between planes in the air j
d. Search and rescue operations (locate survivors)
e. Submarine to surface or air .
f. Precision location of point or, time in space for assessment of missile
function | ( j .■ ■ .
g. Establishment of points on a trajectory

3. Colored and White Smokes j

a. For daytime signalling
b. For screening
c. For spotting
d. For marking targets
e. Thermal attenuating screen 1
f. Dissemination o f chiemical agents
g. Tracking and acquisition
h. Rescue

4. Tracers
a. To trace trajectorie i of projectiles or rockets
b. For self-destruction o f ammunition after a definite time interval

5. Incendiaries !
'll i ■
a. F or use against ground targets
b. For use against airjciraft targets ,
c. F or emergency document and equipment destruction

6. Pyrotechnic Delays j '

Time delay for explosive trains . ,
7. Photoflash. Bombs andl! 'Cartridges j•
Aerial night photography ,
8. Spotting and Tracking

2-2

j
 AMCP 706-185

; :-v.t '
■ : . TABLE 2-1 (cont’ d)

9. Atmosphere and Space Studies .

10. Simulated Ammunition for Troop Training
11. Rocket Igniters
12. F uel Igniters fo r Ramjet Engines and Guided Missiles
13. A ircraft Engine Igniters
14. W ater Markers
15. Heat Sources
16. Special Devices

reaction within a mixture of a fuel and an oxidint. luminous intensity through an appropriate colored
Additives or modifiers may be included to produce filter to the total luminous intensity.
more saturated colored fiames, to adjust burning e. Visibility. Applied to illuminating and sig­
rates, to produce colored smoke clouds, and to nal devices; measured in terms of brightness and
increase storage life and processing safety. • other qualities.
Pyrotechnic devices are employed in such a f. Efficiency. Relates the output to the original
large variety of munitions that classification is weight or volume of compositions; fo r illuminating
difficult. These devices are, however, tabulated, or signaling it is expressed as candle/seconds per
with their principal uses, in Table 2-1. gram or per milliliter; for smoke-producing devices
efficiency is considered to be the percent o f chem­
2-1.2 CHARACTERISTICS OF PYROTECHNIC ical vaporized based either on the weight of chem­
COMPOSITIONS1-2-4®-7 ical originally contained or on the total weight of
The applicability of a specific pyrotechnic mix­ munition, depending on the requirements of the
ture for a particular application is governed by evaluator.
many “ yardsticks.” Consideration must be given, g. Color and volume o f smoke. Compared to
not only to the terminal effectiveness and output standard charts or by observers’ ability to detect
desired, but also to overall performance and re­ and recognize, at prescribed distances, the color
producibility, and processing and storage char­ and the total obscuring power (T O P ).
acteristics. Precise and analytical determination
2-1.2.2 Processing and Sensitivity Characteristics
o f the various parameters involved requires .con­
Information on the processing, storage, ship­
tinued research to develop improved evaluative
ping, and sensitivity characteristics o f pyrotechnic
methods. , .
compositions can be found! in Part Two o f this
The more important characteristics of pyro­
series, AMCP 706-186.
technic compositions used for military purposes
may be stated as follows: 2-1.2.3 General Functioning Characteristics
: ■ . 1 '. ■ ^
a. Ignitibility. The ease with which a pyro­
2-1.2.1 Perform ance Characteristics technic composition ignites, determined by standard
a. Heat o f reaction, cal/gm or cal/cc. May be tijne-to-ignition tests described in Part Two o f this
used as a; basic criterion for selection o f fuel-oxi­ series, AM CP 706-186.
dizer combinations. • b. Hygroscopicity. The ease with which a com­
b. Burning rate, inches/second, inches per position picks up moisture at a preselected tem­
minute, seconds/inch. Applied to consolidated mix- perature and relative humidity.
tures and measured as a linear rate. c. Reaction characteristics. Fundamentally im­
c. Luminous intensity, candela or candlepower. portant are the heat o f reaction and rate o f reaction
Visible output or illumination in candela. o f a pyrotechnic composition; To make a consoli­
d. Color value. The color quality of a colored dated composition burn propagatively, sufficient
pyrotechnic flame taken as the ratio o f the apparent heat must be evolved and the rate o f reaction must

2-3
AMCP 706-185

be of sufficient magnitude to more than compen-1 2-1.3 Constituents in Pyrotechnic

sate for heat losses. ' | , j Compositions1’2'4’8'7
In addition to the heat of reaction and the rate f The constituents upon which the performance
of reaction, display characteristics are influenced i of pyrotechnic compositions and devices is depen­
by many other factors. Some of the more impor- i dent include a basic fuel and oxidizer combination
tant include: 1 j, with other ingredients. These may consist of
dyes, color intensifies, retardants, binding agents,
1. Granulation or particle size of ingredients 1
water-proofing agents, and substances to create a
2. Composition of ingredients
specific effect.
3. Purity of ingredients
Typical ingredients in each of these categories
4. Burning surface area
are:
5. Heat transfer characteristics
6. Flare case material and configuration 1. Oxidizing Agents. Nitrates, perchlorates, per­
7. Loading pressure oxides, oxides, chromates and chlorates. These are
8. Presence of moisture all substances in which oxygen is available at the
9. Degree of confinement high temperatures of the chemical reaction in­
10. Ambient temperature and pressure volved. In addition, fluorinating agents such as
Teflon and Kel-F are finding use as oxidizing
11. Method of ignition
agents.
12. Length-to-diameter ratio
2. Fuels. Metal powders, metal hydrides, red
13. Method and energy of dissemination
phosphorus, sulfur, charcoal, boron, silicon, sili-
14. Bomb burster geometry i(
cides. When these substances are finely powdered,
15. Velocity, acceleration and aerodynamics of
they readily undergo an exothermal oxidation with
device ■. j|
the formation of corresponding oxides and the evo­
lution of heat and radiant energy.
The importance of a particular influential fac­
3. Color Intensifiers. Highly chlorinated or­
tor may vary considerably with the application.
ganic compounds, such as hexachloroethane
Factors such as the average particle diameter, spe­
( C2Cle), hexachlorobenzene (CeCle), polyvinyl­
cific surface, shape, and distribution will affect the
chloride, and dechlorane (C 10 CI1 2 ). These com­
burning rate of consolidated pyrotechnic mixtures.
pounds are utilized to produce specific spectral
Changes in the general characteristics of the flare
. emitters in pyrotechnic flames.
case and the area of the burning surface combine
4. Retardants., Inorganic salts, plastics, resins,
to influence the output of flame producing items. waxes, oils. These are used to slow down the reac­
With pyrotechnic delay compositions, the|burning tions between the oxidizing agent and the powdered
rate is of primary significance and may bb varied metal to produce the desired burning rate. Some
by changes in the percentages and particle size of behave merely as inert diluents while others par­
the ingredients in the composition, incorporating ticipate in the reaction at a much slower rate than
additives, varying the compaction, and tty other the main constituents.
means. Nonconsolidated pyrotechnic photoflash 5. Binding Agents. Resins, waxes, plastics, oils.
mixtures used in flash items are influenced by the These are added to prevent segregation and to ob­
'i ■
method of ignition, ratio of length to diameter, tain more uniformly blended compositions. In ad­
burster geometry, and degree of confinement. dition, they serve to make finely-divided particles
In addition, there are many other factors pe­ adhere to each other when compressed into pyro­
culiar to the specific item under consideration that technic items and. help to obtain maximum density
may exert varying influences on performance. In and burning efficiency^ Binders also frequently
the design and development of new pyrotechnic desensitize mixtures which are otherwise sensitive
munitions, a fresh approach should always, lie. con­ to impact, friction and static electricity.
sidered, using the data available on existing de­ 6. Waterproofing Agents. Resins, waxes, plas­
vices only as a guideline. tics, oils, dichromating solutions. These are used

2-4
 AMCP 706-185

[JABLE 2-2
COMPARISON OF SOME PROPERTIES OF PYROTECHNIC
COMPOSITIOI IS W ITH EXPLO SIVES

Impact

Cal/gram

Brisance,
densable
Noncon­

Ignition
cc/gram

Crushed
Volume,

Temp*,
.* f*

Grams
*

Sand
Gas
a s •

°C
Composition mo m .5

PYRO TECH N IC:

Delay
Barium chromate 90
Boron 10 48<i 13 0 650 — 12

Delay
Barium chromate 60
Zirconium-nickel alloy 26
Potassium perchlorate 14 49' f 12 0 485 56 23

Flare
Sodium nitrate 38
Magnesium 50
Laminae 5 145 3 74 8 640 60 19

Smoke
Zinc 69 ;
Potassium perchlorate 19
Hexachlorobenzene 12 61 6 62 8 475 23 15

Photoflash
Barium nitrate 30
Aluminum 40
Potassium perchlorate 30 2147 15 7 700 100 26

H IGH E X P L O S IV E :
TNT 106 0 1000 48 475 100 14
RDX 1240 600 60 260 13 5

B LA C K PO W D ER 684 272 8 288 32 16

* 5-second value Bureau of Mines *** Picatinny Arsenal

as protective coatings on metals such as magnesium, than one function, thus simplifying the composition
aluminum and zirconium-nickel alloys to reduce of some pyrotechnic mixtures.
their reaction to atmospheric moisture.
7. Dyes for Smokes. Azo and anthraqmnone 2-1.4 Comparison of Pyrotechnic Mixtures
dyes. These dyes provide the color for smokes used and Explosives1•2i9-10 '
for signaling, marking, and spotting. Pyrotechnic mixtures can be devised to produce
Many of the above substances perform more as little as 200 calories per gram o f mixture or in
AMCP 706-185 i

excess of 2000 calories per gram. Reaction tem­ i explosives.

peratures exceed 3000°K in some cases. | ' A comparison of some of the more important
Such amounts o f energy and the high tempera­ properties of pyrotechnic compositions and ex-
tures attained can be extremely dangerous. In gen­ 1 plosives is given in Table 2-2. As indicated in this
eral, because the quantity o f gas produced (if: less, ) table, pyrotechnic compositions, in general, are not
and the release of energy is at a lower rate, the 1 as sensitive to heat as explosives. Impact values
terminal effects produced by pyrotechnic composi­ i listed indicate that some pyrotechnic compositions
tions are less severe than those produced tly high 1 are at least as sensitive to shock as explosives.

I ;
REFERENCES
1. G. Weingarten, Chemistry of Pyrotechnics, { 5. L. Katz, “ Pyrotechnics in Missile Design,”
oral presentation at Picatinny Arsenal, Dover, j Ordnance 44, 334 (1959).
N. J., 1955. J j 6. TM 9-1910, Military Explosives.
2. D. Hart, Research and Development of Mili- •
. 7. TM 9-1370-200, Military Pyrotechnics.
iary Pyrotechnics, Picatinny Arsenal, Dover, . 8. H. Ellern, “ Military Pyrotechnics,” Ord-
N. J., 1955. j| , i nance 44, 662 (1960).
3. S. Sage and R. W. Evans, “ Pyrotechnic Re­ 9. T. C. O ’Hart, Elements of Ammunition, John
search Comes o f A ge,” Ordnance 48, 262 ! W iley & Sons, N. Y., 1946.
'(1964). j . I 10. T. L. Davis, Chemistry o f Powder and E x-
4. H. Ellern, M odem Pyrotechnics, Chemical I plosives, John W iley & Sons., N. Y., 1943.
Publishing Co., 1961.
 AMCP 706-185

C H A PTE R 3

PHYSICAL-CHEM ICAL RELATIONSHIPS

The output characteristics o f a pyrotechnic Similar expressions can be written with T and p as
munition are determined, to a large extent, by the the dependent variable. I f a system has n com­
temperatures to which the reaction products ire ponents, Ti-l composition variables must be speci­
heated as a result of the chemical reaction between fied.
the fuel and oxidizer. The maximum temperature
of the reaction products depends on: (1) the state 3-1.1 TH E GASEOUS STA TE
of the products at the reaction temperature, (2) The gaseous state is characterized by changes
the heat evolved by the exothermal chemical reac­ in volume with changes in temperature and pres­
tion, and (3) the rate o f heat production and heat sure. Gases normally have no bounding surface
loss. Physical-chemical relationships allow the and, therefore, tend to completely fill any avail­
state of the! products, the energy released, and the able space. A knowledge of the behavior of gases
maximum reaction temperature to be calculated. with changes in temperature and pressure is es­
The rate o f heat production and heat loss, which sential because of the importance of the gaseous
are influenced by the ambient temperature snd state at the high temperatures involved in pyro-
pressure, confinement, and many other inter re­ chemical reactions.
lated factors, can also be calculated for certain Gaseous products formed in the combustion of
simple cases. However, for most reactions, these many pyrotechnic mixtures may range from es­
quantities must be determined experimentally. sentially zero, for most thermites and some types
The physical-chemical relationships which are of delay mixtures, to 15 to 20 percent for light-
applicable to pyrotechnics are summarized in this producing compositions, to 50 percent for some
chapter, and pertinent examples are given to il­ smoke-producing mixtures. A t the high tempera­
lustrate their application. tures produced by the burning o f pyrotechnic
compositions, many substances not usually con­
3-1 STA TE OF A SYSTEM sidered gaseous will exist in the gaseous state.
i ■ _
The state o f any system (gas, liquid, or solid) The formation of gas, both as a permanent product
can be described by specifying a sufficient num her and as an intermediate product which exists only
o f its properties such as mass, volume, temperatu re, during the reaction, is indicated in light-produc­
and pressure. These properties are classified IS: ing mixtures by the presence o f a flame. Gaseous
(1) extensive properties which depend on the size combustion products are necessary in smoke-pro­
of the system, and (2) intensive properties wh ich ducing mixtures to aid in the formation of dis­
are independent of the size of the system. It 18 persed, particulate matter and to carry this matter
unnecessary to specify all the properties o f a sijys- into the atmosphere.
tern in order to characterize its state; two indep::n-
dent variables, commonly the intensive variables of 3-1.1.1 Ideal Gases
pressure and temperature, are sufficient for a givien The behavior of gases at low pressures and
amount'of pure substance. A mathematical expn high temperatures is often approximated by an
sion for this relationship is an equation of stite equation o f state known as the ideal gas law:
which, for one mole o f a pure substance with vol-
W
ume as the dependent variable, has the form : 'pv = nRT (3-2)
. a
V = f(T ,p ) (3 ll) where p is the pressure, v is the volume, n is the

3-1
AMCP 706485

number of moles, B is the universal gas constant, be g^ven in weight units of a particular gas in-
T is the absolute temperature, W is the weight of |stead of in moles. In this case:
gas, and M is the molecular weight of the gas, us­
ing any set o f consistent units. The density d of m _R (3-5)
B - If
an ideal gas at various temperatures and pressures
is: where M is the molecular weight of the gas, and R
is the universal gas. constant.
W_ pM
d= (3-3)
v BT
; 3-1.11.3 Real Gases
The ideal gas law applies, strictly, toj a hypo- ! • *
thetical gas, which is composed of mass points be­ In a real gas, the forces acting between the
tween which no forces are acting. At the high molecules as well as the volume of the molecules
temperatures and relatively low pressures pro­ cause deviations from ideal behavior. Several equa­
duced by burning Unconfined pyrotechnic com­ tions o f state have been proposed to more closely
positions, the ideal gas law is fairly accurate; At approximate the behavior of real gases. Some of
the higher pressures which may be produced when - these equations of state include:
a confined pyrotechnic composition is burned, the Van der Waal’s Equation :
behavior may deviate appreciably from that of an
ideal gas. [p + (v — nb) = nBT (3-6)

34.1.2 The Universal Gas Constant and Standard |where o is a correction for the forces between mole­
' . Conditions . |: ! cules of a real gas, and b, termed the co-volume,
It has been determined that one mole of an j ; is a correction for the volume of the molecule.
ideal gas occupies 22.414 liters at 273.16?K and j The units used for a and b must be consistent with
one atmosphere. Then, from Equation 3-2: I those used for the other variables.

liter-atm A bel’s Equation:

R - P ! - (1 ) (22414) _
T “ (273.16) “ 0 08205 °K mole (p ) (v — nb) = nRT (3-7)
' - . - ■ . (3-4) where b ' is the correction for the volume of the
The universal gas constant B has the units of molecules. This equation, which is a modification
energy per degree-per mole. It may be calculated j of Van der Waal’s Equation, applicable where the
from Equation 3-4 for one mole of gas at standard : pressure is high, has been quite widely used for
conditions. The value of B must be consistent with calculations involving explosives and propellants.
the units of pressure, temperature, andi:volume Virial Equation:
used in the ideal gas law. Some values I t B in­
clude: I pv ™ n B T ^1 -J- -|-------^ (3-8)

Value Units
where the coefficients B, C, etc., vary with tem-
liter atmospheres
0.08205 ] perature and are called the second, third, etc.,
gram mole degree Kelvin virial coefficients. This particular equation is a
psia cubic feet | very general equation of state for real gases. By
10.73
pound mole degree Rankine using enough terms, the values calculated from
calories • ij, the above equation can be made to agree with ex-
1.987
gram mole degree Kelvin (perimental data as closely as desired.
BTU 4
1.987 Compressibility Factor
pound mole degree Rankine *
' . ‘ ’ '! ■ The deviation of a gas from ideal behavior can also
In some references, including many o f those deal­ be expressed by the use o f a compressibility factor
ing with rocke propulsion, a gas constant ^R1'may K where:

3-2
 AMCP 706-185

Bedeeed Pireeroi*

Figure 3-1. Compressibility Factors as a Function o f Reduced Pressure

pv allows a value for any one of the t^roe variables

K = 3-0)
nRT p, r, ami T to be calculated in terms of the other
variables with a fair degree of accuracy. The com­
or, in terms of reduced variables:
pressibility factor can be determined experi­
mentally or by calculation using a suitable equa­
K .= (Constant) (3-10)
tion of state.
in which a reduced variable is the variable div idcd
by its value at the critical point, i.e.:
3-1.1.4 Gas Mixtures
P. = (P/Pr), T r = ( T / T r ), and Vr = V / V c (3 11) Gas mixtures are normally treated by Dalton’s
Law, i.e.. „
The critical point is defined when the proper­
ties of a liquid and gas phase which are in equi­
librium become identical. The p, v, and T q lan- Ptntal — Pi -f- Ps -f" - - - - — S Pi (3-12)
<=1
tities, associated with this critical point, are de­
fined as p,'. tv, and T r. Therefore, as predicted by where the partial pressure p, of each o f the com­
the law of corresponding states, if K is plotted ponents is defined as the pressure which would be
against pr \at a given T r, a single curve will result exerted if it occupied the total volume at the same
for all gases as shown in Figure 3-1. The com­ temperature. (Jus mixtures can also be treated by
pressibility factor estimated from these curves the Amagat additive volume law :

3-3
AMCP 706-185

■ application of both of these laws to real gas mix­

V,otal = V1 + V2 ^--------- = S V i (3-13)
<=*1 ' tures is somewhat more difficult.1

where the volumes of the individual components

3-1.1.5 Sample Calculations
Vi, v2, etc., are the volume each would occupy at
Example O ne: Analysis of the product gases
the (total) pressure and temperature of the mix­
produced by a burning fuel block composition,
ture. For ideal gas mixtures, the results obtained
containing ammonium nitrate and charcoal, indi­
with this equation will be the same as thpsie ob­
cates that the reaction taking place could be repre-
tained by use o f the additive pressure law. The
; Sented by the overall reaction :

6NH4N 08( s ) + 4C (s) -> l l B 20 ( g ) + C O (g) + 3C 02(g ) + 6N2(g ) - f H2(g)

(a ) The volume o f gas produced per gram o f mix­

_ Molescoj
ture burned at standard temperature and pressure Pcot = {P lolal)
can be calculated from the above reaction and the 2 Moles*,,»ai
ideal gas law. The reaction produces 22 irloles of = 3/22 (1) = 0.14 atmosphere
product gases from 6 moles of NH4N 0 8 (480 Example T w o: A cylinder having a volume of
grams) plus 4 moles of charcoal (48 grams) or a pne liter is pressurized to 200 atmospheres with
total of 528 grams of fuel block. carbon dioxide at a temperature o f 40°C. The
Moles of gas per gram of fuel block turned: amount of carbon dioxide can be calculated b y :
22 (a) Assuming carbon dioxide behaves as an ideal
= 0.041 moles per gram
528 gas:,

Volume o f gas produced (S T P ) per gram of pvM (2 0 0 )(1 )(4 4 )

v= = 343 grams
fuel block burned is : RT ~ (0.082) (313)

, nRT _ (0.041) (0.082) (273) ! (b) Assuming that carbon dioxide behaves as a
~ P ~ 1 Van der W aal’s gas:
, = 0.918 liters per gram

(b) Since the actual temperature of the product

gases is 1000°C, the calculated volume at this tem­
[ p+(f^][«-(^)>] =^
perature and one atmosphere would be considerably
greater: For C 0 2, a = 3.59 liters2 atm m ole"2; b = 0.0427
liter mole-1
1273
Fiooo°o= 273
(0.918) = 4.28 liters per gram

(c ) The partial pressure of one o f the gaseous

products may be found by using the ideal gas law
and moles o f the component desired and the total
= - g - (0.082) (313) . .
volume for n and V. The partial pressure of carbon
dioxide would be calculated as follows:
Solving cubic equation in w : w — 625 grains
nc0,RT (3/528) (0.082) (273) j (c) Use of the generalized compressibility chart,
P COj =
V total = 0.918 ! ! Figure 3-1:
= 0.14 atmosphere J Critical pressure carbon dioxide = 72.9 atmospheres
,1 Critical temperature carbon dioxide = 304.2°K
Since the partial pressure is proportional, to the
mole fraction of each gaseous component, a simpler n _^ 2 2 . — 2 7 5
method would be: ! P r~~ 7 2 . 9 ” 2:78
 AMCP 706-185

313 . -0 .0 5 2 2 3 (540,000) , i „
1.03
: ’ Tr ~ 304.2 “ ><*» = ----------2873 ' +-,14'22
log p = 2.32 j.
Prom Figure 3-1, K = 0.42 p = 210 min mercury j ' '
pvM > (2 0 0 )(1 )(4 4 K . „ Q ■" The vapor pressure o f small droplets, such as
W~ KR T ~ (0.42) (0.082) (313) ~ mist droplets, is higher than the bulk Vapor pres­
\. i i
sure. I f p0 is the bulk vapor pressure o f [the liquid,.
The experimentally determined value is 835 grams,
the vapor pressure o f a droplet p is given b y :

3-1.2 THE LIQUID STATE '’ = * ( 1 + f i « r ) i <M5>

A liquid, like a gas, has no definite shape and,
where y is the surface tension, M is the molecular
hence, takes the shape of the vessel in which it is
weight, d is the density of the liquid, r is the radius
placed. The surface o f a liquid, in the absence of
o f the drop, R is the universal gas constant, and
other forces, will tend to contract to a minimum
area and is responsible for many of its charac teris­ T is the absolute temperature. j '
tic properties. The molecules o f a liquid ars leas
mobile than those in gases but more mobile than 3-1.2.2 Boiling Point .
those in solids. - ' The temperature at which the equilibrium
In pyrotechnic reactions, liquids are formed vapor pressure of a liquid equals the ambient pres­
by the melting of solids and condensation o f vapors. sure on the surface of the liquid is known as the
Liquid fuels must be vaporized before sustained boiling point. I f the ambient pressure is one at­
combustion will take place. The burning of many mosphere, the temperature at which the' liquid boils
solid fuels, including most o f the metal fuels, in­ is termed the normal boiling point, j For many
volves the formation and vaporization o f a liquid liquids, the normal boiling point is approximately
phase as a step in the combustion process. two-thirds o f the critical temperature.. According
to Trouton’s Rule, the number o f calories required
to vaporize one mole o f many liquids, including
3-1.2.1 Vapor Pressure some of the metals, is about twenty-one times its
The pressure exerted by a vapor, in equilibrium normal boiling temperature (degrees K elvin). By
with a liquid, is the vapor pressure of the liquid. use of Trouton’s Rule, the heat of vaporization of
The vapor pressure increases with temperature some of the metal fuels can be approximated if the-
until the critical temperature is reached above boiling temperature is known.8 i
which the liquid cannot exist. The vapor pressure Lithium has a boiling point o f 1331°|C (1604°K)
at the critical temperature is termed the critical and its reported heat o f vaporization is 32,190
pressure. The increase in vapor pressure with tem­ calories per mole. Applying Trouton’s Rule:
■ . ■ , ; { ,
perature can be approximated by the empirical AZIvop = 1604(21) = 33,700 calories per mole
equation :2 ,
3-1.3 THE SOLID STATE
— 0.05223a
lo g p = + b (3-14) Solids have a fixed shape and volume with the
individual units (atoms, molecules or ions) so
where p is the vapor pressure in milimeters o f mer­ firmly bound together that there is little freedom
cury, T is the absolute temperature °K, and a and for translational motion. Crystalline solids exhibit
b are empirically determined constants tJe each orderly internal arrangements and exhibit a sharp
liquid. For example, aluminum oxide in tile tem­ melting point. Crystals whose properties are dif­
perature range 1840°C to 2200°C has constants of ferent along different axes of the crystal are called
540,000' and 14.22 for. a and b, respectively. A t anisotropic; if-th e properties are the same, they
2100°C, the vapor pressure o f the liquid would be: are called isotropic. Amorphous solids (such as

3-5
AMCP 706-185

glass) may be regarded as super-cooled liquids of

high viscosity. They have indefinite melting points
/ 7 Z
•
7 4=71
and undefined internal arrangements. •
The properties of solids are important to the 1
study of pyrochemical reactions, which involve l /
solid ingredients reacting to produce mainly solid
products. Intermediate steps in the reaction in­ (I) (2) (3)
volve liquid and gaseous phases; however, some Simple Face-centered Body-centered
pyrochemical reactions may proceed by a solid- cubic cubic lattice cubic lattice
solid reaction mechanism. lattice .
There are 230 possible crystal forms which can
Figure 3-2. Cubic Lattices
be grouped into 32 classes which, in turn, can be
referred to one of the following six crystal systems: 3. Body-centered cubic lattice. One unit at
each corner of the cube and one unit in the
1. Cubic. Three axes of equal length inter­
center of the cube.
secting each other at right angles.
2. Tetragonal. Three axes intersecting each X-rays may be used to determine the internal
other at right angles with only two of the structure of crystalline materials, which can be
axes equal in length. S calculated by Bragg’s Law:
3. Hexagonal. Three axes of equal length in a )tX = 2 d s in 0 (3-16)
single plane intersecting at 60° angles, and
where n is the order of reflection, X is the wave­
. a fourth axis of different length and per­
length of the X-rays, d is the distance between two
pendicular to the plane of the other three.
planes, and 0 is the angle of reflection.
4. Rhombic. Three axes of unequal length in­
X-ray techniques are employed to identify
tersecting at right angles.
many solid products of combustion from pyro­
5. Monoclinic. Three axes of unequal length,
technic reactions.4 This is especially useful when
two of which intersect at right angles.
analysis of a particular product’s mixture would
6. Triclinic. Three axes of unequal length,
not be practical by wet, chemical methods and
none of which intersect at right angles.
where retention of the sample is desired.
The macroscopic symmetry of crystals is due Solids can be divided into three classes based
to the regularity of the arrangements of the ele­ upon their thermal and electrical conductivities-.
mental particles (atoms, ions, or molecules) in a 1. Conductors or metals which have high con­
lattice consisting of a three-dimensional repetition ductivities which decrease with an increase
of some structural unit of fixed dimensions. The in temperature.
unit cell is the smallest unit o f the crystal lattice 2. Insulators which have low conductivities.
which retains all the symmetry of the macroscopic 3. Semi-conductors which have. intermediate
crystal. In general, there are several possible ar­ conductivities which increase with rising
rangements of elementary particles which will temperature, usually as c~-4/r where A is
have the symmetry associated with a given crystal , a constant and T is the absolute temperature.
system, such as the cubic system.
The thermal and electrical conductivity of pyro­
There are three possible arrangements of space
technic ingredients may be contributing factors
lattices for the cubic system. As illustrated in
affecting the performance of a particular item.
Figure 3-2 they are: 12
*
The thermal conductivity, which is of greater
1. Simple cubic lattice. One structural unit significance, influences the conductive heat trans­
at each corner of the cube. fer characteristics. These properties become very
2. Face-centered cubic lattice. One unit at important in devices dependent on a functional
each corner of the cube and one unit in the transfer of heat such as a “ pyro-switch. ” Such
center of each face of the cube. devices may be normally closed.or normally open

3-6
 AMCP 706-185

and will either be conducting or nonconducting fol­ discussed showing their application in the field of
lowing the pyrotechnic reaction. pyrotechnics. Selected calculations, including those
The properties of solids are markedly affected for adiabatic flame temperatures, which are im­
by defects5 in crystal structure. Small amounts of portant to the overall analysis of chemical reac­
impurities in an insulating material may make the tions, are also presented.
material a semi-conductor. Such doped materials
may also exhibit enhanced chemical activities. De­ 3-2.1 THERMODYNAMIC RELATIONSHIPS
parture of a crystalline compound from chemical Thermodynamics is based on three laws and the
stoichiometry, due to incorporation of extra latoms implications derived from these laws. The applica­
into the1crystal at interstitial sites or to vacancies tion of certain thermodynamic relationships de­
caused by the absence of atoms from normal sites, rived from the three laws is a useful tool for use
also results in semi-conductivity. in. predicting the performance and outcome of
Point defects, including those in which an ion many physico-chemical systems.
moves from its lattice site to an interstitial posi­
tion (Frenkel defect), or those in which a pair o f
3 2.1.1 First Law of Thermodynamics • '■
ions of opposite charge are missing from their lat­
The first law of thermodynamics is a statement
tice site (Schottky defect), do not alter the exact
of the law of conservation of energy, i.e., that
stoichiometry of the solid but do provide a means
energy can be neither created nor destroyed.
by which atoms can move in the solid phase. Linear
The first law of thermodynamics can be ex­
defects,' dislocations, provide another means for
pressed mathematically:
atoms to move with respect to each other in the solid
phase. These defects provide mechanisms f o : many AE = q — w , (3-17)
of the processes which occur in the solid state.
where q is the energy in the form of heat, trans­
They provide sites at which chemical reactions
ferred into or out of the system; w is the energy,
and physical changes can take place readily. The
in the form of work transferred to or from the
point of emergence of a dislocation at the surface
system; and AE is the change in internal energy.
is a site of increased chemical reactivity.
If the system absorbs heat, q has a positive value;
The presence of crystal defects in pyre technic
if the system does work, w has a positive value.
ingredients can have a marked influence on the
The value of AE depends only on the initial and
course of the reaction and, therefore, influence the
characteristic behavior (including stability tind out­ final state of the system. The quantities q and w
depend on the path taken from the initial to the
put) of pyrotechnic compositions.
final state. For a cyclic process, i.e., a process
which has the same initial and final stage, AE — 0
3-2 THERMODYNAMICS
so that q == w. ,
Thermodynamics is the study of the quantita­
tive relationships between heat and other forms of 3-2.1.1.1 Heat Effects at Constant Volume and
energy. In all cases, energy can be expressed as Constant Pressure
the product o f two factors, an intensity factor (i.e„
The heat released by a pyrotechnic reaction can
temperature difference), and a capacity fa c W (i.e.,
raise the temperature of the reaction products,
heat capacity). In the reaction o f a pyrotechnic
cause phase changes, and cause other chemical re­
composition, the chemical energy is converted into
actions (such as dissociation) to take place. I f a
other forms of energy, primarily heat and work.
chemical reaction or physical change takes place at
The products of combustion are heated to the reac­
constant volume, and only pressure-volume work
tion temperature, and, if unconfined, work can be
is considered, the amount of work done is zero and
done against the atmosphere.
the heat effect accompanying the reaction is equal
In the following paragraphs, certain basic laws
to the change in internal energy.
of thermodynamics, thermochemistry, chemical
equilibrium, the concept of free energy, etc., are qv = AE (3-18)
AMCP 706-185

Chemical reactions, including many pyrotechnic 3-2.1.1.2 Heat Capacity

reactions, and physical changes may also take place The heat capacity o f a system is defined as the
at constant pressure where only pressure-volume quantity of heat required to raise the temperature
work is considered and the heat effect is equal to 1°C or, expressed mathematically:
the internal energy change plus the work done in
expansion. C = -% (3-24)
qP = b E + pbv (3-19)
Under conditions o f constant volume, dq = dE,
In this case, it is convenient to use another thermo­ Equation 3-18, and the heat capacity at constant
dynamic property, the enthalpy H, defined by: volume is equal to the change in internal energy
with temperature, or:
H = E + pV (3-20)
(3-25)
Then, for a chemical reaction or phase change oc­
curring at constant pressure, when only pressure- While the internal energy E is a function of the
volume work is considered: three variables T, P, and v ; only two are required
to define the system. A derivative, therefore, with
AH = AE + pAv (3-21)
respect to only one variable T is expressed as a par­
and the heat effect at constant pressure is equal to tial derivative with the subscript v denoting
the change in enthalpy:
the variable to be held constant.
qp = AH (3-22) A t constant pressure, the heat capacity includes
both the heat absorbed' to increase the internal
If gaseous products are assumed to behave ideally: energy plus the heat equivalent o f the work term
p dv. Since, under these conditions, dq = dH,
C iH = :k E + &nRT (3-23)
Equation 3-22, the heat capacity at constant pres­
where An = i n (products) — i n (reactants) for sure is equal to the change in enthalpy with tem­
the gaseous materials involved in the reaction. perature, or:
Therefore, pyrotechnic reactions involving solid
reactants and the formation of gaseous products
where heat is evolved (exothermic) will have a * -( £ ) . ( 3 -2 6 )

higher heat of reaction at constant volume, AE (q „), The heat capacity at constant pressure can be
than at constant pressure, AH (q p). In the latter calculated by equation o f the form (either o n e ):
case, qp is reduced by the heat equivalent of the Cp = a + bT + cT2
increased gaseous products, AnRT. These relation­ Cp = a + bT + cT ~ 2 (3-27)
ships can be used to obtain values equivalent to the
where a, b, and c are constants. This type equa­
standard heat of reaction from bomb calorimetric
tion applies over a more or less limited range of
measurements made at constant volume.
temperatures and for many thermochemical cal­
Pyrotechnic reactions take place under condi­
culations it is more convenient to use an average
tions o f either constant volume, constant pressure,
heat capacity defined b y :
or combinations of both. Constant volume condi­
tions occur for delay systems that are obturated, rr2
and constant pressure systems occur for flares, sig­ J CrdT
nals, smokes, and the like. In photoflash items, such
as cartridges or bombs, the confined composition -W <3'28)
functions under constant volume conditions when When necessary. Cv can be obtained by subtracting
initiated and it then continues to react at constant R (the universal gas constant) from the value for
pressure when dispersed as the case ruptures. Cp.

3-8
 AM CP 706-185

Heat capacity values are essential for many capacities of solids at higher temperatures.6 Where
thermochemical calculations involving pyrotech­ these values are not available, the room tempera­
nics. The temperature attained by the products of ture value may be used in conjunction with a value
a pyrotechnic reaction will depend, in part, on the o f 7.25 calories per gram-atom per degree-Kelvin
heat capacity o f these products. Calculations o f for the next transition point, assuming a linear in­
the heat balance for a given system utilize the crease of Cp with temperature.
heat capacity to obtain the enthalpy change in The heat capacities o f molten inorganic sub­
going from one temperature and/or state to an­ stances do not differ greatly from those o f solid
other. The latest tables, however, provide enthalpy materials. When handbook values are unavailable,
changes directly, making it unnecessary to calcu­ K op p ’s Rule may also be applied to compounds by
late heat capacities independently. assigning the following values o f atomic heat
capacities to the atoms o f the liquid: C, 2.8; H,
3-2.1,1.2,1 Heat Capacity o f Gases 4.3; B, 4.7; Si, 5.8; 0 , 6.0; F, 7.0; P, 7.4; S, 7.4,
and to most other elements a value of 8.0.
According to the kinetic theory o f gases, the
Other methods for estimating heat capacities
heat capacity of ideal gases, and of monotomic real
o f liquids and solids are available.6 In most cases,
gases such as helium and argon, to relatively high
calculations are unnecessary, as the values have
temperatures is :
been experimentally determined and may be ob­
Cv = 3 /2 B = 3 cal/gmole °K (3-29) tained from handbook tabulations.
The heat capacity of liquids and solids decreases
Cp = C„ 4* R = 5 cal/gmole °K (3-30)
considerably with a decrease ip temperature and
Diatomic real gases, including gases such as oxygen is zero at absolute zero. For temperatures below
and nitrogen, and linear polytomic molecules have 50°K, the Debye Equation applies and:
two degrees o f rotational freedom in addition to
the three degrees o f freedom associated with trans­ c - 16i 5 r3 calorie__________
1 ' 8 s degree-Kelvin gram-atom
lational motion. A t normal temperatures the heat
(3-33)
capacities o f these gases are approximate!^:
where T is the absolute temperature in degrees-
Cv as 5 /2 B — 5 cal/gmole ,°K (3-31)
Kelvin, and 8 is termed the characteristic tempera­
Cp as Cp + B = 7 cal/gmole °K (3-32) ture and is defined b y :

3-2.1.1.2.2 Heat Capacity of Liquids and Solids 8 = (3-34)

. *c
According to the law o f Dulong and P etit, the
molar heat capacities o f solid elements (specially where h is the Planck constant, k is the Boltzmann
constant and vm is the maximum vibration fre­
the metals) Cp and Cp are approximately f calories
quency. These values may be found in a suitable
per gram-atom per degree-Kelvin. This is in agree­
handbook.
ment with the values o f 3B, i.e., 5.96 calories per
gram-atom per degree-Kelvin, suggested by kinetic
theory. - [ 3-2.1.2 Second Law o f Thermodynamics
The molar heat capacities o f solid compounds The second law o f thermodynamics may be ex­
can be estimated by using K op p ’s Rule which states pressed in many ways. A very general statement
that the heat capacity o f a solid compound is ap­ is that any spontaneous change will render a sys­
proximately equal to the sum o f the heat capacities tem and its surroundings closer to an ultimate state
o f the constituent elements. In using this rule, the o f equilibrium from which no further change can
following atomic heat capacities are assigned to spontaneously occur. That is, any isolated system
the elements: C, 1.8; H, 2.3; B, 2.7; Si, 3.8; O, left unattended will change toward a condition of
4.0; F, 5.0; P, 5.4; S,'5.4; and all others, 6.2. maximum probability. In order to obtain a quan­
Other methods are available for estimating heat titative measure o f the probability or randomness

3-9
AMCP 706-185

of a system, the concept o f entropy has been estab (A d ),.,- < 0 (3-3(0
lished.
For pyrotechnic reactions, many of which proceed
The absolute entropy S of a substance in a par­
at. eonstant. pressure and temperature, the Gibbs
ticular state— under specified conditions of tem­
free energy /•' is a more useful function. The driv­
perature, volume and pressure and in a known state
ing force or change in free energy is important an<.
o f aggregation; solid, liquid, or gas— is propor­
is expressed by:
tional to the logarithm of the probability of finding
the substance in that state. AF = AH - TAS (3-40)

8 — k ln W (3-35) In this case, the criterion of spontaneity is:

(A F) jy* 0 (3-41)
where k is Boltzmann’s constant, and W is the
probability. As a consequence of Equations 3-38 and 3-40, addi­
Entropy, like internal energy, depends only on tional statements may be made regarding the spon­
the initial and final scales o f a system and. for an taneity of chemical reactions. These are summa­
infinitesimal reversible process, is defined by the rized in Table 3-1.
equation: At ordinary temperatures, entropy effects arc
small so they have little effect on the direction of a
d8 = d q (™— ■ (3-36) chemical reaction unless the difference in energy
AF or AH between reactants and products is rela­
where d q {rev) is the heat absorbed from the sur­ tively small. At higher temperatures, such as those
roundings in a reversible process, i.e... a process resulting from pyrotechnic reactions, the relative
carried out in such a manner that it could be re­ importance of the change in entropy increases until
versed by an infinitesimal change in external con­ it becomes a dominant factor. Hence, all chemical
ditions. Entropy has the same unils as heat ca­ reactions which involve an increase in entropy will
pacity, i.e., ealories per gram-atom per dcgree-Kel- occur spontaneously if the temperature is high
vin. enough. A discussion of free energy and the equi­
By using entropy, the second law can be ex­ librium constant is presented iu Paragraph 3-2.3.
pressed mathematically •.
3-2.1.3 Third Law of Thermodynamics
AS system -|- AS surroundings 0 (3-37)
According to the third law of thermodynamics,
Every spontaneous change in a system, therefore, the entropy of a perfect crystalline substance al
is in a direction such that its entropy, plus that of 0°K is zero. Although it. is impossible theoretically
its surroundings, increases. However, if the sys­ to attain absolute zero, the validity of the third law
tem alone is considered, spontaneity of chemical has been checked by experimentation. It can also
reactions may be treated b> taking two driving be shown that the entropies of all pure chemical
forces into account; a tendency to adopt the lowest compounds in their stable states at 0°K are zero
energy and a tendency to adopt the highest en­ because their formation from the elements is:
tropy. If the two changes are opposed, the system AS„ — 0. This law states that absolute entropies
will proceed in the direction of the larger change. or so-called third law entropies can be determined
If the two quantities are exactly equal, no change from heat capacity data extrapolated to 0°K which
will occur and the system is said to be at equi­ can he used in equilibrium calculations:
librium. The net driving force is termed the Work
Function or Helmholtz free energy -4, and at con­
(3-42)
stant temperature :1B>ie

Ad. = A2? — TAS (3-38)

where , the increase in entropy, is ob-
For a spontan eous process at constant volume and
constant temperature, A d is always negative: To

3-10
 AMCP 706-185

TABLE 3-1
C R ITERIA OF SPONTANEITY

Conditions Type of Reaction Criteria

General Reversible AS (total) = 0

Spontaneous AS (total) > 0
E, v constant Reversible AS (isolated system) = 0
Spontaneous AS (isolated system) > 0
T, v constant Reversible AA = 0
Spontaneous AA < 0
T, p constant Reversible AF = 0
Spontaneous AF < 0
S, v constant Reversible AE = 0
Spontaneous AE < 0
S, p constant Reversible AH = 0
Spontaneous AH < 0 .

tained for each phase by graphical integration and 4. Whether or not the reaction is at constant
AH.pc volume or constant pressure.
the entropy increase due to a phase change,
The specific influence of these conditions is de­
is determined for each of the phase changes. The
scribed in the paragraphs which follow. .
Debye Equation (Paragraph 3-2.1.1.2.2) is used
for the temperature range 0°K to approximately
50°K as experimental data are difficult to obtain 3-2.2.1 Heats o f Reaction
in this temperature range. Absolute entropies can The heat effect associated with a pyrotechnic
also be calculated by the method of statistical or other chemical reaction is the heat o f reaction.
mechanics.5 The heat of formation is the heat of the reaction
associated with the formation o f a compound from
3-2.2 THERM OCHEM ISTRY its elements. The heat o f combustion is the heat of
Thermochemistry is the study of the heat Effects the reaction associated with the complete com­
accompanying chemical reactions, the formation of bustion o f a substance in oxygen. The heat o f ex­
solutions, and changes in state such as fusiojn and plosion is the heat o f reaction associated with the
vaporization. Since the amount of heat liberated rapid explosive decomposition of a material in an
from a pyrotechnic reaction strongly influences the inert atmosphere.
characteristic output, an understanding o f the For pyrotechnic reactions at constant pressure,
principles and application of thermochemistry is if only pressure-volume work is considered, the
of vital importance. heat effect qv can be obtained from the enthalpy
The heat evolved (or absorbed) in a chemical change for the reaction as follows:
reaction depends upon :
q9 s= AH (reaction) = HH (products)
1. The properties of the products and reac­ — 22T (reactants) ' (3-40)
tants, and the amount o f these substances in-
volved. I f the reaction is a standard state reaction,
2. The physical state of the substances in­ where the reactants in their standard states react
volved. to give the products in their standard states and
3. The temperature and pressure at which the the standard heats o f formation AH r° ( f ) o f the
reaction takes place. _ elements is assumed to be zero at any given tem-

3-11
AM CP 706-185

AH°T

Figure 3-3, Effect o f Temperature on Enthalpy Change for Chemical Reaction

per&ture, then the standard heat o f reaction AHT° 3-2.2.2 Effect o f Temperature on the Heat of
(reaction) is: Reaction
As illustrated schematically in Figure 3-3, the
A B r° (reaction) = AH ( f ) r ° (products) heat o f .reaction at any temperature T and constant
— A jff(/)j-° (reactants) (3-41) pressure is :
Jt
The actual choice of standard states is somewhat
arbitrary. Normally, the standard state is the most A H r0 = & H t°R + 2 Cpd T -|- AHpc'j (reactants)

stable state at one atmosphere pressure and at the T

given temperature. (Most tabular data are given
at 0°K or 298°K.) T
+ 2 ( J CpdT + A ffp^ (products) (3-47)
Most thermochemical calculations are based on
tabulated standard heats o f .formation. The heat
T«
effect at constant pressure (qf ) can be calculated where AZ?T0 is the heat o f reaction at temperature
by: T , & H ° tr is the heat of reaction at a reference tern-

(qp) r (reaction) = AH T (reaction) sas

AflV° (reaction) (3-45) perafure Tr, 2 ( f \ d T + AHpC ^ (reactants) is

Unless the actual pressure is high, no appreciable T

error is introduced. the heat evolved or absorbed in cooling or heating
Similarly, the heat effect at constant volume the reactants from T to Tr, including that evolved
(q„) can be obtained b y : or absorbed as a result o f phase changes AJTpc.

A ' *
(qB) r (reaction) = AE (reaction)
Similarly, CpdT -f- Affpr'j (products) is the
s£ AE t ° (reaction) = 2A E ( f ) r° (products)
— 2A E ( f ) r ° (reactants) (3-46) Tr

3-12
 i-.

AMCP 706-185
. '-‘-i* -p ’
' -y
heat absorbed or evolTed in heating or cooling These tables can also be used for calculations
the products from TR to T. According to Equation of free energy changes for chemical reactions. This
3-47, if the heat evolved by cooling the reactants is shown in Paragraph 3-2.3.5
from the higher to the lower temperature is greater
than the amount absorbed in heating the products 3-2.2.4 Bond Energies7
from the lower to the higher temperature, the heat Bond energy (B .E .) is defined as the average
o f reaction at the higher temperature will be great­ amount of energy per mole required to break a
er than that at the lower temperature.; particular type of bond in a molecule. Bond, ener­
In cases where reactions begin and end at the gies may be calculated when heat o f combustion
same temperature and where no changes in phase data are available. However, of greater utility is
are involved, the standard heat of reaction at the estimation o f the heat o f reaction from bond
temperature T is defined b y : energy data for compounds for which no enthalpy
data are available. In this case:
T
AHt ° = A ffr ° _ +
/ A C,dT (3-48) AH — B.E. (bonds broken) — B.E. (bonds formed)
-■ (3-51)

where ACp — ECp (products) — 2C P (reactants), Bond strengths or bond dissociation energies may
and H t° j, is the standard heat o f reaction at the differ from mean bond energies derived solely
K l»
reference temperature TR. This is known as Kirch- from thermochemical data on molecules and atoms.
hoff’s Equation and, for small temperature
ranges, heat capacities may be treated as constant 3-2.3 FR E E ENERGY AND EQUILIBRIUM
and the equation reduces t o : A state of chemical equilibrium exists in any
AHT° = AH t ° r + ACp(T-TB) (3-49) chemically reacting system when no further change
in composition with time can be detected provided
F or other cases, experimental heat capacity data
the temperature and pressure are not altered. The
expressed in the form shown in Paragraph 3-21.1.1.2
criterion of equilibrium is that the change in free
must be used; however, if enthalpy tables are avail­
energy of any possible reaction under these condi­
able, heat capacity data need not be considered as
tions shall be zero. 1
such. 1
Where data are required at temperatures above (AF)r,j» = 0 (3-52)
those listed, it may be necessary to extrapolate the
In order to estimate maximum flame temperatures
data to the desired temperature
from pyrotechnic reactions, a knowledge o f the
3-2.2.3 Enthalpy Tables . equilibrium concentrations o f the combustion prod­
ucts is required in addition to information on the
Calculations o f heat o f reaction at different
heat released. I f a state of equilibrium exists among
temperatures are simplified if tabular enthalpy data
the product species, the equilibrium composition
are available. Tables 3-2 for solid magnesium ox­
for the combustion products is fixed at a given
ide, 3-3 for solid aluminum oxide, 3-4 and 3-5 for
temperature and pressure (or volume) when the
solid and liquid sodium oxide, and 3-6 for gaseous
atomic composition is specified.
oxygen, contain these data. In these' tablet, stan­
Pyrotechnic reactions often involve the oxida­
dard heats o f formation AHf°, at different tempera­
tion o f a metal to form a refractory oxide. This
tures, are tabulated. In other tables only values
reaction limits the maximum temperature attain­
for the enthalpy function, H ° — H rR°i along with
able to the vaporization temperature o f the metal
the heat o f formation at some reference tempera­
oxide whether this oxide decomposes on vaporiza­
ture, usually 0°K or 298.93°K are tabulated. The
tion, or not. The metals commonly used as fuels
heat o f reaction at any temperature becomes:
in pyrotechnics decompose on vaporization. In
B tb °) (products) most cases, the metal decomposes to yield metal
— S(JT° — H T r °) (reactants) (3-50) atoms; however, a few metal oxides, such as alum-

3-13
AMCP 706-185

TABLE 3-2
THERMODYNAMIC PROPERTIES OF SOLID MAGNESIUM OXIDE
Magnesium Oxide (MgO) (Solid) Mol. Wt. = 2832

kcal. mole*1
'- ( F ° - H > ) /T ' ISO—II
XI TJO298 A H °, A F 9, ' Log Kn
T, °K. c°p S°
0 .000 .000 INFINITE - 1.235 -142.702 -142.702 INFINITE
100 1.865 .608 12.488 - 1.188 -143.156 -140.918 307.981
200 6.380 3.369 7.184 ^ .763 -143.559 -138.501 151.340
298 8.906 6.439 6.439 .000 -143.700 -135.981 99.672

300 8.939 6.494 6.439 .017 -143.701 -135.933 99.022

400 10.148 9.252 6.807 .978 -143.705 -133.340 72.860
500 10.854 11.598 7.537 2.031 -143.654 -130.755 57.150

600 11.323 13.621 8.386 3.141 -143.583 -128.181 46.688

700 11.656 15.393 9.263 4.291 -143.513 -125.619 39.218
800 11.905 16.966 10.130 5.469 -143.467 -123.067 33.619
900 12.098 18.380 10.969 6.670 -143.425 -120.521 29.265
1000 12.251 19.663 11.775 7.888 -145.541 -117.799 25.744

1100 12.375 20.837 12.546 9.119 -145.529 -115.025 22.852

1200 12.478 21.918 13.283 10.362 -145.538 -112.252 20.443
1300 12.565 22.920 13.986 11.614 -145.567 -109.478 18.404
1400 12.638 23.854 14.658 12.874 -176.047 -106.235 16.583
1500 12,701 24.728 15.301 14.141 -175.712 -101.261 14.753

1600 12.756 25.550 15.916 15.414 -175.375 - 96.309 13.155

1700 12.804 26.325 16.505 16.692 -175.034 - 91.378 11.747
1800 12.845 27.058 17.071 17.975 -174.693 - 86.467 10.498
1900 12.882 27.753 17.616 19.261 -174.351 - 81.574 9.383
2000 12.915 28.415 18.139 20.551 -174.008 - 76.699 8.381

2100 12.946 29.046 18.644 21.844 -173.665 - 71.844 7.477

2200 12.971 29.648 19.130 23.140 -173.321 - 67.004 6.656
2300 12.994 30.225 19.600 24.438 -172.979 - 62.178 5.908
2400 13.016 30.779 20.054 25.739 -172.636 - 57.368 5.224
2500 13.035 31.311 20.494 27.041 -172.295 - 52 672 4.596

2600 13.052 31 822 20.920 28.346 -171.955 - 47>90 4.017

2700 13.068 32.315 21.333 29.652 -171.616 - 43.018 3.462
2800 13.082 32.791 21.734 30.959 -171.280 - 38.264 2.986
2900' 13.095 33.250 22.123 32.268 -170.945 - 33.618 0.626
3000 13.107 33.694 22.501 33.578 -170.613 - 28.785 2.097

(JANAF TW m odynunic Tabkg, Interim Table Inued December 81, 1960)

inum oxide, decompose to yield a mixture of other chemical reaction is directly proportional to the
oxide molecules. Typical of the decomposition re- “ active masses’ ’ of the reacting materials. For
action is the following general reaction:8 any chemical reaction:
MxO, (1 ) z ± x M (g ) + y /2 0 2(g ) (3-53) aA + bB + . . . ^ gQ + Hh . . .
where M represents a metal element. Since the where the capital letter indicates a chemical species
reactions are reversible, the degree of decomposi- an(j the small letter indicates the number of moles
tion will depend on the oxygen partial pressure as 0f eac), gpeejes.
well as the temperature. At the high temperatures An equilibrium constant for this reaction, desig-
produced by pyrotechnic reactions, many other nated K, can be written in terms of concentrations:
equilibria, such as the dissociations of gaseous
products, relatively unimportant at lower tempera- ^ _ k (f) _ [(?]* [H ]* (3-54)
tures, must be considered. k (r ) [A ]°[B ]8

3-2.3.1 Chemical Equilibrium where the open brackets [ ] indicate a concentra­

According to the law o f mass action as stated tion term, k ( f ) is the specific rate constant for the
by C. M. Guldberg and P. Waage,® the rate of a forward reaction, k (r ) is the specific rate constant
 AMCP 706*185

TABLE 3-3
THERM ODYNAM IC PROPERTIES OF SOLID ALUMINUM O X ID E

E*
A lu m in u m O x id e ( a lp h a AI2O 3) ( C r y s t a l) M o l 101.960

II
____cal. mole'1 deg.'1 kcal. mole' I
T, °K. C°p S° -(F °-H XX©-J1
ll XI©298 A H ', A F 0, ‘ Log Kp

0 .000 .000 INFI NITE - 2.394 -397.494 -397.494 INFINITE

100 3.069 1.024 24.184 - 2.316 - -398.697 -392.241 857.201
200 12.223 5.946 13.711 - 1.553 -399.838 -385.329 421.047-
298 18.889 12.174 ' ■ 12i174 .000 -400.400 -378.078 277.125

300 18.979 12.291 12.174 .035 -400.406 -377.940 275.316

400 22.986 18.339 1 2 .# 2 2.147 -400.555 -370.418 202.378
500 25.345 23.752 14.598 4.577 -400.475 -362.891 158.612

600 26.889 28.517 16. 529 7^193 -400.304 -355.389 129.444

700 27.969 32.749 18.549 9.940 -400.098 -347.920 108:620
800 ' 28.758 36.537 20.565 12.778 -399.889 -340.481 93.011
900 29.354 39.961 22.533 15.685 -399.697 -333.066 80.875
1000 29.814 43.078 24.434 18.644 -404.522 -325.301 71.091

1100 30.176 45.938 26 261 21.644 -404.181 -317.396 63.058-

1200 30.464 48.574 28 012 24.674 -403.823 -309.522 56.369
1300 30.995 51.032 29 689 27.745 -403.437 -301.680 50.715
1400 31.290 53.339 31 297 30.859 -403.019 -293.868 45.873 ,
1500 31.620 / 55.509 32.839 34.004 -402.581 -286.086 41.681

1600 31.920 57.559 34 321 37.181 -402.119 -278.334 38.017

1700 32.220 59.503 35 (745 • 40.388 -401.635 -270.612 34.788
1800 32.490 61.353 37 117 43.624 -401.133 -262.920 31.921
1900 32.760 63.116 38 439 46.886 -400.613 -255.254 29.359
2000 33.000 64.803 89.716 50.175 -400.075 -247.619 27,057

2100 33.220 66.419 40.949 53.486 -399.521 -240.011 24.977

2200 33.450 67.969 42:ll42 56.819 -398.956 -232.427 23.088
2300 33.670 69.461 43 .|298 60.175 -398.374 -224.872 21.367

2400 33.880 70.898 ■ 44.1418 63.553 -397.779 -217.339 19.790

2500 , 34.100 72.286 45 505 66.952 -397.172 -209.834 18.343

2600 , 34.310 73:627 46 561 70.372 ‘ -396.550 -202.354 17.009

2700 34.520 74.926 47 588 73.814 -395.915 -194.898 15.775
2800 34.735 76.186 48 587 77,277 ' -536.375 -184.157 14.373
2900 34.940 77.408 49 560 80:760 -535.307 -171.598 12:931
3000 , 35.140 78.596 50 508 84.264 -534.227 -159.072 11.588

3100 ' 35.340 79.751 51, 433 87.788 -533.132 • : -146.584 10.334
3200 35.530 80.876 52 335 91.332 -532.028 -134.135 9.161
3300 35.720 81.973 53 217 94.894 -530.908 -121.718 8.061
3400 35.906 83.042 , 54 078 98.476 -529.777 -109.338 7.028
3500 36.095 84.085 54 921 102.076 -528.634 - 96.992 6:056

(JANAF Thermodynamic Tables, Interim Table Issued March 31,1934)

for the reverse reaction, and K is the equilibrium stant. The expression in terms of partial pressures
constant. The concentration can be expressed as •for the equilibrium constant, therefore, will in­
a partial pressure or as a mole fraction in addition clude only terms for the gaseous materials.
to the more common concentration units. For alctual The equilibrium between phases is an important
systems, activities or fugacities should be used in­ type of heterogeneous equilibrium. The free ener­
stead of concentrations.6,9 gies of the vapor and liquid phases are the same
When more than one phase is present, as is true which leads to the derivation of the important
for most pyrotechnic reactions, the equilibrium is Clausius-Clapeyron Equation :9
heterogeneous. Since the partial pressures ojf the
dp p&H
gas phases in equilibrium with the solid phases are (3-55)
W = RT2
constant at a given temperature, they can be as­
sumed to be incorporated into the equilibrium con­ fn this.equation, p is the vapor pressure in milli-
AMCP 706-185

TABLE 3-4
THERMODYNAMIC PROPERTIES OF SOLID SODIUM OXID E
Sodium Oxide (NaaO) (Crystal) Mol. W t = 61.982

Weal, mnle'1
' rjo u© Lor K,,
T, °K. c1 S° -(F°-H °,«i)/T ' rl —xl ns A H °, A F °,

0
100
«uu
208 17.436 17.990 17.990 .000 - 99.400 -90.126 66.060

300 17.464 18.098 17.990 .032 - 99.398 -90.067 66.610

400 18.442 23.264 18.687 1.827 -100.647 -86.862 47.467
600 19.430 27.476 20.034 3.720 -100.601 -83.417 36.460

600 20.418 31.106 21.684 5.713 -100.428 -79.995 29.137

700 21.406 34.327 23.178 7.804 -100.138 -76.612 23.918
800 22.394 37.249 24.767 9.994 - 99.737 -73.277 20.017
900 23.382 39.944 26.297 12.283 - 99.235 -69.998 16.997
1000 24.370 42.469 27.788 14.670 - 98.641 -66.780 14.694

1100 26.368 44.828 29.231 17.167 - 97.966 -63.629 12.641

1200 26.346 47.077 30.626 19.742 -143.686 -69.626 10.869

1300 27.334 49.224 31.974 22.426 -142.423 -52.670 8.864
1400 28.322 61.286 33.280 25.209 -141.067 -45.817 7.162
1600 29.310 63.274 34.647 28.090 -139.615 -39.064 6.691

1600 30.298 66.197 36.778 31.071 -138.067 -32.409 4.427

1700 31.286 67.064 36.975 34.160 -136.420 -26.864 3.324
1800 32.274 68.880 38.142 37.328 -134.681 -19.401 2.366
1900 33.262 60.661 39.280 40.605 -132.846 -13.044 1.600
2000 34.260 62.382 40.392 43.980 -130.916 -6.791 .742

(JANAF Thermodynamic Table* Interim Table laued June SO, 1002)

meters of mercury, T is the absolute temperature, 3-2.3.2 The LeChatelier Principle

R is the universal gas constant, and AH is the heat The LeChatelier principle states that if a stress
of vaporization in calories per gram-mole. I f AH is brought to bear on a system in equilibrium the
can be considered constant over the temperature system will adjust itself to diminish the applied
range o f interest, then: stress. For example, in the decomposition of a
metal oxide in a confined system, the partial pres­
log p ~ ( ~ i w ‘) ( i r ) + Constant (3'56) sures will increase and the reaction shifts to the
left. A higher temperature is required to decom­
This equation is of the same form as the empirical pose the oxide.
equation given in paragraph 3-1.2.1 relating change When heat is absorbed by a chemical reaction,
in vapor pressure and temperature. An equation an increase in temperature favors the reaction; on
of similar form relates the sublimation pressure the other hand, if heat is evolved by the reaction,
and temperature. an increase in temperature will favor the reverse
The heterogeneous metal oxide decomposition reaction.
equilibrium illustrated by Equation 3-53 is im­
portant to the study o f pyrotechnic reactions. The 3-2.3.3 Free Energy and the Equilibrium Constant
expansion for the equilibrium constant for this For any chemical reaction the change in free
reaction in terms of partial pressures K t can be energy is given by.
written:
AF = R T l n ~ (3-58)
Kp = (p * )« (3-57)

where p<>2 is the partial pressure of the oxygen and where K is the equilibrium constant. Q is a con­
pit is the partial pressure o f the metal vapor. tinuous function similar in- form to K (Equation

3-16
 AM CP 706-185

TA B LE 3-5
THERM ODYNAM IC PROPE RTIES OF LIQUID SODIUM O X ID E
Sodium Oxide (NaaO) (Liquid) Mol. W t = 61.982

nd. molft*1Hug-1
T, °K. 8° ...)/T ‘ no TTO
n -n tss
o; A H °, AF°f Log Kp
0 .
100
200
298 27.000 17.889 17.8 39 .000 - 93.996 -84.691 62.077
300 27.000 18.056 17.890 .050 - 93.977 -84.632 61.652
400 27.000 25.823 18.949 2.750 - 94.320 -81.562 44.661
600 27.000 31.848 20.948 5.450 - 93.468 -78.470 34.298
600 27.000 36.771 23.188 8.150 - 92.587 -76.553 27.619
700 27.000 40.933 25.433 10.860 - 91.688 -72.787 22.724
800 27.000 44.538 27.601 13.550 - 90.777 -70.148 19.163
900 27.000 47.719 29.663 16.250 - 89.864 -67.624 16.421
1000 27.000 50.563 31.613 18.950 - 88.958 -65.201 14.249
1100 27.000 53.137 55 21.650 - 88.069 -62.872 12.491
1200 27.000 56.486 24.350 -133.673 -59.704 10.873
1300 27.000 57.647 27.050 -132.396 -5 3 .6 0 3 9.009
1400 27.000 69.648 29.760 -131.122 -47.679 7.427
1600 27.000 61.511 32.460 -129.851 -41.655 6.069
1600 27.000 63.263 36.160 -128.584 -35.816 4.892
1700 27.000 64.890 37.860 -127.317 -30.056 3.864
1800 27.000 66.433 40.550 -126.065 -24.371 2.959
1900 27.000 6 7 .8 0 3 43.250 -124.797 -18.765 2.157
2000 27.000 69.278 46.950 -123.543 -13.209 1.443
2100 27.000 70.696 47.429 48.650 -122.289 - 7.725 .804
2200 27.000 71.862 4 8 .p l 51.350 -121.041 - 2.297 .228
2300 27.000 73.062 49.562 54.060 -119.795 3.070 - .292
2400 27.000 74.201 50.665 56.760 -118.554 8.390 - .764
2600 27.000 76.303 51.523 59.460 -117.316 13.649 - 1.193
2600 27.000 76.362 52.468 62.150 -116.084 18.866 - 1.586 ,
2700 .27.000 77.381 53.362 64.850 -114.857 24.031 - 1.945
2800 27.000 78.363 54.238 67.550 -113.637 29.151 • 2.275
2900 27.000 79.310 55.086 70.260 -112.421 34.234 - 2.580
3000 27.000 80.226 55.909 72.950 -111.213 39.269 - 2.861

(JANAF Thermodyn*mio T ib ia, Interim Table baaed Jane SO, 1062)

3-54) but which applies to the “ concentrations” partial pressures. For example, the equilibrium
or partial pressures o f the products and reactants constant for the decomposition of a metal oxide,
at any time during a particular reaction. F or real Equation 3-57 is related to the standard free energy
gases and other substances, the K and Q should be change for the reaction, Equation 3-59, as follow s:
terms o f activities or fugacities. I f the reaction is
AF° = - R T l n K , = - R T In ( p .2(> )«"*(p i,„> )-
a standard state reaction, the hypothetical reac­
(3-61)
tion in which the reactants in their standard spates
at one atmosphere react to give products in their where pot is the partial pressure of the oxygen and
standard states at one atmosphere, Q becomes \inity P m is the partial pressure o f the metal vapor.
and ' :■ ■ "• j Hence, the stability o f the oxide can be calculated
&F° — — R T l n K (3-59) from frequency data.
For a gaseous reaction involving gases whichl can
be considered ideal:
A F ° = — R T ln K p (11-60) 3-2.3.4 Free Energy Calculations
where K p is the equilibrium constant in terms o f Standard free energy changes for chemical reac-
AMCP 706-185

TABLE 3-6
THERMODYNAMIC PROPERTIES OF OXYGEN
Oxygen, Diatomic (Os) (Reference State—Ideal Gas) Mol. Wt. = 32.00

ml. mnln-1 flfiflV1

T, °K. ’ c; s° -(F °-H °,„)/T ' 11°
n -nuo(os AH°» AF°t Lot? Kp
0 .000 .000 INFINITE - 2.075 .000 .000 .000

100 6.741 41.622 66.142 - 1.362 .000 .000 .000

200 6.871 46.233 49.641 - .682 .000 .000 .000
298 7.020 49.004 49.004 .000 .000 .000 .000
300 7.023 49.047 49.004 .013 .000 .000 .000
400 7.196 51.091 49.282 .724 .000 .000 .000
600 7.431 52.722 49.812 1.466 .000 .000 ooo
600 7.670 64.098 60.414 2.210 .000 .000 .000
700 7.883 55.297 51.028 2.988 .000 .000 .000
800 8.063 66.361 51.629 3.786 .000 .000 .000
900 8.212 57.320 , 52.209 4.600 .000 .000 .000
1000 .8.336 58.192 52.766 5.427 .000 .000 .000
1100 8.439 68.991 63.295 6.266 .000 .000 .000
1200 8.527 69.729 63.801 7.114 .000 .000 .000
1300 8.604 60.415 54.283 7.971 .000 .000 .000
1400 8.674 61.056 54.744 8.835 .000 .000 .000
1600 8.738 61.666 66.185 9.706 .000 .000 .000
1600 8.800 62.222 55.608 10.583 .000 .000 .000
1700 8.858 62.757 56.013 11.465 .000 .000 .000
1800 8.916 63.205 56.401 12.364 ooo .000 .000
1900 . 8.973 63.749 56.776 . 13.249 .000 .000 .000
2000 9.029 64.210 57.136 14.149 .000 .000 .000
2100 9.084 64.652 •
r>7.483 19.054 .000 .000 .000
2200 9.139 65.076 r7.819 15.966 .000 .000 .000
2300 9.194 65.483 53.143 16.882 .000 000 .000
2400 9.248 66.876 58.457 17.804 .000 .000 .000
2600 9.301 66.254 58.762 18.732 .000 .000 .000
2600 9*364 66.620 59.067 19.664 .900 .000 .000
2700 9.406 66.974 59.344 20.602 .000 .000 .000
2800 9.456 67.317 59.622 21.545 .000 .000 .000
2900 9.603 67.650 69.893 22.493 .000 .000 .000
3000 9.561 67.973 60.157 23.446 .000 .000 .000
3100 9.596 68.287 60.415 24.403 .000 .000 .000
3200. 9.640 68.592 60.665 26.365 .000 .000 .000
3300 9.682 68.889 60.910 26.331 .000 .000 .000
3400 9.723 69.179 61.149 27.302 .000 .000 .000
3600 9.762 69.461 61.383 28.276 .000 .000 .000
3600 9.799 69.737 61.611 29.254 .000 .000 .ooo
3700 9.836 70.006 61.834 30.236 .000 .000 .000
3800 9.869 70.269 62.053 31.221 .000 .000 .000
3900 9.901 70.625 62.267 32.209 .000 .000 .000
4000 9.932 70.776 62.476 33.201 .000 .000 .000
4100 9.961 71.022 ! 62.682 34.196 .000 .000 ooo
4200 9.988 71.262 62.883 35.193 • .000 .000 .000
4300 10.015 71.498 | 63.081 36.193 .000 .000 .000
4400 10.039 71.728 63.275 37.196 .000 .000 .000
4600 10.062 71.954 63.465 38.201 .000 .000 .000
4600 10.084 72.176 63.652 39.208 . .000 .000 .000
4700 10.104 72.393 63.836 40.218 .000 .000 •ooo
4800 10.123 72.606 64.016 41.229 .000 .000 .000
4900 10.140 72.814 64.194 42.242 .000 .000 .000
6000 10.166 . 73.019 64.368 43.267 .000 .000 .000
6100 10.172 73.221 64.640 44.274 .000 .000 ooo
6200 10.187 73.418 64.708 45.292 .000 .000 .000
6300 10.200 . 73.613 64.875 46.311 .000 .000 .000
6400 10.213 73.803 65.038 47.332 .000 .000 .000
6600 10.226 73.991 65.199 48.363 .000 .000 .000
6600 10.237 74.176 66.358 49.377 .000 .000 .000
6700 10.247 74.366 65.514 60.401 .000 .000 .000
6800 10.268 : 74.636 65.668 51.426 .000 .000 .000
6900 10.267 74.710 66.820 62.462 .000 .000 .000
6000 10.276 74.883 66.970 63.479 .000 .000 .000

(JANAT Thermodynamic Tablet, Interim Table leaued March SI, 1941)

3-18
 AMCP 706485

tions AF t° can be calculated from the standard the equilibrium constant with temperature is more
free energies o f formation, A F r ° ( / ) : ; complicated.

AFT° = 2 A F r ° ( / ) products = SA F r " ( / ) reactants

. , (3-i 32)
3-2.3.5 tabulated Free Energy Values
Standard free energy of formation of the eleme nts Calculations involving free energy changes at
in their standard state at one atmosphere pressure any temperature are made easier if tabulated values
and at the given temperature is taken as zero. are available for the standard free energy of for­
The standard free energy change and the associ­ mation at various temperatures. Tables 3-2, 3-3,
ated equilibrium^constant (Equation 3-58) are 3-4, 3-5, and 3-6 contain this information in ad­
functions of temperature. The change in free dition to the information on standard enthalpies of
energy, the enthalpy change A ff, and-the tempera­ formation. In these particular tables, the stan­
ture are related by the Gibbs Helmholz equation dard free energies of formation of the compound
which, for a standard state reaction, is: ' from the elements in their standard states, along
with the equilibrium constant for the formation
A /f° — AF° — dAF° d (R T In K )
(3-63) reaction, are tabulated for various temperatures.
dT dT
In other tabulations the free energy function
If A # 0 can be considered constant over the range
of temperature, or is an average value: - Ft
is tabulated for various temperatures
AF° AH °
= - l o g Kp= + -j- Constant (3-64)
RT 2.3RT along with the standard free energies of formation
at some reference temperature, where T is the reac­
I f AH ° cannot be treated as a constant over the
tion temperature and T r is the reference tempera­
temperature range, the calculation of the change in
ture. .

Then:
AF t ° — EAF t° ., ( /) products — EAFTj{ &( / ) reactants (3-65)

—Ft,
+ ST (J -l products — S T {^—T
.__reactants

The reference temperatures normally used are two temperatures is related by:
298°K or 0°K. The free energy change at these

AF298° = E A H °(/) products — EA£fo(/) reactants (3-66)

F<mh° — H
+ 2298 ^ products — 2298 ( ~ ^ 2 9 8 ~ ~ ) reactants
298

3-2.4 ADIABATIC FLAME TEMPERATI calcnlations assume adiabatic conditions, i.e., no

The heat produced by an exothermic reaction heat is lost to or gained from the surroundings,
raises the temperature o f the products formed to and all the heat released is utilized in raising the
the reaction temperature. This maximum tenipera- temperature o f the products and unreacted reac­
ture can be calculated from a knowledge <jf the tants to the flame temperature. A t constant pres­
equilibrium composition of the combustion products sure, where the heat effect associated with a given
and of the energy released by the reaction. The reaction is equal to its enthalpy change :

2V '
AHr® — 0 (reaction) - f SA7J (dies) -(- 2A H pe + s j c j (products) dT (3-67)

Tr

3-19
 . AM CP 706-185

composition of the combustion products allowing

for all elements and equilibrium relationships.10
The calculation of the adiabatic flame temperature
is an iterative process for which use o f a high
speed computer is recommended.
For simpler cases, where the number o f product
species is small, the flame temperature can be cal­
culated by a trial and error process until a tem­
perature is found at which all the energy released
by the chemical reaction will be absorbed.
The calculation of the adiabatic temperature
for some chemical reactions, including those involv­
ing the oxidation of metals, can be simplified by
preparing an enthalpy or heat-content graph. This
(PRODUCTS), KOU./MOL

graph consists of a plot o f the heat content (above

the selected reference temperature for the reaction
products) as a function of temperature, using
tabulated values for H r ° — H t r °\ H t° — H 00or
heat capacity; heat of fusion; heat of vaporization;
and heat o f dissociation. The heat of reaction is
—

located on the ordinate of the plot and the hori­

zontal line is drawn from this value until it inter­
sects the heat content curve.11 The adiabatic flame
temperature is read from the abscissa.

3-2.5 SAMPLE THERMODYNAMIC

CALCULATIONS
The following sample calculations have been
selected to illustrate the application of thermo­
dynamics to pyrotechnic reactions.
Example 1. The adiabatic flame temperature
Figure 3-4 . Enthalpy o f Aluminum Oxide Versus
Temperature for aluminum burning in a stoichiometric amount
of oxygen can be calculated as follows. The overall
where AH Tb° is the enthalpy change for the reac­ stoichiometric reaction is :
tion at a reference temperature TB; EAH (diss) is
2A1 (s) + 1.502 ( g ) A l 2Os ( s )
the summation o f the enthalpy changes associated
with the dissociation of gaseous products and with The heat of reaction at 298°K is the same as the
ionization if the flame temperatures are sufficiently heat o f formation of A12C>3 (s) ~ 400 kilocalories
high; EAHpc is the summation of the enthalpy per mole. (See, paragraph 3-2.2.) The heat con­
changes associated with phase changes in the reac- tent plot for this reaction is given in Figure 3-4
where the reference temperature is taken as 298®K.
/•Tt Approximately, 400 kilocalories are released in
tion products; and E l C„ (products) dT is the
the formation of solid aluminum oxide at the
reference temperature of 298°K. As shown in
Ts .
amount of heat necessary to raise the reaction Figure 3-4, approximately 140 kilocalories of this
products to the flame temperature. energy are required to raise one mole of aluminum
Before calculating the enthalpy change for the oxide to its boiling point. The difference (400 to
reaction, equations must be obtained for the molar 140 kilocalories)'ib'consumed in vaporization o f the

3-20
 AM CP 706-185

f Example 2. The adiabatic dame temperature

> ^ for magnesium burning in air (20% oxygen, 80%
nitrogen) can be calculated in a similar manner.
The reaction, in this case is:

M g(s) + .502(g ) + 2N2(g ) -> M gO (s) -f- 2N2(g)

>^--144 4C4L The heat of reaction at the reference temperature
of 298°K is the heat of formation o f M gO (s), or
144 kilocalories per mole. Figure 3-5 is a heat con­
tent plot for the products o f this reaction where
it is assumed that magnesium oxide vaporizes by
dissociation into atoms. It must be noted that the
nitrogen in the air must be heated to the flame
temperature. The adiabatic flame tempex'ature is
rsi KCAL

limited to the boiling point, o f magnesium oxide,

about 3400°K. I f the magnesium were burned in
pure oxygen, the calculated adiabatic flame tem­
perature would still be limited to about 3400°K.
Example 3. Compositions containing magne­
I
sium and sodium nitrate are used in many illu­
minating flares. There are several possible ways
for this reaction to proceed which, in turn, deter­
mine relative amounts o f magnesium and sodium
nitrate required for the stoichiometric (balanced)
AOMM TlCrUHt
TCM
#4P0
C0A*AT
*UU: chemical reaction. Two of the possible stoichio­
metric reactions are:
1 --------- 1--------- r
(000 woo oooc 1. 5M g(s) -(- 2NaNOa(s) - » 5MgO(s)
TEMFflMTimC. K + Na20 ( s ) + N 2(g )
and: •
F igure 3 -5 . Enthalpy o f Products o f M agnesium -A ir
Reaction 2. 6M g(s) -f- 2NaNOs(s) - » 6MgO(s)
+ 2Na(s) + N2(g )
liquid aluminum oxide. The vaporization of
For the first reaction, the ratio o f the weight of
A l2Oa (1 ) at approximately 3800°K may taki place
sodium nitrate required to weight o f magnesium is:
as follow s:
A120 s( 1) -* 2 A 1 0 (g ) -f- 0 ( g ) * 2(85)
= 1.40
5(24.3)
F or this reaction, the standard enthalpy change i s :
and for the second reaction is:
= 456 kilocalories per mole
As there is not enough energy available to va].porize 2(85)
= 1.166
all the aluminum oxide, the maximum temperature 6(24.3)
is limited to the boiling point o f aluminum oxide, or
The heat of reaction for the first reaction at 298°K
approximately 3800°K
is:
^H°zss = [5 ( - 1 4 3 .8 )4 - — 99.4) — [5 (0 ) + 2( - 115.0) ] = - 588.4 kilocalories
and for the second reaction i s : , ' V
= [ 6 ( - 1484 ) + 2 ( 0 ); [6 (0 ) + 2( — 115.0) ] — — 632.8 kilocalories

3-21
 AM CP 706-185

Prom the heat content plots for the two reactions, in the hot (over 2500°K) portions o f the flame
Figures 3-6 and 3-7, the adiabatic flame tempera­ plume can be selected from thermodynamic con­
ture is nearly the same for both reactions: approxi­ siderations in the following manner.
mately 3280°K for the first reaction, and 3400°K At 2500°K, the free energy change associated
(the boiling point of magnesium oxide) for the sec­ with the reaction:
ond reaction. -­
Na20 ( l ) 2Na(g) + .502(g)
The reaction equation which best represents
the reaction to produce the products which exist is given by Equation 3-62 (Paragraph 3-2.3.4).

A F 02 boo->x = [2 (0) + .5 (0 )] - [1( - f 13.649)] = - 13.649 kilocalories

and by Equation 3-64 (Paragraph 3-2.3.4)

However, the first reaction better represents the
— (2) (2.3) (2500) log Kg overall reaction to form the products which are
~ 13649 - — — m o --------------; stable at room temperature since similar calcula­
K p = 15.4 tions indicate that Na20 ( s ) is the more stable
sodium-containing species at room temperature.
A lso: K p - (P K,) » • (P 0 i ) » = (4P 0s) 2 • ( P o ,) * Example 4. IM-11 is a widely used incendiary
mixture. It consists of 50 percent magnesium-
and: (P o j) = -746 atm
aluminum alloy (50/50) and 50 percent barium
nitrate by weight. This mixture is fuel rich and
Since the calculated (P 0 l) is greater than the
if all the fuel is to burn, extra oxygen must be
partial pressure of oxygen in the air, 0.2 atmo­
obtained from the air. I f it is assumed that suffi­
sphere, the compound Na20 (1) is not thermo­
cient oxygen is available to oxidize the metal fuels,
dynamically stable at 2500°K. Therefore, these
a balanced reaction can be written.
calculations indicate that the second reaction better
On a basis of 200 grams of IM-11, the moles of.
represents the stoichiometry of the overall reac­
each constituent are: Ba(N Os)2, 100/261.4 = 0.38;,
tion leading to the formation of the product species
Mg, 50/24.32 = 2.06; Al, 50/26.97 = 1.86. A c­
present at a flame temperature of 2500°K.
cordingly, the reaction i s :

2.06Mg + 1.86A1 + .38Ba(NOs) 2 + 1.480s + 5.92N2 ,38BaO + 6.30N2 + 2.06MgO + ..93A1S0«

The heat, o f reaction at 298°K is:

A ff0M8 = [.38( - 133.5) + 6.3(0) + 2.06( - 143:7) + .93( - 400.4)]

- [2.06(0) + 1.86(0) + .38( — 237.06) + 1.48(0) + 5.92(0)] = 628.6 kilocalories
• . 'f . .
The heat content diagram for this system is shown
tion, to be burned at low altitudes where oxygen
in Figure 3-8. As indicated on this diagram, the
is available from the atmosphere, can be estimated
adiabatic flame temperature is approximately
by assuming that the amount of magnesium in
3400°K.
excess of the stoichiometric amount which can be
Less heat is evolved if it is assumed that oxygen
vaporized by the stoichiometric reaction, based on
from the air is not available for the reaction.
the amount of sodium nitrate, can burn in the air.
Example 5. The optimum composition for a
For the magnesium-sodium nitrate system the
magnesium-sodium nitrate illuminating composi­
stoichiometric reaction is (see Example 3 ):

6M g(s) + 2NaN08(u) - » 6MgO(s) - f 2Na(s) + N2(g )

for which the heat o f reaction Aff'ggg is 632.8 kilo- which could be vaporized by this amount of energy
calories. The number o f moles of magnesium n is : ,
■ , ■ ' ■■■' ■■ . ■ ■
 AMCP 706485
<PfiOOUCT$». KCAL

Figure 3-6. Enthalpy o f Products o f Magnesium-Sodium Figure 3-7. Enthalpy o f Products o f Magnesium-Sodium
Nitrate Flare {Reaction ?) ' . Nitrate Flare (Reaction 2)

AH° 29B 632.8

n= = 15.52 moles
AH [M g(v)13f)0°K -L M g(s)298°K ] ~ 40.75

so that the weight percentage o f ! magnesiu^n for

the. optimum composition would b e : f 1

" r “ ■ (6 + « ) (MW, tig ): (21.52) (24.3) >c

X 100 = 75.5%
(6 + n) ( M W Mg) -f-'2(MWNaNOg) (21.52) (24.3) - f 2(85.01)

where M W stands for the molecular weight

culations on these sheets are for a reference tem­
perature 298.15°K and one atmosphere pressure.
3-2.6 SUMMARY OF THERM OCHEM ICA
CALCULATIONS 3-3 CHEM ICAL KINETICS .
! , •, 41 ' •
Results of thermochemical calculations such as Chemical kinetics is concerned with the veloc­
those illustrated in the foregoing examples, ;an be ity of reactions and the intermediate steps (mech­
summarized as shown in Tables 3-7 and 3-8. All cal- anisms) by which the reactants are ultimately
AMCP 706-185

TABLE 3-7
EXAMPLE OF TF.ERMOCHEMICAL CALCULATIONS:
LANTHANUM-POTASSIUM PERCHLORATE REACTION
THERMOCHEMICAL CALCULATIONS*

% M olW t &Hf Density, g [nil

REACTANTS l
Lanthanum (s) i 72.6 138.92 0. 6.15
Potassium Perchlorate(s) 27.4 138.55 103.6 2.52

PRODUCTS |
Lanthanum Oxide (s) 85.5 325.84 458 6.51
Potassium Chloride(s) 1 14.5 74.56 104.2 1.99

REACTION CALCULATIONS
8La + 3KC10<. ----- > 4La208 + 3KC1
Stoichiometric: 8(138.92) + 3(138.6) ------ > 4(325.84) + 3 ( 74.56)
Thermal: 8 (0 ) + 3 (1 0 3 .6 ) ----- > 4(458) + 3(104.2)
W t Reactants, g 1521.2
Theoretical Density (calc.), g/m l 4.41
Heat o f Reaction (calc.), Kcal 1834
cal/g 1205
cal/ml 5330
Adiabatic Temp (calc.), °K App. 4750
Gas Volume (calc.), liters 0

EQUIVALENTS
1 .0 g L a = 0.445 gK C 104 = 1742 cal
1.0 g KC104 = 2.650 g La = 4400 cal

TH EORETICAL OPTIMUM COMPOSITION

Lanthanum, % 85
Potassium Perchlorate, % 15

" A l l calculations refer to 298.16°K.

converted into the products. As most pyrotechnic 3-3.1 MOLECULARITY OF REACTIONS

reactions involve heterogeneous systems, the rela­ The simple, iintermediate reactions by which
tively simple kinetic equations developed for the reactants are ultimately converted into products
homogeneous systems are useful but not adequate. can be classified as:
These equations do, however, provide background
for understanding o f the chemical kinetics involved 1. Unimolecular. A reaction in which only one
in a heterogeneous reaction. It is to be noted that molecule reacts to yield the product (s).
the rate of a pyrotechnic reaction, which is affected 2. Bimolecular. A reaction in which two mole-
by external temperature, pressure confinement, eules (o f the same or o f different kinds)
composition, particle size, consolidation, and other react to yield the product(s).
interrelated factors, is usually best determined ex­ , 3. Termolecular. A reaction in which three
perimentally. molecules, react to form the prod u ct(o).
. '■ - •. I

3-24 ■

*
 AMCP 706-185

TABLE 3-8
EXAM PLE OF THERMOCHEMICAL CALCULATIONS:
ZIRCONIUM-OXYGEN REACTION
THERMOCHEMICAL CALCULATIONS*

% M o lW t AH f Density, g j ml

REACTANTS
Zirconium (s) 74.3 91.22 0 6.49
Oxygen (g) '
25.7 32.0 0

PRODUCTS
Zirconium Oxide (s) LOO 123.22 261.5 5.6

REACTION CALCULATIONi ?
Zr(s) + 0 2(g) — Zr02(s)
Stoichiometric: 91.22 + 32 ----- > 123.22
Thermal : AHr 0 -f O -----» 261.5
W t Reactants, gs 123.22
Theoretical Density (calc.) g/ml '— .
Heat of reaction (calc.), Kjcal 261.5
cal/g 2120
Adiabatic Temp (calc.), °K App. 4500
Gas Volume, liters/g 0

EQU IVALENTS
One g Zr = 0.346 g O2 — 2860 cal
One g O2 — 2.89 g Zr = 8250 cal

* A ll calculations refer to 298,.15' K.

4 -
(There are few, if any, termoleculir reac­ tions, k is the specific rate constant, and the ex­
tions.) ponents m, n, and 0, are empirically determined.
For gaseous reactions, concentrations are often ex­
The overall reactions occurring in the burning of 1
pressed in terms of partial pressures. Similar
pyrotechnic composition consist of a sequence
expressions could be written for the disappearance
of many simple intermediate unimolect lar, bi­
of other reactants or for the appearance of any of
molecular and termolecular reactions.
the products. -
. ■ . The overall order of the reaction is the sum of
3-3.2 ORDER OF REACTION
the exponents of the “ concentration” terms. The
I The instantaneous rate of a chemical reaction, order of a reaction, with respect to one reactant, is
as measured by the rate of disappearance of one of
the exponent of the concentration term for that
its reactants, can be written:
reactant. Examples are:
— dA
dt (3-68) Zero O rder: —k (3-69)

where; the minus sigh indicates the disappearance The reaction rate is a constant and is independent
of reactant A , the symbol [] indicates c( ncentra- of the concentration of the reactants.

8-25
A ttC P 706-185

ENDOTHERMIC
EXOTHERMIC

Figure 3-9. The Relationship Between Heat o f Reaction and

Heat o f Activation

The reaction rate is proportional to the product

of the concentrations of two reactants or to the
concentration of one reactant squared.
Only a very few reactions follow zero, first,
second, or third order reactions. Most chemical
reactions, especially at the high temperatures in­
volved in most pyrotechnic reactions experimentally
determined, are complicated combinations of many
simpler reactions. These complications include
consecutive reactions, reverse reactions, and side
TEMPERATURE, K
reactions. Hence, it is possible for the. order of a
Figure 3-8. Enthalpy o f IM -V Incendiary Mixture reaction to be fractional.12

First Order:
3-3.3 INFLUENCE OF TEMPERATURE
~ - j ^ J =k\A\ (8-70) o n Re a c t i o n r a t e s
The reaction rate is strongly dependent on tem­
The reaction rate is proportional to the concentra­
perature. A quantitative relationship proposed by
tion of a reactant. In this case, half-life (the time
Arrhenius relating the specific rate constant and
required for one-half of the reactant present at any
the absolute temperature is:
given time to disappear) is independent of the
initial concentration.
K = s exp l RT J (3-73)
Second Order: ■

where k is the specific rate constant, s is a constant,

(3-71)
Ea is the activation energy, R is the gas constant,
or: and T is the absolute temperature. Another some­
what more complicated relationship, based on the
— dj fA ] — k\A\- (3-72)
theory of absolute reactions rates, is :18

3-26
 AMCP 706485

- AH„ In some cases, the reaction of a chain carrier

= (
RT
Nh
exp [ RT
]) with a molecule may produce more than one chain
carrier. This multiplication o f the number o f chain
3-74) carriers, or chain branching, can lead to an in­
finitely rapid rate for the reaction. Explosions
where k is the specific rate constant, R is tile gas
resulting from chain branching are definitely dif­
constant, N is the Avogadro’s number, h is Planck’s
ferent from thermal explosions. In a thermal ex­
constant, Sa is the entropy o f activation, H a is the
enthalpy of activation, and T is the absolute tem­ plosion, because o f the exothermal nature of the
perature. The relationship between the heat of reaction and the difficulties attending heat removal,
activation for the forward and reverse reactions the temperature o f the system rises rapidly and
and the heat of reaction: an extremely rapid reaction or explosion may re­
sult. A branched chain explosion can take place
AH (reaction) = Aflf0 (forward) — AHa (reverse) even though isothermal conditions are maintained.

is illustrated in Figure 3-9 for an exothermic 3-3.5 HETEROGENEOUS REACTIONS

reaction.
In heterogeneous systems, reactions take place
at phase boundaries. While the kinetics of chem­
ical reactions involving more than one phase is less
3-3.4 CHAIN REACTIONS
developed than that for homogeneous systems, the
Theoretical and experimental results indicate overall process includes at least three steps :
that atom-molecule and radical-molecule reactions
normally require much smaller activation energies 1. Transport o f reactants to the phase bound­
than reactions between two molecular species. A ary. e
variety of chemical processes proceed by mech­ 2. Reaction at the phase boundary.
3. Transport o f products away from the phase
anisms which involve free radicals or atoms
in a sequence of reactions forming a, chain These boundary.
processes include thermal and photo-chemical de­ As indicated earlier, a series o f reactions will have
composition processes, polymerization and depoly­ relatively simple kinetics if the rate o f one step is
merization processes under the influence of heat much slower than any o f the others. Heterogeneous
and light, as well as a variety of oxidations and reactions, therefore, are divided into two general
. halogenations involving hydrocarbons which can types: (a) transport rate controlled, and (b) phase
give rise to the production o f flames and ex­ boundary reaction rate controlled.
plosions. . Reactions involving a gas as one o f the reactants
. In a straight chain reaction, a chain carrier— are frequently phase boundary reaction rate con­
which may be a free radical, free atom, or an ex­ trolled at low temperatures and pressures; how­
cited molecule or atom— is produced by some ever, many o f these reactions become transport
suitable primary reaction. This chain carri ;r reacts rate controlled at higher temperatures. For con­
with a molecule to produce another molecule and densed phase reactions, the transport rates will be
another chain carrier which, in turn, reacts with even slower so that reactions are often transport
another molecule to produce another chaij carrier. rate controlled even at low temperatures.
As long as the chain remains unbroken, tie disap­
pearance o f one chain carrier is accompanied by the 3-3.6 IGNITION AND PRO PAG ATIVE
formation of another chain carrier. The chain BURNING
can be broken by the removal of the chain carriers, The burning of solid propellants and consoli­
as the result of reactions between chain carriers dated pyrotechnic mixtures are similar in many
or between the chain carrier and other reactive respects. When raised to their ignition tempera­
materials, or by the collision of a chain carrier ture, they undergo preignition reactions followed
with the wall o f the containing vessel. by an ignition reaction. I f conditions are favorable,

8-27
AMCP 706-185

the reaction front moves at a nominally constant

velocity. Propagative burning involves recurring
ignition as the reaction front progresses, therefore,
ignition and propagative burning processes must
be considered together.

3-3.6.1 Ignition
The overall process of ignition involves heating
a portion o f the combustible—such as a propellant,
pyrotechnic mixture, or a combustible material in
air— to its ignition temperature, the minimum tem­
perature required for the initiation o f a self-sus­
taining reaction. While the overall ignition process
can be stated simply, the mechanism o f ignition
is not known in detail. An ignition stimulus, which
can be reduced to the effect o f heat absorption,
starts a sequence of preignition reactions involving
crystalline transitions, phase changes, or thermal
decomposition o f one or more of the ingredients.
In many cases involving propellants and pyro­
technic mixtures, a gaseous phase is formed and l/T x l(tf °KH
combustion starts in the gaseous phase. This is Figure 3-10. Ignition Time-Temperature Plots for a Binary
true for wood and similar materials where combus­ Pyrotechnic Mixture
tion starts in the gaseous phase after the formation
of gaseous combustible intermediates by thermal where t is the time to ignition at the temperature T
decomposition of the fuel. Combustion o f liquid in degrees absolute; E a, the activation energy, is a
fuels also starts and takes place in the gaseous constant; B is the universal gas constant; and. A
phase. is a constant, depending upon the material. A
The preignition period begins with the appli­ large number o f propagatively reacting systems,
cation o f the ignition stimulus and ends with the such as explosives, propellants, and pyrotechnic
start o f self-sustaining combustion. During this compositions follow this type o f equation. The
period, the rate o f heat transfer to, the rate o f value obtained for activation energy for the igni­
heat production in, and the rate o f heat loss from tion process can be considered a measure of the
that portion o f the material being ignited, are sensitivity o f the composition to heat. It will de­
important. As the temperature rises, the rate of pend, partly, on the specific experimental condi­
the heat producing reactions will increase as pre­ tions.
dicted by the Arrhenius equation (Equation 8-73). Time to ignition is often measured18,14 by
The rate o f heat loss will also increase with tem­ quickly immersing the sample in a suitable con­
perature but, because of the exponential form o f the tainer into a liquid such as molten lead maintained
Arrhenius equation, a temperature may be attained at a constant temperature and observing the time
at which the rate o f heat generation is greater than to ignition. As shown in Figure 3-1017 the results
the rate o f heat loss and ignition will result. obtained are presented in an Arrhenius type plot
The time to ignition can be expressed by an in which the natural logarithm o f the time to ig­
equation similar in form to the Arrhenius equa­ nition is plotted against the reciprocal o f the abso­
tion.18,14 lute temperature. An average value for the activa­
tion energy for ignition can be obtained b y :
. . Eg
#= A e x p -s r
E ‘ = [2.3 (slope)] ft

3-28
 AMCP 706485

though the heats of combustion of metals are rela­

ambient atmosphere
tively high, most o f the heat energy obtained from
this reaction is used up by the heat of vaporization
and dissociation of the oxide. Two models for metal
particle combustion which have been proposed based
on studies o f the burning o f aluminum differ mainly
in the treatment o f the condensed oxide formed by
the combustion reaction.18
As hollow oxide spheres are formed in the com­
bustion of aluminum, one of the models for self­
sustained combustion consists o f a vaporizing drop­
let o f aluminum which is surrounded by a bubble
o f molten aluminum oxide. The reaction rate is
determined by diffusion through the alumina
shell.18
The other model consists, of a vaporizing drop­
let of aluminum surrounded by a detached reaction
zone where the condensed alum inaproduct ap­
pears as fine droplets. The reaction rate is con­
trolled by the vapor-phase diffusion o f aluminum
Figure 3-11: Model for Burning o f Aluminum Particles and atmospheric oxidant to the reaction zone.20
This model, which appears to be most in agree­
where the factor 2.3 is the conversion fad o r for ment with the experimental data obtained for burn­
natural logarithms into common logarithms and B ing aluminum particles,18 is illustrated schemat­
is the gas constant expressed in cal per degree- ically in Figure 3-11. .
mole. Within the limitation o f this model, it is pos­
B y using the data plotted in Figure 3-10, the sible to predict conditions favoring vapor-phase
activation energy E a for ignition of the magnesium fiames, surface combustion, or no combustion. For
sodium nitrate system can be calculated in the fol- those conditions resulting in vapor-phase combus­
lowing manner: tion, the burning rate o f spherical droplets W can
be expressed as:21
Slope o f line: .
W = kr• (3-77)
y% * - yi _ 2.3(log 6 — log 2)
— *1 ~ 1 0 - 8(1.118 - 1 .0 6 4 ) where r is the radius o f the droplet; Je is a constant
involving, among other factors, the latent heat of
'0.7782 - 0.30101
= 2.3X 10® ^ vaporization, and n is a constant normally having
0.054 L) a value near 1. .
= 2.3 X 108( - 5^ ) - 20.35 X 10s
3r3.6.3 Burning o f Solid Propellants
Activation energy: -
The burning o f solid propellants has been exten­
E a = (20.35 X 108)2 sively studied and, in some cases, the mechanism
= 40.7 X 10* cal/mole of burning is reasonably well established. Solid
= 40.7 Kcal/mole propellants can be classified into two general
types, homogeneous propellants and composite pro­
3-3.6.2 Burning o f Bfetal Particles8
pellants. Homogeneous propellants are commonly
A primary characteristic Of the burning o f a called double base, or colloidal propellants, be­
metal is the limitation of the temperature attained cause they consist o f a colloidal mixture o f nitro­
by the boiling point of the resultant ox ide. A l­ cellulose and an explosive plasticizer, usually nitro-

i
3-29
AMCP 706-185

glycerin. Relatively small amounts of other ma­ Tm ■ MAXIMUM REACTION TEMPERATURE

terials are added to improve the properties of the T| - MINIMUM IGNITION TEMPERATURE
propellant. A composite propellant resembles a T, • FUSION TEMPERATURE
pyrotechnic mixture in that it is an intimate mix- - T„ - TRANSITION TEMPERATURE
ture of a fuel (reductant) and an oxidizer. It T„ - AMBIENT TEMPERATURE
AE’, AE", A2", AZ“* ■ LENGTH OF ZONES
consists o f a finely divided, solid oxidizing agent 1 - REACTION ZONE
in a plastic, resinous, or elastomeric matrix which 2 - ZONE OF FUSION
normally provides the fuel for the combustion reac­ 3 - ZONE OF CRYSTALLINE TRANSITION
tion. Solid reducing materials are sometimes in­ 4 - HEAT CONDUCTION ZONE
cluded and other minor constituents may be added Z - DIRECTION
to modify the properties of the binder or to change V • VELOCITY OF BURNING
the burning characteristics.
Combustion processes in solid propellants, as
in pyrotechnic mixtures, are complicated, because
of the several processes involved in the transforma­
tion o f the solid material, at ambient temperatures,
into gaseous, liquid, and solid combustion products
at the flame temperature. In general, for all solid
propellants, the temperature of the propellant a
short distance below the burning surface is not
affected by the combustion of the propellant. In
propagative burning as the burning surface ad­
vances, the unburned propellant is heated, and the
temperature of the material increases to the point
where the propellant decomposes into volatile frag­
«*-------
ments. In some cases, liquefaction may occur prior z
to the chemical reactions which comprise the com­
Figure 3-12. M o d e l fo r Steady State P ro g re td ve Burning
bustion process. •
The solid phase processes for double base pro­
as for a double base propellant, the burning of a
pellants, which take place in a 10-8 to 10~2 centi­
composite propellant involves the formation o f ac­
meter thick layer, are completed at relatively low
tive gaseous intermediates from the fuel and oxi­
temperatures, near 600°C. The gas phase reactions
dant, which then react.
can be considered as taking place in three zones.
The first zone exists adjacent to the burning sur­
face, and is called the fizz zone, where some exo­ 3-S.6.4 Rate of Propagative Burning22
thermic reactions may take place. In the second The steady state burning rate o f a propagative
zone, called the preparation or dark zone, activated burning system is determined, basically, by the
intermediates are formed without heat production.' temperature produced by the reaction and by the
When a sufficient concentration of activated inter­ amount of heat transferred, mainly by conduction,
mediates is developed, the final reaction occurs to the unburned composition. These quantities, in
in the flame zone; this reaction produces the con­ turn, are influenced by the ratio of ingredients, ex­
stant pressure combustion temperature. The thick­ ternal pressure and temperature, rate o f chemical
ness o f each of the zones increases with a decrease reaction, thermal conductivity, particle size dis­
in ambient pressure. tribution, and the porosity of the consolidated com­
The burning of composite propellants, as well as position. v‘
pyrotechnic mixtures involving intimate mixtures I f it is assumed that heat transfer by radiation
of fuel and oxidizer, is more complicated than the and diffusion of material can be neglected— and if
burning of a double base propellant. In general, heat losses from the side are insignificant— the
***•
 AMCP 706-185

model for steady state propagative burning illus­

trated in Figure 3-12 is applicable. It is further
assumed that the burning composition can be sep­
arated into reaction and preignition zones defined
by the limits of the maximum reaction temperature,
the minimum ignition temperature, and the am­
bient temperature, respectively.
Heat, produced as a result of chemical reactions
in the reaction zone, is transferred to the adjacent,
unreacted composition in the preignition zones,
thus affecting physical transitions and initiating
preignition reactions. It is assumed that the tem­
perature gradient across the reaction and jjreigni-
tion zones is constant with time, and that ttje posi­
tion o f these zones changes linearly with time.
Other assumptions are that the specific heat,
thermal conductivity, and density of the composi­
tion remain essentially constant over the tempera­
ture ranges involved.
For this model, the following equation can be
obtained for' the linear rate o f burning V :

S Q N tfilAiYi s exp [ * r ° ]
(3-78)
V= Figure 3-13. D iffe re n tia l Thermal Analysis Thermocouple
S DCm\/T C ircu it ,
where Q is the heat of reaction; s is the Arrhenius
frequency factor; Nt is the number o f fuel particles these conditions, A t in Equation 3-78 is equal to
per unit volume; % is the number of molecules of the mass of a metal particle m, and xt is equal to
tth species, which has an activity A { ; and x< is the 0.67 (as the surface area of a particle is propor­
order o f the reaction. E a is the energy of activa­ tional to its volume to the 0.67th power) plus a
tion, R is the universal gas constant, T the abso­ constant h, defined by the equation. ', ■
lute temperature, D the density, Cm the m ;an spe­
dr/dt=k(m )h
cific heat, and V T the temperature gradie nt. A c­
cording to this equation, the rate o f propagative Other reaction parameters will remain essentially
burning is directly proportional to the net heat of constant when the particle size o f the metal fuel
reaction, specific rate, concentration of reactants, is changed, and:
and specific surface, and is inversely proportional
to the density of the composition, mean specific (3-79)
N» \m, )
heat, and temperature gradient across the reaction
and preignition zones. The rate’ o f burning is also The subscript u refers to the mixture with an un­
proportional to the thermal conductivity. known burning rate, and the subscript s refers to
The effect of particle size on the rate of propa­ standard. The constant h in the above equation
gative burning can be estimated by assuming that often has a value of about 0.18. More accurate re­
the rate o f the chemical reaction is proportional sults are obtained if h is determined experimen­
to the rate o f change in volume of the spherical tally for each mixture.
particles and that the rate o f change in the radius The derived equation does not include a pres­
o f a reacting particle can be expressed us an ex­ sure term ; however, several o f the parameters
ponential function of the particle mast. Under which influence the burning rate are affected by

3-31
 !1

AMCP 706-185

changes in ambient pressure. The pressures depen­

dence of the burning rate v, for many similar
propagative burning reactions at higher pressures,
is sometimes given as:

v = bpn (3-80)
or by:
v = a + bpn

where a, b and n are constants, and p is the pres­

sure. A t the lower pressure normally encountered
in burning of pyrotechnic items, the relationships
Figure 3-14.1. Thermog. a vim e tric Curve fo r Hie In g re d ie n t
between the linear burning rate and the pressure Sodium N itra te
may be more complicated.

3-4 THERMO AN AL YTIC AL TECHNIQUES2®

The thermoanalytical techniques of differential
thermal analysis (D T A ) and thermogravimetry
analysis (T G A ) are versatile experimental tools
which are finding increased application in chemical
research. Differential thermal analysis involves the
heating of either the ingredient or the mixture
under study and a thermally inert reference ma­
terial to elevated temperatures at a constant rate,
while continuously measuring the temperature dif­ Figure 3 -1 4 .2 . Therm ogravim etric Curve fo r the Ingredient
ferences between them as a function of sampled Magnesium
temperature and time.
Although the techniques of D TA have been
widely used in the study of clays, minerals, and
soils, relatively little work has been reported uti­
lizing this method to investigate and characterize
the thermal decomposition of inorganic com­
pounds. In Figure 3-13, a schematic diagram
illustrates the basic measurements required in
DTA. The temperature differential between an
inert reference compound— e,g., ignited AlsOg— and
the material under study is measured and re­
corded as they are both heated to elevated tempera­
tures at a constant rate. The differential tempera­
ture is measured at TD and the sample temperature Figure 3 -1 4 .3 . Therm ogravim etric Curve fo r the Ingre d ie n t
at Tg. • i . Laminae 4116 '
The reference material chosen should be therm­
ally inert and undergo no endothermai or exo­ temperature o f the inert sample is constantly in­
thermal reactions over the temperature range under creasing, an endothermai differential temperature
consideration. Consequently, the inert sample heats results. Conversely, an exothermal reaction causes
at a rate equal to that o f the furnace. When the the sample temperature to increase more rapidly
sample being analyzed undergoes an endothermai than the reference,temperature, and the result is an
reaction, its trmperature remains, relatively con­ exothermal differential. When there is no thermal
stant or increases very slowly. Therefore, since the reaction, the sample and reference compounds heat

3-32
 AMCP 706-185

ture under consideration. Oxidation o f a material

such as a metal powder by a gas, e.g., oxygen or
nitrogen, involves the evolution o f heat and is,
therefore, an exothermal reaction. Oxidation-re­
duction reactions normally are exothermal proces­
ses, particularly when considering reactants such
as metal fuels and solid oxidants. Since these types
of phenomena are indicated by the D T A curves
obtained, these curves may be used to characterize
TEMPERATURE CC)
the system under study in terms o f its thermal re­
F igure 3-15.1. D iffe re n tia l Thermal Analysis C urve fo r the actions, both physical and chemical. Integration of
In g re d ie n t Sodium N itra te areas under endothermal bands also has been used
to obtain a serai-quantitative estimate o f the
amount o f one or more o f the ingredients present.
Thermogravimetry consists o f continuously
weighing a sample as it is heated, either at a con­
stant temperature or to elevated temperatures at
a constant rate. Curves are obtained as a function
of temperature or time. Since thermogravimetric
curves are quantitative representations of weight
changes, they can be related to the chemical and
TEMPERATURE CC) physical changes taking place in the sample as it
is heated, and can often be used to determine the
F igure 3 -1 5 .2 . D iffe re n tia l Thermal Analysis C urve fo r the nature o f the intermediate and final reaction prod­
In g re d ie n t M agnesium
ucts.
Typical results obtained by thermogravimetric
and differential thermal analyses techniques are il­
lustrated by the results obtained in a study of the
pyrotechnic illuminating mixture composed o f 54
percent magnesium, 36 percent sodium nitrate, and
10 percent Laminae.24 The thermogravimetric stud­
ies under normal atmospheric conditions indicate
that all three ingredients undergo thermal reac­
tions involving weight change as a function of
tem perature furnace temperature, as illustrated in Figures 3­
14.1 through 3-14.3. Sodium nitrate exhibits a
Figure 3-15.3. D iffe re n tia l Thermal Analysis C urve fo r the
In g re d ie n t Laminae 4116 weight loss at temperatures from 700°C to 1000°C
which corresponds to a complete conversion to
at the same rate and no differential temperature is sodium oxide. The curve also shows a point of in­
observed. Dehydration of a hydrated or hygr< iscopic flection at about 850°C due to the concurrent de­
substance is an endothermic process as are those composition o f the intermediate product, sodium
o f fusion boiling. Transitions involving trans­ nitrite. Magnesium shows a continuous gain in
formations from one crystal lattice to another, or weight which begins at about 625°G and continues
the free rotation o f ions in a lattice are, most! often, on past the maximum temperature. The curve
endothermal processes; however, there are Several varies in slope, becoming perceptibly steeper at
isolated exceptions to this general rule. Decomposi­ 650°C, and markedly less steep at 680°C. This
tion reactions may be either endothermal or exo­ weight gain is attributed to the successive forma­
thermal depending upon the system and tempera­ tion o f magnesium nitride and magnesium oxide.
 t]

AMCP 706-185
CC) DIFFERENTIAL TEMPERATURE

Figure 3-16.3. D iffe re n tia l Thermal Analysis C urve fo r the

Magnesium -Sodium N itra te M ix tu re {C urve II)

i 3-16.1. D iffe re n tia l Thermal Analysis C urve fo r the

M agnesium -Sodium N itra te ’M ix tu re {C urve I)
DIFFERENTIAL TEMPERATURE (*C)

Figure 3 -1 6 .4 . D iffe re n tia l Thermal Analysis C urve fo r the

Sodium N itrate-Lam inae M ix tu re

dothcnnic crystalline transition at 270° C, imme­

diately followed by endothermic fusion at 306°C.
The differential thermogram of magnesium shows a
double exothermic peak beginning at about 565°C,
which may be due ,o the formation of magnesium
nitride or magnesium oxide on the surface of the
metal, or to reaction with the glass tube. The
Figure 3 -1 6 .2 . D iffe re n tia l Thermal Analysis C urve fo r the double peak culminates in the endothermic fusion
Sodium N itra te -C a rb o n M ix tu re . o f magnesium. The D TA curve o f polymerized
a Laminae displays only one broad, endothermic
Polymerized Laminae first shows a continuous band, beginning at about 250° C, with a peak tem­
weight loss, extending from about 100°C to 500°C, perature o f 371°G. However, it appears as though
which markedly changes in slope at 350°C. This several overlapping reactions are responsible for
loss is followed by another loss,.ending at 625°C, the heat absorption. A t 305°C, a colorless liquid
which represents a loss in weight equivalent to the condenses on the upper part o f the sample tube. A t
initial weight o f the sample. This loss is due to 332°G, there are dense, white fumes escaping from
chemical degradation o f the polymer to carbon, the tube. A t 479°C, after the endotherm is over,
which is then completely oxidized. ■ the sample gives off dense, yellow fumes and some
The D T A curves for the ingredients are illus­ charring is observed in the tube.
trated in Figures 3-15.1 through 3-15.3. The only As shown in /Figures 3-16.1 through 3-16.5, the
thermal effect exhibited by sodium nitrate is en- binary fuel mixture, magnesium-Laminac, gives
. ■ * '
' ii.
3-34
 AMCP 706-185

TEMPERATURE CC) TEMPERATURE CO

F igure 3-16.5. D iffe re n tia l Thermal Analysis Curve fo r the Figure 3 -1 7 .2 . D iffe re n tia l Thermal Analysis C urve fo r the
M agnesium -Lam inae M ix tu re ' Magnesium -Sodium N itrate-Lam inae C om position

nitrate are very small because only very small, sam­

ples were used. The fuel-rich system 60-40 mag­
o 40 -
nesium-sodium nitrate* Curve II, used in the test,
uj !2 % /8 2 % /6 % ignited at 560°C. The DTA curve shows the endo­
o: thermic crystalline transition of sodium nitrate at
3
$ 265°C, 'and its fusion at 305°0, in addition to the
£ 20
O. sharply exothermic ignition. The stoichiometric
s mixture. Curve 1. for the reaction:
hi

' Mg - f NaN03 MgO - f NaN02

containing only 22 percent magnesium, ignited at

hi
a. 613°C and displayed endothenns at 270° and 310°0
h •which were caused, respectively, by the crystalline
Q transition and fusion of sodium nitrate. Sodium
20 nitrate-Laminac ignited with an apparently small
JL evolution of heat at 417°C that may have been due
100 200 300 400 500 600
to a combination o f small sample size and forma­
TEMPERATURE CC)
tion of gaseous products. The differential thermo­
F igure 3-17.1. D iffe re n tia l Thermal Analysis Curve fo r the gram exhibits the crystalline transition of sodium
M agnesium -Sodium N itra te -C a rb o n C om position nitrate at 268°C and its fusion at 297°C. A broad,
shallow endotherm, during which a colorless and
D T A evidence of the thermal decomposition of the then a yellow liquid condenses on the sample tube,
Laminae present by several shallow endetherms culminates in ignition. The sodium nitrate-carbon
prior to the sharply endothermic fusion o f mag­ system exhibits the crystalline transition o f sodium
nesium. The magnesium fusion endotherm is fol­ nitrate, successfully followed by sodium nitrate
lowed by an exothermal reaction, probably the ‘fusion, and then ignition at 467°C. ■
oxidation of molten magnesium. The absence o f any DTA curves for the two ternary compositions
exothermal peak prior to magnesium fusion sug­ are shown in Figures 3-17.1 and 3-17.2. The mix­
gests that, although the Laminae does not react ture containing magnesium, sodium nitrate, and
with the bulk o f the metal, it protects the solid carbon is very similar to the sodium nitrate-carbon
magnesium from reaction with* air. This four binary mixture; i.e., it ignited at 455°C immedi­
binary fuel-oxidant mixtures did ignite. For all ately following the crystalline transition and fusion
the ignitible sodium nitrate compositions run on o f the sodium nitrate. The mixture containing mag­
the time-base apparatus, the endotherms corre­ nesium-sodium nitrate-Laminac ignited at 489°C.
sponding to the crystalline transition of sodium The first thermal phenomena observed were the

3-35
AMCP 706-185

crystalline transition and fusion o f sodium nitrate from the second exothermal reaction. These and
at 270°C and 299°C, respectively. There was a related results indicate that it is not feasible to
small, sharp exothermal reaction beginning at write preignitidn or combustion reactions for the
373°C, and another beginning at 450°C, with peak systems containing Laminae due to the complexity
temperatures of 405°C and 485°C, respectively. of the polymer and the uncertainty of its com­
Ignition occurred as the system was recovering bustion products.

REFERENCES
I. M. T. Howerton, Engineering Thermodynani- cation of the Absolute Reaction Rate Theory
. ics, Van Nostrand Co., Inc., Princeton, N. J., to the Ignition of Propagative Reaction Sys-
1962­ terns. The; Thermal Ignition of the Systems
2. Handbook of Chemistry and Physics, 45th Lithium Nitrate-Magnesium, Sodium Nitrate-
Ed., The Chemical Rubber Co., 1964-65. Magnesium,” Journal of Physical Chemistry
3. G. Custard, G. Francis, W. Schnackenberg, 60. 867-71 (1956).
Small Arms Incendiaries, A Review o f the 15. S. Gordon and C. Campbell, “ Pre-ignition
History and Development, A Vols, Frankford and Ignition Reactions of Pyrotechnic Sys-
Arsenal Report R1407, 1956. terns, Proceedings of. the Fifth Symposium
4. Reilly and Rae, Physico-Chemical Methods, on Combustion, Reinhold Publishing Corp.,
2nd Ed., Van Nostrand Co., Inc., Princeton, N. Y „ 1955.
N. J., 1932. v 16. II. Henkin and R. McGill, “ Rates Explosive
5. Walter J. Moore, Physical Chemistry, 3rd Ed., Decomposition o f Explosives, ’ ’ Industrial and
Prentice-Hall, N. Y., 1962. Engineering Chemistry 44, 1391-5 (1952).
6. O. Kubaschewski and E. Evans, Metallurgical 17. M. Gilford, S. Gordon, G. Weingarten, Ther­
Thermochemistry, John Wiley & Sons, N. Y., mal Parameters Associated With the Ignition
'■ 1956. ■ ’ ; ■ ... ' - ■ .■ of the Magnesium-Sodium Nitrate Systems,
7. Irving M. Klotz, Chemical Thermodynamics, Picatinny Arsenal Technical Note 27, Dover,
Prentice-Hall, N. Y., 1950. New Jersey.
8. Irving Glassman, Metal Combustion Processes, 18. H. C. Christensen, R, H. Knipe, A. S. Gordon,
■ Paper presented at 14th Annual Meeting, Survey of Aluminum Particle Combustion,
American Rocket Society, Nov. 16-20, 1959. Paper presented at Meeting of the Western
9. S. Glasstoiie and D. Lewis, Elements of Phys- States Section of the Combustion Institute,
teal Chemistry, Van Nostrand Co., Inc., Prince­ University of Utah, Salt Lake City, Oct. 26-27,
ton, N. J,, I960. ’ 1964. ; ' . . .. '
10. AMCP 706-282, Engineering Design Hand­ 19. W. M. Fassell, C. A. Papp, D. L. Hilenbrand,
book, Propulsion and Propellants. and P. P. Sernka, The Experimental Nature
II. J. B. Conway, A. V. Grosse, Powdered Metal of the Combustion o f Metallic Powders, Solid
Flames, Office of Naval Research, Contract. Propellant Rocket Research, Academic Press,
N9-ONR-87301, Washington, D. C. N. Y., 1960.
12. Keith J. Laidler, Chemical Kinetics, McGraw- 20. T. A. Brzustowski, Vapor-Phase Diffusion
Hill Book Co., Inc., N. Y., 1950. Flames in the Combustion of Magnesium and
13. S. Glasstone, K. J. Laidler, and H. Eyring, Aluminum, Ph.D. Thesis, Princeton Univer­
The Theory of Rate Processes, McGraw-Hill sity, 1963.
Book Co., Inc., N. Y., 1941. 21. D. K. Kuehl, The ignition and Combustion
14. E. S. Freeman and S. Gordon, “ The Appli­ of Small Diameter Aluminum Wires, Paper
 AMCP 705485

REFER'ENCES (cont’ d)
presented at Western States Section o f the 23. S- Gordon and C. Campbell, Differential Ther-
Combustion Institute, University o f Utah, $alt mol Analysis o f Inorganic Compounds, Pica-
Lake City, Oct. 26-27, 1964. tinny Arsenal, Dover, New Jersey.
22. Eli Freeman and Garry Weingarten, A Ther­ 24. V. D. Hogan and S. Gordon, Pre-ignition and
mal Theory for Bates o f Propagative Burring,
Picatinny Arsenal Technical Report 2596, Sodium Nitrate-Laminae, Picatinny Arsenal
Dover, New Jersey, 1956 (DDC A D 218 171) : Technical Note 23, D over,. New Jersey, 1958.:

8-87

i
i". f '
ft
 AH CP 706-185

CH APTER 4

V S IB IL IT Y

4-1 INTRODUCTION and the cones. The central portion o f the retina,
In the design and development of military the fovea, is populated exclusively by cones, and is
pyrotechnic devices for illuminating a selected the area of color perception. The region immedi­
area, and for-visual signaling when other methods ately surrounding the fovea is known as the para-
of communication are impractical or imposs ible, fovea and contains the rods, which do not recog­
an understanding o f human visual performance nize colors. The eye has two distinct states—the
is important. The complex tasks performed in light-adapted state and the dark-adapted state.
modern military operations require sufficient light The eye is in the light-adapted state when the field
in order that unfamiliar objects can be located luminance is about 10~8 candella per square foot,
and recognized against their backgrounds. and is dark-adapted at luminances below this. How­
Signaling by methods which depend on sight are ever, the eye is not fully dark-adapted until it has
commonly used in military tactics, in training ex­ been exposed to the low level o f luminance for
ercises, and in evaluation of performance o f Mili­ about 30 minutes. Only two to three minutes are
tary items during development programs. Tlhese required for the transition for the dark-adapted to
signals derive from packaged units designed to the light-adapted state.
emit smoke, flame, or light, or otherwise to give In the light-adapted state both the rods and
visual indication of some event, e.g., the markirg of cones are receptive to light. In the dark-adapted
a particular spot on the ocean, or to trace the tra­ state only the parafovea, composed of rods, is ac­
jectory of missiles or other moving devices. ” hey tive, with the results that color differences are not
may be coded by color to convey information re­ recognized and that faint signals are best seen when
lating to different types o f events or a sequence of off to a side (looked at “ out of the corner of the
events. For example, a red signal might be used eye” ) rather than when looked at directly.
to indicate the arming o f a fuze and a green signal
to indicate when functioning occurs. Signals for 4-2.1 BRIGHTNESS CONTRAST
marking purposes can be used to aid in tracking
An object can be distinguished from its back­
enemy submarines, to allow submerged submarines
ground (or from another object) because it has a
to make their positions known, to locate tow tar­
different color or brightness. It has been shown
gets, and to call attention to survivors o f air crushes
experimentally that differences in brightness are
or sinkings.
usually much more important than'differences in
color. The brightness contrast C is defined by the
4-2 VISION equation:
Inasmuch as vision is a sensation recorded by
the eye, it is important to consider some oi! the
properties and characteristics of die eye. The
functioning of the eye involves a complex of where B is the brightness o f the object and B' is
physical, physiological, and psychological factors. the brightness o f the background. I f an object is
Light falling upon the eye acts as a stimulis to not as bright as its background, the brightness con­
produce a sensation which, in the simplest case, is a trast is negative and approaches a value o f —1 as
sensation of brightness. a limit. When the object is brighter than its back­
The eye contains two types o f receptors, the rods ground, the contrast may be very large, for ex-
 AMCP 706-185

C0 = (Ct? -j- Cc2) ' 4 (4-2)

where C6 is the brightness contrast, and Cc is the

achromatic brightness contrast, equivalent to the
chromatic component of the contrast. As chromatic
components of contrast are rarely over 25 percent
o f the total and are invariably associated with
brightness contrasts greater than 25 percent, visi­
bility, under field conditions, depends primarily on
the brightness contrast. This is especially true for
objects viewed at a distance since the scattered light
LOO B (CANDLES/M*)
from all sources tends to still further dilute the color
contrast. Where brightness contrasts are limited,
Figure 4-1. Thresholds o f Brightness-Contract for 80%
as in the case of signal flags or panels, color dif­
Detection for Five Angular Fields (Minutes o f Arc)
ference may increase visibility. However, at or near
ample, a bright light on a dark night. The bright­ the limit o f visibility, the hues of chromatic target
ness contrast in daylight or in artificially produced are not perceptible. This is particularly true for
white light, where the difference in brightness is violet, blue, green, and yellow stimuli. Orange,
due mainly to , the amount of light reflected by red-purple, and red appear reddish or brownish
the object as compared to its background, seldom under these circumstances.
exceeds a value of 10. I f an area has been camou­
flaged, the brightness contrast may be 0.1 or less.
4-3 ATTENUATION OF CONTRAST
If the brightness ratio B/B' approaches unity,
The apparent contrast (both brightness and
a stage is reached where an object can no longer
achromatic) between an object and its background
be distinguished from its background.
is reduced when viewed through a medium which
While the threshold contrast varies with eacli
scatters and absorb light. For a homogeneous
individual., average values as shown in Figure 4-1
medium like the atmosphere, containing both the
depend on the angle which the object subtends at
observer and the object, the amount of contrast
the observer's eye and the mean level o f illumina­
reduction is governed by the balance between the
tion. For daylight conditions, a value of 0.02 is
light transmitted from the object, and its back­
generally accepted as an average value for the
threshold contrast or limen. ground, and the space light contributed by the
intervening medium. I f the medium is stratified,
Visual acuity is often expressed as the re­
as would be the case when a smoke screen is located
ciprocal of this angle in minutes of a rc.' An acuity
between the object and the observer, reflection due
value of 1.0 is accepted as a standard for normal
to multiple-scattering may still further reduce the
vision even though, under ideal conditions, much
apparent contrast.
greater detail can be resolved.
In general, if the inherent brightness contrast
Up to about one-fifth second, the photochemical
between two objects, or o f an object and its back­
reciprocity law applies and the product of the il­
ground, is given by Equation 4-1, the apparent
lumination times the duration is a constant. It has
brightness contrast Cx, when viewed at a distance,
been demonstrated in threshold measurements o f
will be: ..
visual performance that, in those cases where
the duration is longer than one-fifth second (as is ( B - B ') e - O *
true for most cases of interest in pyrotechnics), (4-3)
B 'e -f + O
this is not applicable.
where B is the brightness o f the first object and B'
4-2.2 O V E R A LL CONTRAST is the brightness o f the second object or the back­
The overa’ l contrast C0 between an object and ground, (1 is the'scattering coefficient, x is the dis­
its background is approximately: tance, and Q is' the glare scattered and reflected by

4-2
 AM CP 706-185

(slant) range B ; C is their inherent contrast; B

is the brightness of the object; B' is the brightness
of the background (or second o b je c t); and $ is
the scattering coefficient.
I f the atmosphere is optically homogeneous,
i.e., the apparent brightness of the sky is not
changed by moving toward or away from the
horizon, this equation reduces to:

Cx = Ce~»* (4-5)

where Cx is the apparent contrast at a distance x.

The meteorological range, the horizontal range
for which the transmission of the atmosphere is
two percent, is given b y : •

= In 0.02 — (4-6)
p p •

The meteorological range is the distance at which a

large black object, which has an inherent contrast
of —1, can just be recognized against a daytime
sky. Visibility, as normally reported, is about %
the meteorological range. The meteorological ranges
for typical weather conditions are given in Table
4-1.
I f the object is viewed against backgrounds
F igure 4 -2 . A p p a re n t C o n tra st as a Function o f Distance other than the sky, the expressions are more com­
plicated. The apparent contrast at an effective
a cloud in the same direction as the light from the distance R of a target against any background is
object. The object will be visible only if ths ap­ given b y .
parent contrast is greater than the threshold con­
trast or “ limen” for the particular total illumina­
tion level. * 1+

where C is the inherent contrast between the ob­

4-3.1 ATTENUATION OF CONTRAST ject and its background, B H/B’ is the ratio o f the
BY THE ATMOSPHERE brightness of the horizon sky in the direction of the
The apparent contrast between two distant object to that of the background, and (3 is the scat­
objects, or a distant object and its background, is tering coefficient. I f the ratio B h/B' is one, this
reduced as shown in Figure 4-2 when they are equation reduces to the equation applicable to the
viewed through an atmospheric aerosol. This re­ visibility o f an object against the horizon sky.
duction in apparent contrast limits the maxi mum The calculation of the visibility o f an object,
distance at which targets and signals can be seen. when viewed from above, is complicated due to the
The most general expression for the redaction stratification o f the atmosphere. I f this stratifica­
o f contrast by the atmosphere is: tion can be considered continuous, the scattering
coefficients will vary regularly and in a predictable
O j = J r C e -o * . (4-4) manner. Normally, however, this is not true, and
- t.vy the effective optical range R is taken as the hori­
C j is the apparent contrast between, two objects, zontal distance containing as many scattering
or an object and its background 'at the effective particles as are found in the slant path R. The

4-3
AMCP 706-185

TABLE 4-1
METEOROLOGICAL RANGE FOR TY PICAL W E A TH E R CONDITIONS

Daylight Attenuation
Visual Coefficient, B, Transmission,
Weather Range, V Per Sea Mile Per Sea Mile
Dense fog 50 yards 156.4 0.0240
Thick fog 200 39.1 0.0210
Moderate fog 500 15.6 0.024
Light fog 1000 7.82 0.022
Thin fog 1 sea mile* 3.91 0.02
Haze 2 1.95 0.141
Light haze 3 1.30 0.272
' 4 0.98 0.376
Clear 5 0.782 0.457
6 0.651 0.521
■ 7 0.559 0.572
8 0.488 0.614
9 0.434 0.640
Very clear 10 0.391 0.676
11 0.356 0.700
12 0.326 0.723
14 0.279 0.756
16 0.244 0.783
Exceptionally clear 18 0.217 0.805
20 0.196 0.823
24.1 0.162 0.85
37.1 0.105 0.90
71.8 0.051 0.95
Theoretically pure air 167 0.0234 0.976

*1 aea mile equals 1.15157 statute miles or 6080 feet

effective optical range R is related to actual path the smoke may occupy only a relatively narrow
by: region between the target and the observer. Under
these circumstances, the intensity of illumination
21,700 ( , — R sin 0
Sin 0 \ l 21,700 may vary greatly depending on the relative loca­
tion of the object, the observer, the smoke cloud,
where 0 is the angle that the slant path R makes
and the source(s) of illumination, so that the
with the horizontal. Plots of this equation for
quantify of smoke required for obscuration is a
various values of 9 , applicable for intermediate
values of the slant range R, are presented in Figure highly variable quantity. Because of the compli­
4-3. The values o f the true altitude are indicated cated way in which the incident light is scattered
by the dashed lines on this diagram. as a function o f angle and because of multiple
scattering, the vdegree to which light will pene­
4-3.2 OBSCURATION OF VISION trate a cloud cut only be approximated. While a
BY A R T IF IC IA L SMOKE CLOUDS major fraction* of the light scattered by particles
The influence of artificially produced smoke near the optimum size for a screening smoke is
clouds on visibility is complicated by the fact that scattered in the forward direction, some light is
 AMCP 706-185

SLANT
(YARDS)

RANGE
RANGE

(F E E T )
SCANT

«0«r« 4-3. Optical Slant Sang* Diagram tar the Optical Standard Atmotphan
4-5
 AMCP 706-185

reduce the illumination on the target and back­

ground, will increase the effectiveness of a smoke
screen.

4-4 V IS IB IL IT Y OF TARGETS AND SIGNALS

The distance at which a ship, low-flying air­
craft, shoreline, or other target, and also the dis­
tance at which a signal can be seen against its
background depends mainly on (1) the perceptual
capacity of the observer at the level of brightness
to which his eyes are adapted and (2) the apparent
contrast between the target and its background
and the angle it subtends at the eye of the observer.
The angle, subtended by a target area, depends on
Acuity and Contrast the size and shape of the object. For a circular
target at a distance o f X yards, the angle a sub­
scattered in the backward direction. If a cloud is tended by a circular target A square feet in area, is :
of a sufficient depth and concentration, essentially
all o f the light not absorbed by the cloud will re­ a_ minutes of arc (4-10)
X
turn to and be scattered from the same side of the
cloud that it entered and the cloud will behave as As the apparent contrast is also a function of the
a white body diffusely reflecting the light which distance, calculations intended to determine the
falls upon it. range at which a target or signal can be sighted
For a thinner cloud, part of the incident light must be a series of successive approximations. In
will penetrate to the target and background. The addition, because of the curvature of the earth,
apparent contrast o f the target against its back­ the target or signal, or the observer, must be ele­
ground, in this case, is : vated for sighting long distances. The geometrical
range for various heights is given b y :5*
Ck (4-9)
X = 1.325 (tf-H i,) (4-11)
where I 0 is the effective intensity o f the incident
light, M is the reflectivity o f the target, M is the where H is height o f target or signal in feet, ft, is
reflectivity o f the background, (1 is the scattering height of observer in feet, and X is the distance
coefficient, R is the effective distance from the tar­ in miles.
get to observer, and f is the fraction of inci­
4-4.1 V IS IB IL IT Y OF TARGETS
dent light which penetrates to the target. The
amount of light reaching the target, as well as the UNDER A R T IF IC IA L ILLUMINATION8
attenuation of the contrast between the target and It is impractical to require that normal visual
its background, depends on the number o f scatter­ acuity (resolution of one minute of visual arc) be
ing particles which, in turn, depends on the product maintained when the illumination is provided by
of the concentration o f the smoke and the thickness pyrotechnic flares since there is a practical limit
of the cloud. to the intensity. The intensity should be such that
The effectiveness o f a smoke screen also depends targets, having a size and a contrast with the
on the relative location o f the smoke target back­ background that is typical of field conditions, can
ground and light source. The effect o f these changes be readily located and recognized. Intensities
in relative locations is complicated, and has not greater than this minimum are excessive. As shown
been worked out in detail. In general, anything in Figure 4-4, illumination levels between 0.1 and
which tends to increase the effective brightness of 10.0 foot-lamberts (F L )* , which can be obtained
the smoke cloud, as well as anything that tends to • NOTE 1 millilam bert 1 foot-lam bert.

4-6
 AMCP 706-185

TAB LE 4-2 ■4
REFLECTAN CE VALUES (IN PE RCENT) OF VARIOUS TERRAIN
FEATU RES AND BU ILDING M ATERIALS

Object Wavelength in Microns

I. Natural Terrain
a. Sods: 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Dry yellow earth 16 37 55 69 76 82
Wet yellow earth 5 9 25 42 58 67 76
Dry sand 18 28 37 45 52 56 58
Wet sand , 10 15 26 32 37 41 43
Dry red earth 8 8 20 28 33 35 37
Wet red earth 6 6 12 28 22 24 25
Dry brown earth 8 11 15 19 21 23 24
Wet brown earth 4 6 11 14 15 17 19
Dry loain 8 12 18 20 20 21 22
W et loam 5 6 7 9 10 11 11
b. Vegetation:
i Grass 6 8 10 13 .55 67 70
Evergreens 3 4 . 7 6 24 24 24
Straw 7 15 24 33 39 44 46
Dead grass 7 13 20 26 31 35 37
{ Dead brown leaf 6 9 11 27 43 51 69
, Dead yellow leaf 6 .10 23 39 45 48 51
c. Terrain as seen from 4,000 f e d :
■' Green field 4 7 10
Brown field 3 4 5
Yellow-green vegetation 5 8 15
Light sand 12 16 21
Sandy ground .8 12 14
Wet mud 5 8 9
Mud covered with water 4 7 6
Pond water 3 2 1
Water with suspended material 3 4 5
: Dark volcanic rock . * 6 6 7
Black asphalt runway 4 4 4

II. Building Materials

a. Paints: j 4 4 4 4
Black 6 6 11 12
Earth brown 9 15 45 47
Earth yellow ? 6 7 19 21
Earth red 15 24 42 43
' Sand . 16 21 37 41
‘ Desert sand 7 9 16 16
Field drab ‘ ? 4 7 11 9
Olive drab j 4 6 7 5
Forest green
AMCP 706-185

TABLE 4-2 (coat’ d)

Object Wavelength in Microns

II. Building Materials (Continued)

a. Paints ( Continued) : 0.5 0.6 0.7 0.8 0.9 1.0
Dark green 5 7 6 6
Sky gray 33 40 48 45
Haze gray 35 33 24 24
Blue gray 25 27 25 23
Ocean gray 22 20 13 13
Sea gray 14 13 12 10
Slate gray 9 10 9 7
Sea blue 7 6 5 4
Bed 5 5 25 75
b. Materials:
Concrete tiles (uncolored) 28 35 37 37 37 37
Concrete tiles (black) 9 9 9 9 9 9
Slates (silver gray) 19 20 21 21 21 21
Slates (blue gray) 12 13 14 14 15 16
Slates (dark gray) 10 12 12 12 11 10
Clay tiles (Dutch light red) 23 51 64 66 66 65
Clay tiles (red) " 11 28 35 37 40 40
Clay tiles (red-brown) 13 25 30 33 40 41
Dark concrete 13 16 20 17
Light concrete ' 25 32 37 38
Galvanized iron 23 26 27 25
Dirty galvanized iron 9 9 9 9 9 9
Aluminum 45 49 52 53
Steel 29 31 34 35
Granite 10 15 20 22
Asbestos cement 35 43 45 44 41 37
Weathered wood 9 11 8 10
Weathered asphalt 9 10 11 11 11 11
Basalt 5 6 7 6

quite readily with pyrotechnic illuminants, should t-4.2 V IS IB IL IT Y OF SIGNALS

be adequate to detect and identify objects sub­ The requirements for visibility o f a signal vary
tending approximately 5 minutes o f visual arc considerably from one application to another. It
against a terrain background, provided the con­ is not always possible, nor necessary, to provide
trast is greater than 0.1. When the target and its a signal which is visible at extreme ranges. How­
background are illuminated by the same light ever, it is desired that a signal produce the maxi­
source, this contrast will (as is true for daylight mum visual effect over as long a distance as pos­
illumination) depend on the reflectance values for sible and, in some cases, for as long a period as
the target and background. Values for typical possible. In addition, it is often necessary to
materials which might be found in the field are modify signal performance to meet practical size
given in Table 4-2. and weight restrictions. These restrictions are

Nr
4-8

■J
 AMGP 706-185

i'

Figure 4 -5 . E ffect o f D irection o f Illum ination on the

Luminance o f a Smoke Column

Figure 4 -6 . E ffect o f Relative D irection o f Sun a n d Smoke

extremely important for signals carried aboard
■ on Time o f D iscovery
a ircra ft,or submarines.
of visibility, will be effectively the same color as the
horizon.
4-4.2.1 Visibility of Smoke Clouds
The visibility of a relatively small dense smoke
cloud, such as would be produced as a signal, de­ 4-4.2.2 Visibility o f Light Sources
pends on the ability of the smoke particles to Factors which influence the visibility of a light
scatter light, or reflect by multiple scattering, in source are essentially the same as for any other
the direction o f the observer. Factors whhh de­ object. The visibility of an illuminated visual
termine, to a large extent, the visibility of a smoke angle of approximately one degree or less is de­
cloud include: (1 ) illumination o f the smoke cloud, pendent principally upon the total light emitted
and (2) contrast o f the cloud against a back­ by the area. For a steady point source:
ground.
The effective brightness o f the cloud depends F = -^ 2 = 3-5 X 10~9 H 1/2 lumens/cm2 (4-12)
on the relative location of the observer and cloud,
as well as the intensity and direction of the inci­ where F is the threshold value of flux density (in
dent light. This effect is indicated in Figure 4-5 lumens per square centimeter), C is the threshold
for a relatively dilute, laboratory smoke column. intensity o f the source (in candles), X is the dis­
These results, due to the tendency toward forward tance from source to observer (in centimeters),
scattering, indicate that a smoke column is many and H is the background brightness (in candles
times as bright in the direction o f the sun as it is per square centimeter). The illumination pro­
opposite to the sun. The effect o f the relative di­ duced at the observer’s eye is reduced because of
rection o f the sun and smoke is also illustrated in atmospheric attenuation in accordance with the
Figure 4-6 where, as expected, the time !of dis­ following equation:
covery is the least when the relative .positions re­
sult in 'a maximum cloud brightness! Color of a E m= -^ 2 exp [-3 .9 1 2 (4-13)
relatively dense cloud results from multipie scat­
tering and absorption. The color intensitjy in a where /„ is the intensity o f the source and X K is
dilute cloud may be less because of. the deduced the meteorological range. This equation is valid
multiple-scattering efficiency. I f the particles mak­ only when X is large enough that the light may be
ing up the cloud are the wrong size (too small, considered as a point source. The maximum angu­
normally), the color produced may be changed lar size of the light source, which can be con­
and/or suppressed. The apparent color of the sidered as a point source, varies with the adapta­
cloud will change with distance and, near the limit tion brightness as given in Table 4-3.

4?
AMCP 706-185

TABLE 4-3
MAXIMUM ANGULAR SIZE OF LIGHT SOURCE AS A FUNCTION
OF ADAPTATION BRIGHTNESS

Adaptation brightness Maximum angular size

(foot-lamberts) (minutes of arc)
1,000 0.708
100 0.708
10 0.750
1 0.891
io-» 1.30
io - 2 2.82
1 0 -» 6.68
10- « 8.55
io - 8 15.0

A flashing point-source light, where the flashes values of T as low as 1.0 second) because of the
are of short duration (less than 0.2 second), must lower visibility of short flashes (according to
have, in general, a higher candlepower than a Blondel and Rey). I f T is greater than 1.0 second,
steady light in order to be seen. It has been found the finding time is also longer because the eye
that the threshold intensity F, required for visi­ may pass over the light location during the off
bility of a light of duration t0 seconds, is given interval. It was found that a light of ten times
b y :4 ' threshold intensity was almost always located at
the first flash while three flashes were needed if the
Fto = F , (t0 + 0.21) (4-14)
light were only five times the threshold.
where F , equals the threshold intensity o f a steady The effect of selective transmission by some
light.. Thus, when a flash lasts several seconds so types of atmosphere is also important when con­
that 0.21 is negligible, the threshold is the same sidering colored lights. Table 4-5 indicates the
as for steady light. However, as shown in Table magnitude of selective absorption of components
4-4, for small values of t0, where F will be larger of sunlight by the atmosphere.
than F „ this is no longer true. These ratios aire not
changed greatly for candlepowers up to 50 times 4-4.3 ESTIMATION OF V ISIBILITY
threshold for flash durations from 0.05 second up The estimation Of visibility can be simplified
to 1.0 or 2.0 seconds. by the use of nomographic visibility charts pre­
For situations in which it is not known where a pared for this purpose. A chart for circular tar­
flash will appear in the field of view, the finding gets, which has been adapted from the more com­
time is quite important. The two variables o f ma­ plete charts available, is given in Figure 4-7. To
jor importance in the conspicuity (short finding use this chart for determining visibility along a
time) of a flashing light of a candlepower well horizontal path, a straightedge is laid across the
above threshold intensity are: (1) the time interval chart in such a manner that it connects the value
between flashes T, and (2) the duration of each of the inherent contrast between the object and its
flash t0 in seconds. A flashing light is most con­ background with the value o f the sky-background
spicuous when T lies between 0.5 and 1.0 second brightness ratio (this sky-background ratio is unity
and tB is between 0.25 and 0.75 second.2 Decreas­ if the background of the target is the .horizon
ing T or increasing t0/T increases the finding time sky), extended to intersect the zero liminal tar­
because of reduction o f flicker. I f t0 is below 0.5 get distance line. The straightedge is then re­
second, the average finding time is increased (for located so that it connects this point with the

4-10
 AM CP 706-185
• i 'i

TABLE 4-4 '

VISIBILITY OF FLASHING LIGHT COMPARED TO STEADY LIGHT

Flash Duration, . Ratio of Flashing Light ~

seconds . to Steady Light
1.0 *r 1.2
0.5 ’ f , . *1.4
0.4 , 1.5
- 0.3 1.7
0.2 ; 2.0
0.1 v 3.1
0.05 . 5.2
0.025 . 9.4
0.01 , • 22.0

- ’ ' " ;
TABLE 4-5
ABSORPTION OF SUNLIGHT BY ATMOSPHERE

Wavelength, Angstroms Percentage Transmitted

4000 47.5
, ‘ 4500 , 55.3
.. 5000 62.4
- 6000 68.2 -
7000 .75.6
8000 j 80.1

These figures represent the relative transmission for the different

wavelengths during the day under average clear conditions with the sun
at the zenith, and they may vary greatly under other conditions. It must
be remembered.that a light ignal can be seen at a much greater distance
than the distance at whicl its color can definitely be distinguished. >

value for the meteorological range. The intersec­ A can be calculated, for targets which subtend a
tion o f the straightedge and the curve for the small angle at the observer’s eye, by the equation:
correct general illumination level locates th|e lim-
inal target distance. A = * ( A. sin 0 ) (4-15)
The procedure for estimating the visibility for
slant paths is somewhat more complicated, espe­
where R is the first approximation o f the optical
cially if the atmosphere is stratified. I f no optically
slant range estimated by use o f the nomograph, R
dissimilar strata are present, the optical slant range
is the corresponding slant range for a sighting path
can he determined in the same manner as the visual
which makes an angle 6 with the ground, and A
range, along a horizontal path. The actual slant
range can then be approximated by the use of Equa­ is the area o f the target. This value, for A is now
tion 4-18 or Figure 4-3. Because the slant range used to calculate a better value for the optical,
is normally greater than the optical slant range, slant range R and corresponding slant range R.
the effective area of the target is less than its actual The nomographs are also useful when stratifi­
area and the predicted slant range Will bo high. cation o f the atmosphere causes an effective discon­
A better value can be obtained, if an effective area tinuity in the meteorological range-altitude rela-

4-11
AMCP 706-185

Bh
X

(YARDS)
ff
VALUES OF
X % > N >

METEOROLOGICAL RANGE (MILES) X

Flgura 4-7'. Visibility Nomograph

4-12
 AMCP
Al 706-185
.. ; . ' ^* -

TABLE 4-6
SK'r BRIGHTNESS

Ambient Brightness,
Condition millilamberts
Hazy* 10,000
Clear 1,000
Light Overcast 100
Heavy Overcast 10
Twilight ’ 1
Deep Twilight 0.1 ,
. Full Moon . 0.01
Quarter Moon 0.001
Starlight 1 0.0001
Overcast Starlight 0.00001

•The maximum brightness condition which is likely to be encoun­

tered is that of the sky onl a slightly hazy day at noon.6

TABLE 4-7
SK X-GROUND RATIO

Sky-Ground
Sky Condition Ground Condition Ratio
Overcast Fresh Snow 1
Overcast Desert 7
Overcast Forest 25'
Clear Fresh Snow 0.2
Clear Desert 1.4
Clear Forest 5

tionship. Let it be assumed, for example, that there off. Because of the problems involved, the estima­
is a ground haze which has a top at 5000 feet, and tion of slant ranges i9 less satisfactory than the esti­
that the meteorological range is five times greater mation o f horizontal range. Where experimental
above the haze boundary than below it. For this values are not available, typical values for the sky
type o f visibility problem, a line is constructed brightness are given in Table 4-6 for various am-
on the optical slant range diagram, Figure 4-3, .bient conditions. Typical values for the sky-
from the Origin to the intersection o f the curve for ground ratio are given in Table 4-7.
the desired viewing angle 9 , with the dashed line It is to be noted that the nomograph predicts
representing the true altitude nf 5000 }eet. A a distance at which the target is liminally visible.
second curse (which has five times the slope o f the I f the contrast value is divided by two before using
original curve) is drawn starting at this point. the nomograph, the result obtained is the sighting
The relationship between B, the optical slan t range, range, the distance at which the object can be
and R, the slant range, follows the resultant curve. seen with threshold confidence. For the object
I f the actual boundary o f the ground haze is dif­ to be easily seen, the contrast values should be
fuse, the; sharp change in slope can be rounded divided by at. least four.

4-18
AMCP 706-185

IN T E N S IT Y (CANDLES)

I lIPIII II I I I I 1 m i 888 _
n - 8 SS o
(3 <3 6 <3 d 6 6 d _

(YARDS)
(YARDS)
DISTANCE

DISTANCE
TARGET

TARGET
U M IN A L

U M IN A L

f/ fir TTfff if |(■ f r “ j m T j r ' n r - r r

i i 8 q 1 iA
8
O.

| 8 85 8 O
N —
o

M ETEO R O LO G ICAL RANGE (YARDS)

Figure 4 -8 . Visibility Nomograph for Signal Lights

4-14
 !*xjr

AM CP 706-185

.vvW,.i

TABLE 4-8
IN CREASE IN LLUMINATION REQUIRED FOR
PO SITIVE RECOGNITION

Field Factor .
Applied to Threshold DetectibiUty of
Candlepower IAght Source
..." 1 Light source difficult to find even if loca­
tion is known.

2.5-5 Light source moderately difficult to find if

location is approximately known and ob­
server is on steady platform and has long
time for search.
5-10 Light source easy to find under circum­
stances above.
20-30 Light source easy to find under reasonable
circumstances at night, for example,
search field no greater than 100 degrees,
observer can give his full attention. Diffi­
cult to find in daytime unless observer
knows where to look.
100-150 Light source can be found under strenu­
ous circumstances at'n igh t, and under
most circumstances in the daytime if the
search field is not too large. .

Square objects are as visible as circular objects foot-lamberts will be liminally visible on a clear
of the same area. Objects o f other shape) are, in day, when the meteorological range is 20,000
general, less visible. \ yards, can be estimated in the following manner:
Figure 4-8 is a visibility chart for predicting As sky brightness on clear day is approxi­
the range at which signal lamps and other point mately 1000 foot-lamberts, the contrast of target
sources o f light will be liminally visible. To use against sky as background is:
this chart, a straightedge is placed across the chart
so that it connects the meteorological raige with 10-1000
= -.9 9
the intensity of the light source. The intersection 1000
of this straight line with the curve for the proper The sky-ground ratio is 1.0 since the object is being
sky brightness level is the liminal target distance. viewed against sky. To obtain liminal target dis­
For signaling purposes at this, distance wh ere posi­ tance from nomograph, connect (as shown in F ig­
tive recognition is required, the illumination value ure 4-9) with a straightedge a sky-ground ratio
should be increased as indicated in Table 4-8, of 1.0 with a contrast of 0.99 and mark intersec­
tion of straightedge with the' zero'lim inal dis­
4-4.4 ILLU STRATIVE E XA M PLE S tance line. Connect this point with the meteoro­
l.a. The distance at which a uniform circular logical range o f 20,000 yards. The liminal target
target of 100 square feet with a brightness of 10 distance is read where this straight line intersects

4-15
AM CP 706-185

(YARDS)
R
or
VALUES

Figure 4-9. Visibility Nomograph Showing Calculation

4-16
 AM CP 706-185

(Y A R D S )
(YARDS)

O IS T A N C E
DISTANCE

TARG ET
TARG ET

L IM IN A L
L IM IN A L

Figure 4-10. Viability Nomograph tor Signal Lights Showing Calculation

4 -1 7
AMCP 706-185

with the curve for the ambient illumination, 103 ditions is approximately 6,900 yards. The sight­
foot-lamberts. The liminal target distance, in this ing distance and the distance at which the target
case, is approximately 11,000 yards. could be seen easily would also be calculated in
l.b. The sighting range is calculated in the the same manner as illustrated for Example l.b.
same way except that the effective contrast i s : and l.c.
3. The distance at which a signal having an
intensity o f 2,500 candles would be liminally vis­
ible on a foggy night when the meteorological
The sighting range is approximately 9,000 yards. range is 5,000 yards, can be estimated using the
l.c. The distance at which this target could signal light nomograph. A straightedge is placed
be seen easily under field conditions: across the nomograph for signal lights so that it
In order for a target to be seen easily, the connects the meteorological range, 5,000 yards, with
contrast values must be divided by at least 4.0. the candlepower, 2,500 candles, as shown in Figure
Under difficult field conditions, the contrast value 4-10. The liminal distance is given by the inter­
might have to be divided by a number as large as section of this line with the curve for the illumina­
100. The effective contrast range, therefore, is tion level 10“ 3 foot-lamberts.
4. The intensity required for a spotting charge
0.99
f r o m = 0.25, to = 0.01 to be seen at 2,000 yards over water and toward a
4 100
rising sun on a clear day, can be estimated by
and the distance at which the target could be seen use of the signal light visibility nomograph. Un­
easily might be as low as 2,000 ,yards (2,000 to der these conditions, the illumination level would
7,500 yards). i approach 104 foot-lamberts. The meteorological
2. The distance at which the same target would range is assumed to be approximately 30,000 yards,
be liminally visible under the same conditions, if a clear day. The intensity required for a light
it were to be observed against a background having source to be liminally visible under these condi­
a brightness o f 200 foot-lamberts can be calcu­ tions is obtained from the signal light nomograph
lated. (Since the target and background are both by connecting the meteorological range, 20 miles,
illuminated by the same light source, the reflectance with the point of intersection of a liminal target
of the background is approximately 20 times that distance of 2,000 yards, and the curve for the gen­
of the target.) In this case, the sky-ground ratio eral illumination level (approximated by dotted
is 1000/200 = 5.0, and the contrast is : curve on Figure 4-10). The intersection o f this
line with the zero liminal distance line gives the
10-200
-0 .9 5 candlepower required, about 4,000 cahdles. In
200
order to be seen readily under these field condi­
As indicated in Figure 4-9, the determination of tions, the intensity values should be multiplied (see
the liminal range is the same as outlined for Ex­ Table 4-8) by 100 to 150, yielding a required in­
ample l.a. The liminal distance under these con­ tensity of 4 X 104 to 6 X 104 candles.6

REFERENCES
1. Visibility Studies and Some Applications in 3. R. C. Casperson, H. P. Lenzyck, R. C. Channel,
the Field o f Camouflage, Summary Technical Visibility Data as it Applies to Pyrotechnics,
Report o f Division 16, National Defense Re­ Contract DAI-28-017-501-GRD-(P)-1294, Dun­
search Committee, Vol. 2. lap and Associates, Stamford, Connecticut,
2. F. E. Cady and H. B. Dates, Illuminating En­ 1955.
gineering, 2nd Ed., John W iley & Sons, N. Y., 4. A. Blondel and J. Rey, Jour de Physique,
1928. Radium, 1911.
 AMCP 706-185

5. R. D. Dwiggins, Factors A ffecting' Signalling Sources for Night Aerial Reconnaissance Pho­
by Visual. Methods, NAVORD 6034, Bureau tography, Final Report, Contract DA-36-039-
of Naval Weapons, Washington, D. C., 1957 SC-78333, Denver Research Institute, Univer­
(DDC-AD 162 931). sity of Denver, 1960.
6. R. T. Eckenrode, The Spotting Technique. II. 8. Aerosol and War Cases, Summary Technical
Effect o f Ambient Illumination Spot Intensity Report of Division 10, National Defense Re­
and Color: Memory Screen Information, TS4- search Committee.
4020, Frankford Arsenal, Philadelphia, Pa., 9. H. L. Greene, W. R. Lane, Particulate Clouds,
1955: Smokes, and Mists, Van Nostrand Co., Lon­
7. R. M. Blount, G. Francis, Study o f Light don, 1957.
 i

AMCP 706-185

CH APTER 5

PRODu CTION OF HEAT

5-1 H ISTORICAL SUMMARY1-5-8 7 8 ployed by the British in the American Revolu­

The systematic use of incendiaries extends back tion as well as by the armies involved in the many
into ancient times when practically any readily European conflicts of the 19th century. The
combustible material was used for both offensive United States Army had incendiary items of
and defensive operations. Incendiary-type com­ ordnance issue in the early part of the 19th cen­
positions were used in fireballs, pots, or crude tury. During the American Civil War, the in­
bombs and hurled against the enemy by means of cendiary projectiles developed by the Union Army
a catapult, or as headings for slings and b)w ar­ and fired against Vicksburg, Charleston, and
rows, and other purposes. Some of the earlier Petersburg were of limited value. A flammable
combustible materials used included oil, pitch, liquid was also developed which could be used
sulfur, resinous woods, and straw. “ Greek fire,” with a flame thrower. These flame throwers
an incendiary mixture which probably contained reached Bermuda Hundred, Virginia, early in
readily flammable substances such as pitch, resin 1865, and may have been used in later battles of
and petroleum, along with quicklime and sulfur, the Civil War.*
was used in the 17th century against ships tents, In general, however, from the beginning of
barricades, cities, and personnel. It was; espe­ modern times down to W orld War I, incendiaries
cially valuable as an incendiary because it was were not extensively used due to the increase in
difficult to extinguish since as water reacted with battle distances, resulting from the introduction of
the quicklime and also spread the petroleum. firearms. In addition, the defensive use of armor
These types o f incendiaries were o f definite value and earthworks left little material that would burn
in all of the wars fought during the Middle Ages on the battlefields. These problems were not solved
and their importance was not diminished until until the advent of the W orld W ar I.
gunpowder was introduced in the 15th century. While both the French and German Armies
During the 16th, 17th, and 18th centuries, had developed incendiary artillery projectiles be­
the basic ingredients in incendiary mixtures con­ fore World W ar I, these projectiles were not used
tinued; to be sulfur and saltpeter to which were to any extent in the early days of the war, prob­
added a number of flammable materials such as ably because they were ineffective against military
resin, pitch, tallow, beeswax, linseed oil, and tur­ targets. The first incendiary munitions used in
pentine. For many years the recognized incendiary this war evidently were incendiary bullets and
projectiles were known as “ carcasses.” i!n their antiaircraft artillery projectiles directed against
earliest form they consisted o f cylindrical bags observation balloons, and flame projectors against
or containers of canvas coated with pi ch and ground troops. These devices, along with in­
bound with iron hoops. The name was suggested cendiary bombing from aircraft, were first used
because o f the likeness o f these iron hoops to the by the Germans in 1915.
ribs o f a corpse. Later, their shape became spher­ Intensive research and development program8
ical; however, their filling remained the same— were established by all the principal belligerents
a mixture of saltpeter, sulfur, resin, antimony in order to obtain improved incendiary muni­
sulphide, and tallow— until carcasses became obso­ tions. White phosphorus was effective against
lete toward the end o f the 18th century.
•W . D. Miles, “ The CiVU W ar,” Part I, Chemistry and
Rockets with incendiary charges were em­ Engineering News, Vol. 39, No. 14, April 3, 1961.
AMCP 706-185

readily combustible material such as balloons. It a limited amount of research and development
was also very effective against personnel as it pro­ was performed oil incendiary munitions in the
duced painful burns and hence caused a de­ United States. The white phosphorus filling for
moralising effect far in excess o f the casualties caliber .30 incendiary ammunition was replaced
produced. Thermite and modified thermite mix­ with a tracer composition. Development work on
tures were widely employed, especially in con­ incendiary compositions was actively resumed in
nection with an additional incendiary material the United States in 1936.
such as “ solidified oil.” Other mixtures contain­ General interest in small arms incendiary am­
ing an inorganic oxidizer such as potassium or munition was renewed during the early years of
barium nitrate, barium or lead oxide, or potas­ W orld W ar II. The DeWilde-Kaufman bullet,
sium chlorate, and a fuel such as carbon, sulfur, designed in Switzerland by 1939, represented a
magnesium, aluminum, or organic combustibles, major step forward in the development of small
were used in small arms incendiary bullets and arms incendiary ammunition in that it would func­
with less success in drop bombs. tion as desired against realistic targets. To elim­
Solid oil (oil mixtures solidified with colloidal inate the serious manufacturing and handling
additives) and flame projector liquids consisting problems associated with this design, it was modi­
o f a heavy viscous oil or tar and a more fluid and fied by British scientists to use the U.S.-developed
flammable liquid were also developed but saw only IM-11 incendiary mix. Modifications of the British
limited use during the war. design were made later by the United States Ord­
In spite o f the tactical and strategic possibili­ nance Department to improve functioning char­
ties associated with the use o f aerial incendiary acteristics and to adapt the design to manufacture
bombs, only a limited amount of the development by mass production techniques. These modifica­
work on incendiary munitions was directed to­ tions, including some changes in the incendiary
ward design of improved munitions o f this type. composition, resulted in the U.S. M l Incendiary
Two general types of aerial incendiary bombs Projectile which played an important role in win­
were developed. The first was the relatively large ning the Battle of Britain by defeating the Ger­
bomb filled with an incendiary mixture, often man air attacks. The development of modified in­
thermite and solid oil, designed to penetrate and cendiary ammunition, including armor-piercing
set fire to buildings and heavy construction. The incendiary ammunition, was started in 1943; how­
second was the scatter type of incendiary bomb ever, only a small quantity of these items had
which consisted of incendiary units in a large been produced by the end of the war.
bomb, or a cluster o f small bombs (the latter being In the Battle of Britain, the Germans used a
the more successful of the two techniques), to 1-kilo magnesium bomb against British cities with
start fires over a relatively large area. great effectiveness. A very effective 4-pound mag­
The increasing use of military aircraft resulted nesium bomb had been developed by the British;
in an increased interest in small arms incendiary however, the United States did not as yet have a
ammunition Bince the employment of incendiary satisfactory incendiary bomb. As a consequence,
ammunition was considered to be one o f the better the British M K-III magnesium bomb was re­
ways for destroying aircraft. The first small arms designed for mass production. A 4-pound thermite
round designed for air-to-air combat was probably bomb was developed as a substitute for the some­
the British Pomeroy projectile with a kieselguhr what superior magnesium bomb and was used in
dynamite filler which had both high explosive General Doolittle’s historic raid on Japan in April
and incendiary functions, and was very effective 1942. A small 2-pound magnesium bomb was also
against German airships. The earliest incendiary developed and when used in clusters was considered
small arms projectile used by the United States, to be more effective against urban German targets
adapted from a British design, employed phos­ than the heavier incendiaries which had been de­
phorus as the incendiary material. veloped for industrial targets. They were also
In the period between the two W orld Wars, only successful against Japanese industrial targets but

5-2
 AMCP 706-185

■>iv-

penetrated too far to be highly effective igainst Starters, igniters and first fires, as adjuncts to
Japanese dwellings. ^ other pyrotechnic devices, have had a history
The development of a small petroleum in­ closely associated with such devices. Information
cendiary bomb was started and led to the develop­ describing the development of early Chinese fire­
ment o f the 6-pound napalm bomb which w is used crackers includes descriptions of fuses containing
with spectacular success in the strategic bombing potassium nitrate (saltpeter), charcoal and sulfur.
of Japan. Other petroleum incendiary mixtures In the 18th century mixtures of potassium nitrate,
were developed, including the IM mixture^ which sulfur, charcoal, and iron filings were widely used
contained finely divided magnesium. Against both for pyrotechnic purposes. They were readily ig­
Europe and Japan, incendiary bombs proved to nited and for this purpose a type of quiokmatch
be very effective weapons, especially when ap­ was employed.
proximately one-fifth of them contained explosive The quickmatch was made from cotton thread
charges to discourage fire fighters. or string, moistened with vinegar or brandy and
Flame throwers were first used in the Pacific coated with a mixture consisting of 16 parts po­
theater on Corregidor by the Japanese against tassium nitrate, 3 parts charcoal and 1 part sulfur.
American troops who were not; equipped \tath the The mixture was worked into the thread by hand,
weapoii. Due to its. proven effectiveness and the after which it was dried and cut into suitable
development of napalm, it was soon used lengths. It was then connected to the pyrotechnic
United States for combat operations in all theaters device and used as its igniter.
of operation, either as a portable unit or mounted A t the beginning o f the 19th century phos­
on vehicles. ; phorus-tipped sticks, that could be readily ignited
After World War II, research and develop­ by friction, were made available and were the fore­
ment directed toward the improvement c f small runner of present day matches.
arms incendiary ammunition were continue d. Em­ Friction starters were developed later in the
phasis was directed toward developing improved 19th century. These employed as a bead a mixture
ammunition with an increased effective! ess per o f potassium chlorate and sugar with gum arabic
round against jet planes at higher altitudes. This as a binder. In the form of matches, these were
work proved valuable during the Korean Conflict ignited by drawing them through a folded piece
when small arm incendiaries were used in the air of sandpaper.
conflict against enemy jet aircraft. Onher in- Typical pyrotechnic munitions in the 19th cen­
cendiavy weapons, including incendiary bombs and tury consisted of rockets, flares, and fireballs which
flame throwers, also were used widely and effec­ could be ignited by a mixture of potassium nitrate,
tively in this conflict by the United Nations forces. sulfur, and arsenic sulfide, which, in turn, was ig­
The effort applied in the development o f in­ nited by a quickmatch. .
cendiary weapons has resulted in peace-time uses During W orld W ar I, pyrotechnic munitions
for these weapons. Pyrogel (or goop), wnich con­ were developed which used compositions more
tains finely divided magnesium, and w iich was difficult to ignite than earlier compositions. In
used in the IM petroleum incendiary mixture, has the period between W orld W ar I and W orld W ar
been found to aid in the burning out o f forest II, limited effort was made to produce more satis­
cuttings. The flame thrower is o f value in fighting factory ignition mixtures for pyrotechnic muni­
forest fires and in destroying unwanted vegeta­ tions. A considerable part of this effort was
tion. Studies into the causes of death py flame directed toward the development of satisfactory
carried out during W orld W ar II have directed starter mixtures for HC smoke mixtures and for
attention of civilian firemen to unsuspected hazards thermite-type incendiaries. During W orld W ar II,
in fighting fires of various kinds. Also, research emphasis was again directed, mainly, toward de­
on the effectiveness o f incendiary ammunition veloping compositions which would meet the im­
against aircraft has been of value in connection mediate needs of the troops. A relatively small
with aircraft fires. amount o f effort has been expended since W orld

5-8
AMCP 706-185

War' II, particularly in connection with the de­ until the projectile arrived at or close to the tar­
velopment of new illuminants. get. Similar crude delay trains were developed
In addition to their value as a source of heat, for incendiary and other projectiles used in early
the utility of combustion processes as a means for naval warfare when ships were made of wood.
measuring and controlling time intervals was Their purpose was not only to delay functioning
recognized early in history. The ancient Chinese, until a projectile reached its target, but also
Greeks, and others used open vessels of oil, crude to further delay functioning so as to maximize its
candles, and similar devices, to ignite either ex­ effectiveness in damaging the enemy ship.
plosives or flammable material at a distance or With the development of improved ammuni­
at some delayed time. In addition to their mili­ tion, more complicated fuse systems with improved
tary applications, such delayed reactions^—cul­ reliability and timing accuracy were required.
minating in the sudden production of fire, smoke, The earliest pyrotechnic delays which were rela­
or a minor explosive phenomenon— were an im­ tively accurate consisted of carefully produced
portant part of many early religious ceremonies. black powder trains or black powder rings. The
The introduction of gunpowder stimulated the delay train was used in fuses requiring a set
development of somewhat more sophisticated delay delay while the ring delay was most often used in
devices. A string or paper impregnated with an those items requiring setting immediately before
oxidizer and elongated trails of powder were some use. In spite of the many problems associated with
of the earliest pyrotechnic delay trains. Present the use of black powder delay compositions, due
quickmatch and firecracker fuses are of this type, mainly to their hygroscopic and corrosive nature,
however, they are normally used as transfer media they served as the basis of most pyrotechnic delay
rather than timers. Puses consisting of an in­ trains throughout W orld W ar II.
gredient such as black powder, contained in a Burning black powder liberates large amounts
tubular cover, will burn reliably and at reason­ of gaseous products which, in most fuse designs,
ably reproducible burning rates. Safety fuse is of are vented to the atmosphere. In the development
this type. It is a lightly wrapped train of potas­ of ammunition, especially antiaircraft ammunition
sium nitrate and black powder burning at a. rate during World War I, it was found that the burn­
of 40 to 120 seconds per yard. The tubular cover ing rate of black powder was affected considerably
now is often impregnated fabric. An effort is by the rotational speeds of the projectile as well
usually made to seal against moisture by the use as the varying ambient pressures. Therefore, the
of wax and plastic coatings. The development of development of a more satisfactory fuse powder
these fuses made possible lavish firework displays composition was started with a low priority after
by crudely timing the sequence of events starting World War I.
with the propagation of the display into the air The first nongaseous delay powder— consist­
followed by a sequence of bursts making up the ing of red lead, silicon, and glycerin (8 4 /1 5 /1 )—
firework display. In addition, their use provided was developed in 1931. Since this composition
the necessary time required for safety of the per­ burned too fast, slower burning powders contain­
sonnel igniting extensive ground displays. Puses ing lead chromate, silicon, and linseed oil (89/10/1)
of essentially the same type were also used in con­ were developed. Lack of personnel and funds, how­
nection with the early commercial explosives used ever, prevented a comprehensive, systematic study
in mining and construction. of the many possible inorganic exothermic reactions
The use of projectiles containing explosives before the start of W orld W ar II. As a result,
was started sometime after the introduction of black powder was again widely used in delay ele­
artillery in military operations. Early projectiles ments during World W ar II.
were filled with gunpowder and closed with a In 1942, a comprehensive study o f possible
wooden plug containing a small diameter hole, gasless delay mixtures was started.22 While this
also filled with powder. This crude fuse was ig­ study was in progress, an urgent need developed
nited by the propelling charge and burned slowly for delay powders to be used in the bombs used

5 -4
 AMCP 706-185

in “ skip bombing.” A composition— containing by mechanical, chemical, electrical, or other stimuli

manganese, barium chromate, and sulfur— which of low energy and produce sufficient heat to cause
had been prepared on a laboratory scale, proved the ignition of other, less sensitive mixtures.
satisfactory in spite of the many difficulties en­ b. First fires, starters, igniters, and similar
countered in proceeding from a laboratory to a less sensitive, but relatively easy-to-ignite mixtures,
production scale.23 The Navy developed, under normally activated by the heat produced by an­
J
contract, a delay mixture containing nickel zir­ other thermal source. The sensitivity level of these
conium, <potassium perchlorate, and balrium mixtures is such that sufficient quantities can be
chromate. which was used satisfactorily in kand used to supply the heat necessary for ignition of a
grenades. While these delay powders— developed third mixture or main charge consisting of a pro­
under wartime conditions— were used, operation­ pellant or pyrotechnic composition. A similar se­
ally, they were far from optimum.24 quence of ignitions is also common to explosive
W ork after the end o f W orld W ar II was di­ items. '
rected toward the development of more satisfactory c. Incendiary mixtures which are used for
gasless delay compositions. The availability of destructive ignition of combustible materials.
certain powdered metal fuels— e.g., zirconium- 2. Compositions which produce heat at a low
nickel alloys and boron— not available earlier, rate: .
helped in the development of the presently used a. Heat powders which produce a controlled
more satisfactory delay powders. amount of heat for applications such as the activa­
The development and use of thermal bat- tion of heat batteries or a controlled evolution of
teries25'2ti required a controlable heat source to gas, and for other purposes.
melt the electrolyte which is solid at norma! tem­ . b. Delay mixtures which are used to ac­
peratures and to activate the battery, Early curately control the time interval between initia­
thermal batteries were activated by weighed quan- tion and final functioning.
tities of loose heat powder, similar to delay c ompo- The rate and control of the heat output from a
sitions, introduced directly into the battery cases. pyrotechnic mixture, as well as the heat transfer
Slightly improved results were obtained when the mechanisms involved, are very important in the
battery was divided into compartments ard the performance o f its function. In this chapter, these
loose heat powder added to each compartment. characteristics are emphasized as regards existing
Better results were obtained when the heat powder heat producing pyrotechnic devices.
was mixed with inorganic fibers and made into
heat paper by conventional paper making tech
5-3 THEORY
niques.2®’27 :
The two important means by which energy can
be transferred are heat and work. Both of these
5-2 INTRODUCTION energy forms are transient in nature since they
Pyrotechnic mixtures, when burned, release exist only when there is an exchange of energy
chemical energy in the form of heat. The heat between two systems or a system and its surround­
energy released is used for the production of light, ings. I f this transfer takes place without a trans­
smoke, gas, and sound. Although the heat effects fe r of mass, and not as a result of a temperature
produced in the surroundings by these itelms are difference, the energy is said to have been trans­
usually incidental and may be undesirable, there ferred through the performance of work. I f the
are a number of pyrotechnic items in which the exchange is due to a temperature difference, the
production of heat is the primary function. energy is said to. have been transferred in the form
Pyrotechnic heat producing mixtures can be of heat. .-
divided into two general categories, namely: The amount o f energy transferred as heat from
1. Compositions which produce heat atl a high a burning pyrotechnic mixtures depends on: (1)
rate: the amount and rate of energy released, (2) the
a. Ignition mixtures which can be initiated products formed, (3) the temperature reached by

5-5
AMCP 706-185

the products, (4) the method by which the energy dizers which have been widely used in incendiary
is transferred, and (5) the characteristics o f the ' compositions are the inorganic nitrates, perchlo­
material being heated, whether unburned pyro­ rates, and peroxides. The total and available oxy­
technic mixture or other combustible. gen for some o f these oxidizers are given in Tables
5-2,2 5-3, and 5-4. Many of the potentially good
oxidizers listed in these tables contain large quan­
5-3.1 AMOUNT OF ENERGY RELEASED1
tities of water in their normally occurring crystal­
The energy released by the reaction of a pyro­ line forms. This reduces the available oxygen from
technic mixture can be calculated by the methods a given quantity o f oxidizer and can affect burn­
outlined in Chapter 3 (Paragraph 3-2.2.1) of this ing (as an inert) as well as stability in storage.
handbook or can be determined experimentally by Approximate decomposition temperatnres are also
bomb calorimetric measurements.
Certain generalizations can be made from the TABLE 5-1
results of these calculations involving metals and HEATS EVOLVED FROM REACTIONS OF
oxidizers which might be considered for heat pro­ ALUMINUM AND VARIOUS
ducing mixtures. For a given fuel, the heat evolved OXIDIZING AGENTS
per unit-volume of the mixture (calculated from
the theoretical density for the mixture) depends Reaction Cal/cc Colfg
on the oxidixer used, as is indicated in Table 5-1
which is a summary of the heat, evolved when alum­ A 1 + NaC10« 7,000 2,600
inum reacts with various oxidizing agents. In A l + NaClOa 6,300 2,500
general, for a given oxidizer action the heat evolved AI + KCIO 4 6 ,1 0 0 2,400
depends on the oxidizer anion in the following de­ A 1 4 -P b (N 0 8 ) 2 5,800 1,500
creasing order: A 1 + KClOs 5,400 2 ,2 0 0

A1 + P b 0 2 4,900 700
C104 > C108 > NOs > M n04 > 8 0 * > Cr!(0 7 >
A1 + CUSO4 4,700 1,400
C r04
Al + CuO 4,600 900
As also shown in Table 5-1 for a given oxidizer Al + NaNOs , 4,400 1,800
anion, copper salts yield more heat than lead com­ A1 + B a (N 0 8 ) 2 4,200 1,400
pounds and either of these yields more than so­ A1 - f P bS 0 4 4,200 , 800
dium, potassium, calcium, or barium compounds A1 + KNOa 4,000 1,800
when reacted with the same fuel. While copper A 1 4 - CaS0 4 3,800 1,300
salts appear best, they are not commonly used A1 + KMnO« 3,600 1,300
because o f the difficulty involved in their ignition. A1 -f- F 6 2 O8 . 3,500 900
The reactions are listed in order of the heat evolved Al + M n0 2 3,400 1 ,1 0 0

in calories per cubic centimeter of mixture; the Al + BaSOa 3,400 900

heat evolved per gram of mixture is also given, for A l -}- FesO* 3,400 800
comparison. In each case, the calculated heat of re­ A l - f Na2 SO* . 3,300 1 ,2 0 0

action is based on a particular (most common) A l - f Pb 8 0 4 3,300 400

stoichiometry for the reaction; the indicated val­ A l -|- Na202 3,100 1,600
ues would vary where different stoichiometries are Al -f- K 2 S 0 4 3,100 1 ,2 0 0

possible. Since the oxidizer exerts the greatest A l - f NH 4 N 0 8 3,000 1,600

influence on the heat of reaction, the replacement A l - f Na2 C r0 4 ' 2,800 1 ,0 0 0

of aluminum with other reducing agents would A l 4 ~ K 2 Cr2 0 7 ■ 2,800 1 ,0 0 0

result in an arrangement similar to that shown A l -j- BftOs ' 2,600 600
in Table 5-1. ; A l 4- PbO 2,500 300
The amount of oxygen available from a given A l 4 - BaCrOa 2,400 600
amount o f oxidizer is the basic criterion upon A l 4 * EaCrOa 2 ,2 0 0 800
which oxidizers are judged. Three classes o f oxi­

5 -6
 AM CP 706-185

TABLE 5-2
OXYGEN CONTENT OF VARIOUS NITRATES

Approx.
Decomp. Oxygen Oxygen
Density Temp, Contained Available
i Nitrate ■ g lee , °C 9l9 9lcc 9 l9 9/ec

1Liquid O2 ~ 1.14 _ 1 .0 0 1.14 1 .0 0 1.14

1Liquid Os 1.71 — 1 .0 0 1.71 1 .0 0 1.71
. Aluminum (4 - H 2 O ) 1 — 130 .77 — .32 —
Ammonium 1.73 2 10 .60 1.04 .2 0 .35
Barium - 3.24 600 .37 ’ 1.19 .31 .99
1Beryllium (4 - ^ O ) 1 T- 10 0 .78 — .39 —
Calcium: ( -f- H 2 0 ) 1 2.36 - 560 .59 1.38 .48 1.14
1 Chromium (4 - HgQ ) 1 ■ — 10 0 .71 — .32 ■
—
Cobalt ( - f H 2 O ) 1 -i— . - 10 0 .59 — 1 .44
; Copper ( 4 - H 2 O ) 1 —r 150 .51 ■
— .42 — '
Iron (F erric) ( + H 2 O ) 1 — 10 0 .47 — .39 ' —
Lead ’ 4.53 470 .29 1.31 * .24 1 .1 0

l Lithium ( 4 - H 20 )? 2.38 260 .69 1.65 .58 1.38

Magnesium ( 4 - H 2 O ) 1 — . ’ 10 0 .75 * — .62 *- —
Manganese — ; 130 .54 — .40 —
Potassium 2 .1 1 400 .47 1 .0 0 .40 .84
Sodium 2.26 350 .56 1.28 .47 1.06
Strontium 2.99 600 .45 1.38 .38 1.13

1 (H2 0 ) indicates that a hydrate o f the nitrate is a common form of the salt. All data
presented in the table, however, are for the anhydrous salt. -
, . 1
in these tables. The thermal decomp osition. used as a measure o f the reducing power
ny of the possible oxidizers has been s tudied compounds.
in detail.8 ■ It should be noted that combustion of liquid
In Table 5-5, reactions are shown between var­ hydrocarbon fuels such as gasoline and kerosene,
ious metallic and nonmetallic reducing agenlte, and which were widely used as incendiaries during
barium peroxide. The heats evolved from reactions both World War II and the Korean Conflict, re­
o f these materials with other oxidizing agents suits in the evolution of about 10 kilocalories per
would generally rank in the same order. gram. This is considerably better on a weight
Some o f the combinations included in Table basis than for the metal incendiary materials:
5-5, such as barium peroxide with tin, chromium', thermite, 0.8 kilocalories per gram ,'and magne­
and zinc, are so insensitive that the peroxide would sium, 0.6 kilocalories per gram. . However, the
decompose before ignition occurred., Conversely, temperature reached by the hydrocarbon-oxygen
red phosphorus and sulfur with peroxides can be reaction is less than that reached by incendiaries
sensitive to the point o f spontaneous decomposition incorporating metal fuels. .
and constitute a hazard. The equivalent heat value
given in this table is the heat evolved for the re­ 5-3.2 HEAT TRANSFER :
actions^ as given in the equations, divided by the The efficiency and performance of pyrotechnic
number o f equivalent weights of reducing’ agent devices are considerably influenced by the various
in the equation. The equivalent heat has been modes and rates o f heat transfer present through-

5-7
AM CP 706-185

■■■■'■ . , TABLE 5-3 . . . ',

OXYGEN CONTENT OF VARIOUS PERCHLORATES

Approx.
Deeomp. Oxygen Oxygen
Density Temp, Contained Available
Perchlorate ■, 9 /cc °c 9 /9 g/cc 9/9 9loc

Liquid Os 1.14 . --- ' 1 .0 0 1.14 1.00 1.14

Liquid Og 1.71 — .. 1 .0 0 1.71 1.00 1.71
Ammonium 1.95 '• — ■ ■ 0 .5 4 1.06 0.27 0.53
Barium (HsO)1 500 .38 .— ■ .33 . —
Cobalt (H 2O) 1 3.33 ;50 1.65 .40 1.34
Copper "■■■. —■ ' 110 .27 — . .16 . —
Iron (H 2 O ) 1 . • — .62 — .■ ■ .29 — .■
Lead (H 2 O ) 1 2.6 100 .31 .99 .24 .63
Lithium (H 2 O ) 1 2.43 410 .60 1.47 .53 1.28
Magnesium (H 2O ) 1 2.60 — .57 1.48 .50 1.30
Potassium 2.52 400 .46 1.16 .40 1.02
Sodium (HaO)1 2.49 480 .52 1.29 .46 1.15

- 7 (H ^O ) indicates that a hydrate o f the perchlorate is a common form o f the Balt.- A ll data
presented in the table, however, are fo r the anhydrous salt.

TABLE 5-4
OXYGEN CONTENT OF VARIOUS OXIDES AND PEROXIDES

.. 1 ■ . Approx.
Decomp. Oxygen 1 Oxygen
Density, Temp, Contained Available
Oxide or Peroxide g lee °c 9/9 9l<* g\9 9 /cc

Liquid Oa ■ 1.14 — ' 1.00 1.14 1.00 1.14

Liquid Os ■ 1.71 1.00 1.71 1.00 1.71
Barium Peroxide (H 2O ) 1 4.96 . .19 .94 .09 .47
Calcium Peroxide (HaO)1 • —- ' 280 .44 . . — ■■ .22 —
Chromium Trioxide (HaO)1 2.7 190 .48 1.30 .24 .65
Iodine Pentoxide 4.80 300 .24 1.15 .24 1.15
Iron (FeaOs) 5.12 —. ■ .30 1.54 . — —
Lead Dioxide 9.38 290 .13 1.26 .07 .63
Manganese Trioxide — ' — .47 .; . — ■' .23 ■
. —
Potassium Peroxide 2.74 ■— . .. .29 .61 .14 .30
Sodium Peroxide (HaO)1 2.81 .41 1.15 .20 .58
Strontium Peroxide (HsO)1 . ■ — .27 .14 —

1 (H jO ) indicates that a hydrate o f the peroxide is a common form o f this m aterial A ll

data presented in this table, however, are fo r the anhydrous form o f these peroxides.
- I

AM CP 706-185

TABLE 5-5
HEAT OF REACTION OF REDUCING AGENTS
W ITH BARIUM PEROXIDE

Heat o f Equivalent ■ ■ '' ' , ;

Reaction ’ Heat
Equation (Kg-cai) (Ky-cal) ' / ; 4 :4 . 4 : i; ■■■

B a02 + M g -> BaO + MgO 126.7 63.4 ■• : 4 . 4 ; . ,• :4

2B a02 -f- Z r —> 2BaO Z r02 219.3 • 54.8 ' • '
• , ■ ■■
3BaG2 + 2A1 - » 3BaO + A120 3 321.8 53.6 ■■ /.■: ■
5B a02 4- 2red P —» 2BaO '-J-. Bas( P 0 4)2 487.6 ; > 48.8 :
186.2 ‘ - ; 1
2B a02 + Ti - * 2BaO + T i0 2 46.6 • ■■■ ' :
2B a02 + Si - » 2BaO + SiOa 162.6 40.7 ■
B a02 4- Mn BaO 4- MnO : 77.1 ’ • 38.6 : : '- 4 '■ 4 4 4 4 !.■
3Ba02 + 2Cr -► 3BaO - f Cr20» 214.8 : 35.8 4 4" i4 V 4 .!
B a02 4- Zn —* BaO 4- ZnO - . ■■ 64.1 . : 32.1 4<4 : i
2B a02 4* Sn—> 2BaO 4 S n 02 .. . 99.3 24.8 44 4 " 4 ; .
5B a02 - f CaSi2 - » 5BaO - f CaO - - 2Si02 236.7 23.7
3 B&O2 - f 2Pe 3BaO 4- F 6 2 O 8 140.3 '. ■■ ,23.4.. ! v ; ./. . ; - V V 4
fisO j 4” Cd BaO 4" CdO / ;.. , 4 5 .8 .:/: . 22.9 ■' , ■ :' r _ '\ V .. •
137.5 22.9 . .. ■ ■ 4 -V■
3B a0 2 4 - W - » 3BaO 4 - WO»
3B a02 4- Mo —*■3BaO 4 MoOj ' -V 118.3 ■ 19.7 4 -V- 4 :.;- :
; ... . 155.8 ; 19.5 ; ■■
2B a0 2 4 - 2 S B a S + B aS0 4 • , 4
B a0 2 4- Ni - » BaO - f NiO 39.0 ■■■4: 19.5 ■. 4 ; ; . \ 4 fi; : 4 ' ,
B a0 2 4- Co -> BaO 4- CoO ' . . > 4 38.1 ■ 19.1 . 4 . 4 . =.. •4 . •',
3B a0 2 4 - 2Sb - * 3BaO 4 - Sb2 0 3 107.8 ; 18.0 ' -4 '■ ■
‘ '4 .4.*' ■ ■. .. ■ \ ■ -
3B a02 4 - 2Bi —» 3BaO + Bi2Os ' ■: 78.9 '
■ ■ ■' 13.2
B a0 2 4 -Cu -*■ BaO - f CuO , .. 16.4 8.2 '. . ; ■' '
2B a0 2 2 S e-> BaSe 4 - BaSeOi 54.3 ' 6.8 .; .
r v ;;4 4 ' : ; ; - ::

out the system. Although extremely complicated transferred by this method is usually small when
mechanisms exist in some cases, a knowledge of the compared with the amount transferred by other ":4
problems involved is important to the improve­ means. The rate of heat transfer q, at which heat 1 .i 4
ment o f pyrotechnic compositions and hardiware flows across an area A , is given b y :
design.
dt
Heat is transferred by one or by a combination q = — kA (5-1)
dx
of the three basic mechanisms: conduction, con­
vection, and radiation. During propagative burn- “where k is the thermal conductivity, and dt/d$
ing, only one of these modes is controlling. is the temperature gradient at the point of in­
terest. The rate expressions for a general three­
5-3.2.1 Conduction dimensional case are more complex. v
In conduction, the heat energy is transferred The thermal conductivity of the pyrotechnic
by molecular motion and free electrons. Materials mixture has been shown to influence the burning
like the metals, which are good conductors ol? heat, rate due to a preheating of the unburned compo­
have a well-ordered crystalline structure and are sition (Paragraph 6-3.5). The amount of preheat­
rich in free electrons. A ll materials condu< t heat ing is usually a function o f the metal content of
to some, extent. In liquids and gases, the amount the mixture due to its higher thermal conductivity.

5-9
AMCP 706-185

The degree of consolidation also affects the rate of the area o f the emitting surface, and T the absolute
heat transfer. The heat conduction along solid temperature. A graybody, or nonselective radiator,
dares has been measured3 by imbedding thermo­ is one in which its emissivity is independent of the
couples in the composition at the time of compac­ wavelength. At a given temperature, the amount
tion. From these data it was possible to construct of energy emitted per unit area at any wavelength
a model for relating the instantaneous tempera­ is less than that from a blackbody. The net heat
ture at a point in the dare to that of the reaction exchange between two bodies in which both the
zone. hot and cold body are graybodies is:
Conduction heat transfer as well as radiation
Qnet = </u— qc (5 -4 )
influence the on-target combustion efficiency of
certain types o f incendiary mixtures. The rate of where the net heat exchange is the difference be­
energy release of the fuel-oxidant reaction, inti­ tween the amount of heat q transferred by radia­
macy of contact, and chemical-physical properties tion to the cooler body, less the amount q trans­
of the target induence the heat transfer rate. ferred from the cooler to the hotter body. This may
Heat is transferred by conduction as well as be written also as:
by the other modes in ignition trains, delays and
qnct — E >,-+rAh<sTh4 — El.<X/,Fr.^itA c’j T r4 (5-5)
heat powders, and should be taken into considera­
tion in establishing design criteria. or by application of the reciprocity theorem:
qnrt = E h0! ,.F ^ rA hs (T h4 — TV*)
5-3.2.2 Convection and Radiation -E ^ F ^ A rid ^ -T S ) (5-8)
Convective and radiative modes of heat trans­ where E is the emissivity, a is the absorptivity, F
fer in pyrotechnics arc more closely associated
is the fraction of the energy emitted by a radiating
with post-combustion phenomena. Convective heat
body that is absorbed by the absorbing body, A is
transfer effects are less important and will only the area of the emitting surface, <s is the Stefan-
be mentioned briefly. Transfer of heat energy by Boltzmann constant, and T is the absolute tem­
convection results from the gross movement of the
perature. The subscripts h refer to the hotter body,
duid transfer medium. The amount q of heat
and the subscripts c,refer to the cooler body.
transferred by convection can be expressed by the
Radiation heat transfer is important in post-
general equation:
eombustion phenomena of pyrotechnic flares since
q~hA(HT) (5-2) it is the primary mechanism by which heat is re­
turned to the reaction zone. This feedback is im­
where h is the heat transfer coefficient, which may
portant to the maintaining of propagative burning
be a complex function of a large number o f prop­
and maximum possible efficiencies in these type
erties including those relating to the duid motion;
reactions. As already indicated, radiative beat
A is the cross-sectional area; and AT is the tem­
transfer mechanisms also influence the efficiency
perature difference. Convective heat transfer ef­
of certain types incendiary mixtures. In this case,
fects may exert an induence on the luminous out­
it. is expedient to produce radiating species which
put and efficiency of dame plumes by moving oxy­
will be readily absorbed by the target.
gen into the combustion area and/or by cooling.
These effects are usually slight and their measure­
ment extremely complicated. 5-3.3 HEAT EFFECTS
Heat transfer by radiation does not require a I f heat is transferred to or from a system, the
transfer medium. The amount of energy emitted temperature of the system usually changes. The
from a heated surface which has blackbody char­ magnitude of the temperature change, depends on
acteristics is: the mass of a system and its heat capacity. These
quantities are discussed in Paragraph 3-2.1. Trans­
q = oAT4 (5-3)
fer of heat may also cause phase changes such as
where a is the Stefan-Boltzmann constant, A is crystalline transition, melting (or freezing), vap-

5-10
 AMCP 706-185

orization (or sublimation), and dissociation, jThe craft structures. It is important that the bullet or
energy involved in these changes in state maj be projectile provide a hole in a self-sealing fuel tank
large in comparison with those involved in the so that some fuel is spilled and ignited by the
raising or lowering of the temperature of the burning incendiary material. This emphasizes the
system. Changes in state brought about by the importance o f widespread distribution of burning
absorption o f heat may be extremely important in particles and long burst duration. Most small arms
initiating combustion since the fuel and oxid izer incendiary compositions are mixtures of metal, or
must in some, cases be converted into the gaseous metal alloys, and an oxidizing compound. These
state for the combustion process to proceed. mixtures when initiated, in contrast to some other
incendiaries, usually burn rapidly; often with ex­
5-4 INCENDIARIES plosive violence. Unfuzed incendiary rounds up to
Incendiary devices are used to initiate destruc­ 2 0 mm sizes are usually initiated by the heat pro­

tive tires in a large variety of targets. While air­ duced from the crushing of the metal nose by im­
craft, buildings, industrial installations,' amnvno­ pact while 2 0 mm and larger sizes are provided
tion, and fuel dumps are among the principal tar­ with fuzes which are initiated by impact.
gets for incendiary attack, incendiarips have proved The functioning of a thin metal nose, nonfuzed,
to be effective against personnel, armored vehicles, small arms incendiary bullet can be divided into
and tanks. In many cases, the psychological ’ear three separate stages :
of fire increases the effectiveness of an iticend arv J. Initiation of incendiary compositions by bul­
ittack as personnel may abandon relatively safe let impact f.ii target.
positions and vehicles thus exposing themselves 2 . Rapid burning and heating of the composi­
to tin* action of other weapons. tion and its combustion pro hots, until a maxi-'
Incendiary compositions and incendiary d< '• iir.i ii (empeinture is reached and the burning
\ices can It classified in many wavs depending on contents burst.from the bullet jacket
their /composition and use. In this handbook, in- Cooling of the products from their maximum
•mdiaries art grouped into three large classes ..temperature, to the 'minimum •ffn-i ivc tempera-
bused on their use: . : ; t ire, i.e,, the minimum tempera', mv necessary
1 Small arms ineendiary ammunition used pri- for fuc! ignition
m anly against aircraft and fuel dumps.
The chain of reaction with fuzed incendiary
2 O ther incendiary munitions including bo fnbs,
rounds, such as 2 0 mm, is similar to that described
grenades, mortar and artillery projectiles to
except that the sensitive fuze starts ignitionUpon
initiate fires in buildings, industrial inst:alia-
impact.
tions, ammunition, fuel dumps and other ta rgets
The degree of penetration before initiation of
in the combat zone, in areas behind the co:mbat
the burst is determined, primarily, by the sensi­
area, and in the zone of interior of the ene:my.
:l. Special incendiary devices used for ert tivity o f the bullet and its ability to carry through
purposes, in connection with guerrilla opiera- target areas to the interior of the aircraft. The
tions, and for the destruction o f material and physical size of the incendiary burst produced also
documents. affects its burst location in the aircraft. This has
been found to he especially important in the case
5-4.1 SMALL ARMS INCENDIARY of sparking-type incendiary compositions since they
AMMUNITION 8 spread throughout a target, area and produce a
Small arms incendiaries are used primarily for very large and effective burst volume.
starting destructive fires in aircraft fuels. The For many incendiary compositions, for which
burst produced serves, basically, as an ign tion the burning time is very short, the effective burst
souree for the fuel carried by the aircraft sinse it duration is the time required for the products to
is unlikely that a small arms incendiary burst of cool to the minimum temperature required for fuel
sufficient intensity or duration would weaken air­ ignition. In other mixtures which contain relatively
AMCP 706-185

TABLE 5-6
SUMMARY OF LIMITS OF FLAM M ABILITY OF VARIOUS GASES
AND VAPORS IN A IR AND IN OXYGEN

O xygen Percentage Below

W hich N o M ixtu re is
Lim its in A ir , % Lim its in O xygen, % Flam mable

N itrogen as Carbon
D ilu ent o f dioxide as
Gas or V apor Low er H igher Low er H igher A ir D iluent o f A i r

H YDRO CARBO N S
6.3 (5.0) 14 15 5.1 61 ' 12.1 14.6
3.0 12.5 15 3.0 66 11.0 13.4
2.2 9.5 2.3 55 11.1 14.3
1.9 8.6 1.8 49 12.1 14.5
1.8 8.4 1.8' 48 12.0 14.8
1.5 1.4 7.8 12.1 14.4
1.4 7.6
2-2 Dimethyl propane........................ 1.4 7.6
1.2 7.5 11.0 14.5
1.2 7.0
1.2 7.0
1.2 1.1 6.7
1.1 6.7
1.0
1.1 1.0 6.0
.8
ft 4.9
.7 5.7
.8 5.4
3.1 2.7 32 34 3.0 80 10.0 14.7
2.4 2.0 10.3 11 2.1 53 11.6 14.1
2.0 9.6
1.6 9.3 1.8 58 11.6 14.0
1.8 9.7 1.7 55
1 8 8.8
1.5 1.4 8.7
2.0 11.5 10.4 13.1
2.5 (2.3) 81
1.4 7.1 11.2 13.9
. 1.4 1.3 6.7
1.0 6.0
1.0
1.1 6.1
.8 5.8
,9 5.9
2.4 10.4 2.5 60 11.7 13.0
1.2 7.7
Ethyl uyulup&ikUhUG............................ 1.1 6.7
1.3 8
1.2
Ethyl cyolobuxAUB•............................ .9 6.6

M IXTU RE S
7.0 72
6.5 36
4.8 13.5 12.0 14.4
Ollifcl jutlulbl jMW............................ 3.8 -6 .5 13-17
1.1
1.4 7.6 11.6 14.4
0.8 5
.7 5
5.3 32 7 70 11.5 14.4
Coal gas...............................................
Coke-oven gas..................................... 4.4 34
35 74
17 20-35 70 70-80
4.7 33
i

5-12
 AMCP 706-185

slow-burning metal fuels, the burning time is an The energy required to vaporize a given quantity
appreciable part of the total burst duration. of kerosene is somewhat less than that. for gaso­
line. The energy must be available, however, at
5-4.1.1 Ignition and Combustion of Aircraft Fuels somewhat higher temperatures because of the lower
It is generally accepted9 ,10 that the combustion volatility of kerosene. The energy made available
of a hydrocarbon: ( 1 ) occurs in the gas phase, for evaporation of fuel by the flame of a self-
( 2 ) involves a chain-reaction mechanism which in­ propagating fire is roughly the same for gasoline
cludes the formation of unstable species such as and kerosene inasmuch as heat of combustion for
free atoms and free radicals, and (3) can occur both fuels lies in the range of 2 0 , 0 0 0 to 2 2 , 0 0 0
only when the concentration of the hydroc irbon BTU per pound.
vapor in the air falls within certain well-defined It is well established16 that fires can be initiated
limits, as illustrated in Table 5-6. 1 1 Normal varia­ by an incendiary bullet penetrating self-sealing
tions in atmospheric pressure do not appreciably aviation fuel cells above the liquid level, if the free
affect the limits of flammability; and, for m os; mix­ space contains air, perhaps because of a previous
tures, there is a straight line relationship between puncture or air leaking into the tank. Rarely, if
the limit of flammability and the initial tempera­ ever, has a fire been started inside the tank by an
ture o f the mixture. 1 2 incendiary bullet striking below the liquid level.
For fuel concentrations within the flammability In fact, during developmental tests of incendiary
zones, a fire or explosion can result from contact ammunition, care was always taken to strike the
with an incendiary source when the temperature of tank below the liquid level with a second shot if
this source is sufficiently high. Various methods the first shot failed to ignite. All effort was toward
have been tried to determine the minimum igni­ developing an incendiary bullet with one shot ig­
tion temperatures for various liquid fuels. A popu­ nition capability below liquid level as this was
lar experimental procedure for such determina­ most difficult to achieve. Success was achieved
tions involves confinement of the fuel vapor and when incendiaries of long burst duration and long
air mixture in a suitable.container and application particle burning time were developed. These long
of external heat until the mixture ignites. I i gen­ burning particles ignite the small spurt of fuel
eral, the hydrocarbons o f a higher molecular weight which is forced through the bullet hole after 30 to
tend to ignite at lower temperatures. There ex­ 50 milliseconds by the pressure wave set up inside
ists, however, an ignition lag18 (Paragraph 3-3.6.1) the tank by the bullet.
which is dependent upon several variables. Flame will propagate in kerosene mist-air mix­
Grades JP-1 and JP-3 aviation fuel have mini­ tures for a wider range of concentrations than in
mum ignition temperatures between 400°F and kerosene vapor-air mixtures. It is impossible to
500°F, with an associated ignition lag from 100 to obtain a concentration of kerosene mist in air
200 seconds. Aviation gasolines have minimum too rich to be ignited if the temperature is be­
ignition temperatures of 800°F to 950°F with an ig­ low the flash point of kerosene. However, at
nition lag of 2.0 to 2.5 seconds. 14 The ignition lag temperatures high enough to produce a vapor
for all hydrocarbon fuels becomes less with i icreas- concentration in air near the upper limit of
ing temperatures. A t the minimum ignitioi tem­ flammability, the mixture may be so rich that it
perature of gasoline, about 900°F, the ignition lag fails to propagate. The initiation of a mist ex­
for-kerosene is in the range of 2 to 1 0 sec ends. 15 plosion takes place after the evaporation o f mist
Fires, therefore, can be initiated and propagated droplets near the ignition source from a local vapor
in a flammable kerosene vapor and air mixture as concentration within the explosive limits. This
readily as in a gasoline vapor and air mixture if vapor ignites to form the initial flame front. Propa­
both mixtures are within the flammability zone. gation of the flame proceeds by evaporation of
Consequently, factors which control the formation droplets which form an inflammable gas mixture
of fuel vapor are of primary importance in de­ in the preheating zone in advance of the flame
termining ignition characteristics. front.

5-13
AMCP 706-185

depends strongly on the ambient pressure and the

supply of oxygen from the atmosphere since these
factors arc important if a self-sustaining fire is to
result from the action of incendiary bullets. In­
formation obtained from tests in partially inert
atmospheres, both in altitude chambers and in actual
flight tests, indicates that damaging fuel fires can­
not be started at very high altitude. Studies with
several pure fuels indicate that the relationship be­
tween spark minimum ignition energy H and
pressure for a fuel-air mixture can be represented
' X* 28% O . 90% A • 79% '
____ I___ I____1____1____I____I___ i___ I____l____I____i _ _ l ____ l _ l ___ l___ ) ,1.— I
b y : 18
0 2 4 6 8 10 12 14 IS

INCHES « H = ~ (5-7)
p"
Figure 5-1. Constant Ig n itio n P ro b a b ility Regions A b o u t a
Fuel Jet o f Gasoline o r Kerosene where p is the pressure, k is a constant which de­
pends on the nature of the fuel, and n is another
Studies of phenomena associated with the pene­ constant having a value o f about 1.82. Even if
tration of liquid fuel tanks show that hydro­
fires are initiated at high altitude, the nature
dynamic forces resulting from the impact of a of the fires, especially at the higher airflows, might
projectile on an aircraft fuel cell produce a pres­
be diffused and low in temperature, thus limiting
sure wave in the stored liquid. A high, positive
the damage produced.
pressure is near the point of tank penetration a
few milliseconds after impact by the projectile.
The fuel spray emerging from the hole made by 5-4.1.2 Nature of a Small Arms Incendiary Burst
the projectile has the normal characteristics of As already indicated, the burst produced by
filament jets with droplets forming at the leading the functioning of small arms incendiaries is funda­
edge of the filament. mentally an ignition source for starting a destruc­
The basic factors which account for the differ­ tive fuel fire in an aircraft. The amount of
ences in flammability characteristics of aircraft energy transferred to the fuel depends on the
fuels are the relative volatility and viscosity of the nature of the combustion process (the temperature
fuels. The relatively low volatility and high vis­ reached and the characteristics of the products of
cosity of kerosene make it considerably more diffi­ combustion), the mode of energy transfer process,
cult to ignite than gasoline. Results of tests (with and the efficiency with which the energy is ab­
fuel jets designed to simulate the fuel spray made sorbed by the fuel.
as a projectile penetrates a fuel tank) presented The maximum temperature reached in an in­
in Figure 5-1 indicate that the probability of a cendiary burst is a measure of both its relative
positive ignition is greater for gasoline than for intensity and duration, as a result of chemical
kerosene at any point in the volume surrounding reactions which occur within the burst to the end
the axis of the jet. The type of fire occurring with of its cooling cycle. A consideration of the burst
the gasoline jet is usually different than that oc­ temperature, and the effects of the physical and
curring with kerosene. Most gasoline fires propa­ thermodynamic properties of incendiary mixture
gate rapidly through the fuel spray. Little, if any, ingredients and their reaction products, comprise
unburned fuel is left in the area. In contrast, an important area o f study concerning an incendi­
nearly all kerosene ignitions are localized, seldom ary burst. The temperature produced by an
propagating more than a few inches from the point incendiary burst can be estimated by calculations
o f ignition so that most of the fuel is left un­ using the methods outlined in Paragraph 3-2.5. It
burned. . is necessary to assume, arbitrarily, the amount of
The effectiveness of incendiary ammunition also atmospheric oxygen available for combustion of the

5-14
 AM CP 706-185

incendiary mixture. The extreme conditions are products from the maximum temperature reached
either: ( 1 ) that the only oxygen available for by the incendiary burst to the minimum effective
combustion is that contained in the mixture eom temperature divided by the temperature differ­
ponents due to insufficient time for the diffusion of ence— and neglecting 2 V since it is very much
atmospheric oxygen into the flame; or ( 2 ) that smaller than 2 V , integration yields:
the surrounding air supplies the additional oxygen
1 \ wi (Ea Eg — EgEa)C
required for complete combustion of the reactants.
r ,3 ) 3 uE se ba
The actual condition is probably somewhere be­
(5-9)
tween. Limited experimental data obtained for
bursts in controlled atmospheres indicate that the I f it is assumed that the radiating area A and
surrounding atmosphere does not enter appreciably emissivities E tt and E s have average values which
into the incendiary reaction so that condition may be assumed constants for the various bursts,
(1) is the,better assumption. The difference in the the terms outside of the parentheses may be con­
sidered a constant K and :
results is small, however, because of the necessity
for heating the nitrogen of the air under assump­
tion (2 ). (See also Example 4, Paragraph 3-2.5.)
The rate of heat transfer from the burst cloud I f k is assumed to be 10® (A ~ 2 X 104 cm2, E B =
to its surroundings depends also upon the method 0.9, E$ = 0 . 1 and m = l ) , the curves in Figure
by which the heat is transferred. Heat c a i be 5-2 result where it is assumed that the minimum
transferred by combustion, convection, and radia­ effective temperature is 800°K.
tion; however,, at temperatures above the ignition If the adiabatic flame temperature can be cal­
temperature of aircraft fuels, heat transfer by culated or experimentally obtained and if the heat,
radiation is probably the dominant method. Itadi- of reaction is known, Figure 5-3 can be used to
ant energy emitted by the liquid, solid, and gaseous estimate an average specific heat. I f Figures 5-2
species in an incendiary burst is a complicated and 5-3 are combined, Figure 5-4 results. As can
function of wavelength, pressure, geometry, and be seen, the cooling time varies directly with the
chemical composition of the emitting molecular average specific heat. The curves also indicate that
aggregate, as well as of temperature. However, any increase in the burst temperature above 2 0 0 0 °K
based on experimental results, it can be assumed results in only a small increase in the cooling time.
that the incendiary burst cloud radiates as a ^ray- Change in cooling times resulting from transfor­
body with a relatively high emissivity. mations is difficult to determine because the details'
The rate of heat transfer from an incendiary of the cooling mechanism are not known.
burst cloud, radiating as a graybody may be ex­ Experimental cooling curves for incendiary
pressed b y : mixtures are given in Figure 5-5. 19 IM-11, 50
percent barium nitrate and 50 percent magnesium-
E BEaa(TB4 — TB4) A
dQ/dO= (5-8) aluminum alloy, is one of the standard mixtures
Ea “t* Eg — E bE s
used in incendiary bullets. IM-23, 50 percent
where A is the total radiating area of the com­ potassium perchlorate and 50 percent magnesium
ponents in the burst cloud, dQ is quantity o f heat alloy, contains no barium nitrate and its calcu­
radiated by the incendiary burst cloud during time lated temperature is higher than that for IM-11.
interval d'B, a is the Stefan-Boltzmann constant, IM-63— 50 percent calcium peroxide, 45 percent
E is the emissivity, and T is the absolute tempera­ red phosphorus, and 5 percent aluminum hy­
ture. The subscript B refers to the burst and the droxide— docs not contain either barium nitrate or
subscript S refers to the surroundings. By com­ alloy, and has a considerably lower theoretical
bining this equation with the equation dQ = rr CdT maximum temperature than IM-11. It is to be
where C is the overall average specific heat— i.e., noted that IM-103, 50 percent red phosphorus and
equals the heat evolved per gram, including that 50 percent magnesium-aluminum alloy, does not
from phase changes, in the cooling of the reaction contain an oxidizer.

5-15
AMCP 706-185

MAXIMUM TEMPERATURE T,» °K

Figure 5-3. Coaling Time to 800°K as a Function o f

Temperature and Heat Capacity, C
Figure 5-2. Maximum Temperature, T, as a Function of
Heat o f Reaction and Average Specific Heat, C
plosive material in addition to its incendiary filler
material.
5-4.1.3 Small Arms Incendiary Fillers Magnesium-aluminum alloys have been an es­
Small arms incendiary ammunition, which now sential.ingredient in most o f the successful incendi­
includes ammunition through 40 mm, has been ary mixtures, and have replaced both white phos­
developed, like other ammunition, to meet the par­ phorus incendiaries and tracer compositions.
ticular needs of the using Services. Important Tracers, first used as incendiaries, employed a
modifications and improvements were made through filler consisting of two parts magnesium and seven­
the years in response to changes in Service needs teen parts barium peroxide for incendiary pur­
or anticipated changes in Service requirements. poses. Until the development o f the highly satis­
Early developments in small arms incendiary am­ factory incendiary filler based on a magnesium-
munition fillers have been discussed in the his­ aluminum alloy (50/50) fuel, with barium nitrate
torical review of incendiaries (Paragraph 5-1). as the oxidizer, changes in tracer mixtures used
Sensitive explosives— including mercury ful­ as incendiaries were limited to those which would
minate, lead azide, and PETN— were employed in improve the performance of metal-oxidant com­
some early incendiary fillers. Other explosives— positions. Numerous incendiary mixtures have been
including tetryl, MOX, TNT, Haleite, and EDNA tested for use in small arms ammunition in the
— also have been tried in smaller nonfuzed in­ period since the beginning of World W ar II. A
cendiary ammunition but have not proved satis­ detailed card file listing o f the incendiary mixtures
factory. High explosive incendiary ammunition which have been given an IM number (approxi­
in 2 0 mm and larger sizes contains a purely ex- mately 1000) is maintained at Frankford Arsenal.

5-16
 AMCP 706-185

figure indicate that an increase in burst duration

and cooling time results with coarser and with
atomized or spherical particles. Firing tests con­
firm these results. Evaluations of magnesium-
aluminum alloys other than 50/50 show that the
50/50 alloy is superior for a variety of applica­
tions whether ground or atomized.
In an attempt to develop improved small arms
incendiary mixtures, a large number of metals and
alloys were evaluated for their effectiveness as in­
cendiary fuels with several oxidizing agents, as
reported in detail in Reference 6 . Some of these
mixtures produced incendiary bursts which have a
longer duration than those produced by IM-11.
These mixtures also have proved to be more effec­
tive than IM-11 in comparative tests against air­
craft targets.

5-4.1.3.2 Oxidizers
A wide variety of materials have been used
as oxidizers in incendiary mixtures. An oxidizer,
for use in mass-produced items which are loaded
0 1000 3000 5000
by automatic machines, must meet a variety of
H r HEAT OF REACTION, col/g requirements in addition to being able to supply
the necessary quantity of oxygen.
F igure 5 -4 . C o o lin g Time to 800°K a t a Function o;1Heat The effects of oxidizer particle size on in­
o f Reaction a n d Specific H eat, C cendiary bursts have been studied. Incendiary
mixtures containing oxidizer particles of compara­
5-4.1.3.1 Fuels tively large size ( 1 0 0 to 2 0 0 mesh) could not be
Incendiary compositions containing magnesium- ignited unless the mixture contained' finely divided
aluminum alloy have been the basis o f most c f the (less than 325 mesh) alloy fuel particles. Mix­
standard incendiary compositions investigated un­ tures containing fine or medium-sized barium
til recent years. Studies have indicated that an nitrate particles would not burn except when
alloy of 50/50 proportions, prepared by grinding mixed with coarse alloy. Alloy particle sizes in
with a particle size range from 60 to 325 mesh, the range specified for IM-11 reacted erratically
is optimum for a wide variety of applications. with either a narrow range coarse or a fine barium
The effects o f variation in the granulation o f the nitrate powder. Specification grade alloy reacted
magnesium-aluminum alloy were evaluated early best with barium nitrate which consisted o f both
in the program, leading to the development of fine and coarse particle sizes. The cooling dura­
IM-11 (composed of 50 percent magnesium- tlum- tions o f the incendiary burst for the few mixtures
inum alloy 50/50, and 50 percent barium nitrate) which could be ignited increased as the particle
which was the basic incendiary mixture us id in size of the barium nitrate was increased, but these
World War II. Figure 5-6 shows the cooling changes were relatively small.
curves and burst duration (the time from ignition Some of the alkali metal and alkaline earth
until burst cloud cooled to 1540°K) curves for nitrates have been more widely employed than
mixtures which contain either the ground or other types of oxidizers because they are available
atomized alloy in a variety o f mesh sizes with at low cost, contain large quantities o f available
some barium nitrate. The results presented in this oxygen, are safe, and can be handled easily.
 AMCP 706-185

2400 -
* 2300 -
#. 220 0 (I M-103)
50% P
W 2 10 0 -
50% Alloy
3 2000 -
< 1900 -
£E leoo (IM-23)
lii
Cl 1700 h 50% KCIO.
2 5 0 % Alio/ X***v
Ui 1600
(IM- II) —
H 1500 -
5 0 % 8a{M09)2
1400 -
1300
1200 j- t , j i .. -i . - t . i. . -L
50 100 150 200 250 300

TIM E , MILLISECONDS

Figure 5 -5 . Time-Temperature Histories fo r IM-1J, IM -2 3 and IM -103

Barium nitrate has been incorporated in over 200 trate but exhibits a lower decomposition tempera­
incendiary mixtures, including the widely used ture. Mixtures containing potassium perchlorate
IM-11 filler, and has been utilized in proportions tend to be more sensitive and to burn faster than
ranging from one percent to 65 percent of the mixtures which contain only barium nitrate as the
total mix. This oxidizer is stable to approximately oxidizer. Ammonium perchlorate has also been
600°C, has a high critical humidity, is easily used as an oxidizer. This material is considered
handled, and is available at moderate cost. Some to be an explosive since the hydrogen contained
compositions in which barium nitrate is used as in the compound can be oxidized rapidly as the
the primary oxidizer are improved, from the stand­ decomposition of ammonium perchlorate' takes
point o f incendiary functioning, by the addition place. This oxidizer-explosive has been used ex­
o f a small quantity of a more reactive oxidizer tensively in the MOX series of metalized ex­
such as ammonium nitrate or potassium per­ plosives and probably contributes to the explosive
chlorate. Ammonium nitrate has been used in energy of these compositions, as well as providing
several incehdiary mixtures as an oxidizer, how­ oxygen for the burning o f the metallic fuel which
ever, it has a relatively low decomposition tempera­ provides the major incendiary effect o f MOX-
ture and tends to sensitize incendiary mixtures loaded ammunition. Ammonium perchlorate is a
in which it is used. Other nitrates are potentially rather sensitive oxidizer and, therefore, is some­
good oxidizers, but are not widely used because of what hazardous to handle. Other perchlorates have
some undesirable characteristic, such as being rela­ been used; but, in general, they are hygroscopic
tively hygroscopic or uneconomical. and, therefore, are difficult to handle in production
The alkali metal perchlorates are the second loading equipment.
most widely used group o f oxidizers for incendiary Some peroxides and less stable oxides can be
mixtures. 2 Potassium perchlorate has been used in used as oxidizers in incendiary mixtures. Lead
many incendiary fillers in proportions varying dioxide is probably the most important member
from 2.5 percent to 75 percent o f the total mixture. o f this group, and it has been used in several
Potassium perchlorate has essentially the same incendiary fillers. It tends to sensitize mixtures
total and available oxygen content as barium ni­ in which it is used, although by itself it is safe

5-18
 AM CP 706-185

5-4.1.3.3 Binders, Lubricants, and Other

- i — |— I— I— r — I 1— i— i— i— I— i— r-

5 0 % A tom ized A llo y

Incendiary Mixture Additives
-1 0 0 ♦ 2 0 0 = 9 3 .3 %
The first metal-fuel incendiary compositions
-2 0 0 *3 2 5 * 6 .7 %
used in small arms ammunition contained only the
metal-fuel and a suitable oxidizer. The mass pro­
duction of small arms incendiary ammunition dur­
ing World War II created problems concerning
pelleting of incendiary mixtures, sticking of com­
pression punches, lumping of mixtures during
handling, and failure of mixtures to flow properly
in the automatic loading equipment. These prob­
50 100 IS O 200 lems were met by adding binders, lubricants and
TIME .MILLISECONDS flow promoters to the then standard compositions.
The amount of additive present in the composi­
Figure 5-6. Cooling Curves for Mixtures Containing tions was small and did not impair the incendiary
Various Particle Sizes and Shapes o f Magnesium Alumi­
functioning of the ammunition, and they were es­
num 5 0 /5 0 Alloy
sential to the successful mass production of in­
cendiary ammunition. Without these additives
and easy to handle. Less oxygen is available from it would have been impossible to achieve the high
lead dioxide than from many of the nitrate and level of ammunition quality that was maintained
perchlorate oxidizers. Its high density has made during World W ar II. Since then, the require­
lead dioxide useful for applications where an in­ ments for mass produced ammunition have become
crease in bullet weight is desirable. even more stringent.
A few additional oxidizers that have been eval­ The two most frequently used binders in small
uated in incendiary mixtures are worthy of men­ arms incendiary mixtures are calcium resinate and
tion. These include potassium chlorate, which is asphaltum. In incendiary filler compositions, cal­
a relatively good oxidizer except for its sensitivity cium resinate is used in amounts varying between
and incompatibility with certain fuels, notably red one and two percent, and asphaltum is used in
phosphorus; strontium chromate, potassium di­ amounts varying between one and five percent. A
chromate, and potassium permanganate have also number of other binders have been tested in sev­
been used. None of these has been found to be eral compositions from time to time. These include
fully satisfactory as oxidizers for incendiary mix Acrawax, dextrin, starch, nitrocellulose, gum
applications. arabic, polyvinyl alcohol, red gum, vistanex (a
One of the most intriguing applications of rubber preparation), and AP-2 (a jellied gasoline
oxidizing materials to the destruction or damaging and aluminum mixture).
of aircraft structures is the direct reaction of an Graphite, in a range of particle sizes, has been
oxodizing agent with the fuel contained in the used successfully as a lubricant to prevent the
aircraft. The idea is appealing because of the sticking of pelleting and compression punches dur­
potential chemical energy release since only oxygen ing the loading of incendiary ammunition. This
or an oxidizing agent is placed in the projectile lubricant is normally added in amounts ranging
and no space is required for fuel. Many ralther from 0.25 percent to 2.0 percent. Stearates of zinc
difficult practical problems are involved in ad apt­ and aluminum have been employed in a number of
ing this principle to realistic target conditions small arms incendiary compositions to prevent
using standard projectile components and fuzing lumps from forming in the mixtures and to im­
mechanisms. Some of the oxidizing chemicals prove the flow characteristics during the automatic
which might be useful in this connection include loading processes. -These ingredients are of some
lF r„ Cl Fa; HrFs, I1C104, OF,, 0 2 F 2, Q»F*, n Io 3 F, assistance in forming pellets of the mix in addition
C102 F, and N FS. to their flow-inducing characteristics. Zinc stearate

5-19
AMCP 706-185

TABLE 5-7
TYPICAL SMALL ARMS INCENDIARY MIXTURES

JM-11 4,9% Potassium Perchlorate

50% Magnesium-Aluminum Alloy (50/50) 2% Calcium Resinate
50% Barium Nitrate
1M-139
JM-21A i 10% Magnesium-Aluminum Alloy (50/50)
48% Magnesium-Aluminum Alloy (50/50) 40% Red Phosphorus
48% Barium Nitrate 47% Barium Nitrate
8 % Calcium Resinate 3% Aluminum Stearate
1 % Asphaltum
IM-142 •
IM-23 46% Magnesium-Aluminum Alloy (50/50)
50% Magnesium-Aluminum Alloy (50/50) 48%' Barium Nitrate
50% Potassium Perchlorate 5% Asphaltum
1% Graphite
IM-28
50% Magnesium-Aluminum Alloy (50/50) 1M-214
40% Barium Nitrate 50% Zirconium (60/80) (lot 6 )
10% Potassium Perchlorate 25% Magnesium-Aluminum Alloy
25% Potassium Perchlorate ( —250)
1M-68
50% Magnesium-Aluminum Alloy (50/50) 1M-241
25% Ammonium Nitrate 50% Zirconium (20/65)
24% Barium Nitrate 25% Magnesium-Aluminum Alloy
1% Zinc Stearate 25% Potassium Perchlorate ( —250)

IM-69 IM-385
50% Magnesium-Aluminum Alloy (50/50) 49% Magnesium-Aluminum Alloy (50/50)
40% Barium Nitrate 49% Ammonium Perchlorate
10% Iron Oxide (Fe 2 0 3) 2% Calcium Resinate

1M-112 MOX-2B (High Explosive Incendiary Fillers)

45% Magnesium-Aluminum Alloy (50/50) 52% Aluminum Powder
5% Tungsten Powder 35% Ammonium Perchlorate
6 % R D X /W ax (97/3) ,
50% Barium Nitrate
4% TNT (Coated on the Ammonium Perchlorate)
IM-136 2% Calcium Stearate
49% Magnesium-Aluminum Alloy (50/50) 1% Graphite

in the amounts of l % - 2 % has been most widely 5-4.1.4 Typical Small Arms Incendiary Bullets
used for this purpose. Aluminum stearate has also Typical incendiary rounds are shown in Figures
been employed for this purpose. 5-7 through 5-10. Illustrated are a caliber .50
incendiary bullet, Figure 5-7, and a caliber .50
5-4.1.3.4 Typical Compositions armor-piercing incendiary, Figure 5-8. A 20 mm
The compositions of 14 small arms incendiary armor-piercing incendiary bullet is shown in Fig­
mixtures, considered to be typical, are given in ure 5-9 and a 20 mm high explosive incendiary
Table 5-7. projectile is shown in Figure 5-10.
 AMCP 706-185

TO TAL WEI GHT: 512 G R A I NS

Figure 5 -7 . Typical C aliber .50 Incendiary Bullet

5-4.2 IN CEN D IARIES FO R GROUND hands of combat troops. Little, if any, effort was
APPLICATIO N directed toward studying those factors concerned
Ground incendiaries include that class of muni­ with the initiation of destructive fires in various
tions used for damage, mainly by combustion, to targets. As a consequence, less is known about
ground targets and are considerably larger than the the factors which might increase the effectiveness
small arms incendiaries previously discussed. In­ of incendiary munitions against ground targets
cendiary bombs, for example, are more effective, than is known about the effectiveness of incendi­
against cities than high explosives, especially when aries against aircraft targets.
antipersbnnel features are included to delly fire
fighting operations. The delay in fire fighting opera­ 5-4.2.1 Ignition and Combustion of Ground Targets
tions allows the smaller fires to grow land unite to Incendiary and other flame-producing weapons,
form a conflagration which is almost impossible to like most weapons used against ground targets, are
control.: In many cases, toxic effects resulting from a source of energy which, when absorbed by the
the use 6 f incendiaries or flame weapons (high car­ target, will cause damage. The amount of energy
bon monoxide con tent-low oxygen content) cause absorbed from the incendiary source by the target
many casualties. In some cases, the psychological is not usually sufficient to produce appreciable
fear prevents effective fire fighting operations and damage but serves only to initiate combustion of
may result in the loss of equipment through aban­ the target in the oxygen of the air. Small fires
donment. started in this manner serve as ignition sources
Because progress in the development of incendi­ for the remainder of the target material, resulting
ary and flame weapons for use against ground tar­ in the spread of the fire. The ignition process and
gets Has been made mainly during times of stress, early growth of the fire are the critical stages in
emphasis has been directed toward the development the development of a damage-producing fire.
of weapons which could be rapidly put into the To initiate burning of a target in air, three

5-21
 AMCP 706-185

TOTAL WEIGHT: 6S2 GRAINS

: ' * .• •

Figure 5 -8 . Typical C alib e r .5 0 A rm or-P iercing Incendiary Bullet

■essentials must be provided, namely: ( 1 ) a source of and a combination of these two. Fillings can also
heat to initiate the fire, ( 2 ) combustible material be classified into those which owe their incendiary
which serves as kindling, and (3) the fuel. All effect to a self-supporting exothermic reaction and
incendiary munitions, except those which are spon­ those which depend oh atmospheric oxygen for
taneously combustible, must contain an initiator. their combustion.
The major part of an incendiary filling serves as
the kindling and the target supplies the fuel. The 5-4.2.2.1 Metal-Based Ground Incendiaries
efficiency of an incendiary depends on the total Incendiaries containing metallic components are
heat output and the rate of transfer of the energy of two types: those which utilize the oxygen of the
to the target so as to initiate a sequence of events air in their combustion, and those in which an
which will result in the burning of the target. oxidizing agent furnishes the oxygen.
Solid materials, such as wood, must be heated to a Magnesium-aluminum alloy used both as the
sufficiently high temperature in order to form the case and in the composition of a tour-pound in­
gaseous intermediates to react with the oxygen of cendiary bomb is an effective incendiary and was
the air. Liquid fuels, as discussed in detail in widely used in World War II in raids against
Paragraph 5-4;2.2.2.1, also must be vaporized be­ German and Japanese onies. Keaction with.oxygen
fore combustion is initiated. i
of the air produces more heat with ui incendiary
metal than with solid oxidizing compounds. The
5-4.2.2 Incendiary Compositions . use of these compounds, therefore, must be justi­
Most of the research on incendiaries has been fied by an increase in effectiveness due to the high­
concerned with quantity and type of combustible er rate of heat release.
used as an incendiary filler. Incendiary fillers can Thermite-type incendiary mixtures, are com­
be basically classified into three categories: metal- posed of approximate oxygen-balanced mixtures
based incendiaries, liquid fuel-based incendiaries. of reducing and oxidizing agents. While there ere

5-22
 AM CP 706-185

-ROTATING BAND, COPPER OR GILDING METAL

BASE MIXTURE
IM -2 1
STARTER M IXTURE
IM —136

-A R M O R -P IE R C IN G STEEL BODY

TOTAL WEIGHT: 1700 GRAINS

F igure 5-9. T ypical 2 0 m m A rm or-P iercing Incendiary Bullet

a large number o f possible combinations Which 2A1 -|- 3FeO -> AI2 O3 -)- 3Fe -j- AH
contain one or more reducing agents with or e or
and gives the stoichiometrical ratio o f one part o f
more oxidizing agents; aluminum (Table 5-1) and,,
aluminum to four parts of ferrous oxide. Since
to a lesser extent, magnesium (Table 5-8) lave
iron oxide scale (hammer scale) is a mixture o f '
been the only reducing agents used in thermite-
ferrous and ferric oxide in various proportions, the
type incendiary mixtures. stoichiometric amount of aluminum required to
M ilitary'thermite for incendiary purposes 18 react with the available oxygen present will also
composed of 2.75 parts o f iron oxide scale anr one vary. i
part o f granular aluminum . 20 The reaction: The ferrous oxide, FeO, content o f the hammer
8A1 -f- 3 Pe 80 4 -> 4 A.I2 O3 -f- 9Fe -j- AH scale has little effect on either the burning time or'
the penetration o f the molten iron produced by the
gives the stoichiometrical ratio of one part of alu-
thermite reaction. A lower ferrous oxide content
minum to 3.2 parts o f iron oxide, FesO*. Feirric
produces a considerably better flame and better ‘
oxide, Fe2Os, reacts as follows:
propagation o f burning; however, for values below
2A1 -f- Fe 2 0 8 —* AI2 O3 - f 2Fe -4 - AH 2 2 percent ferrous oxide, the improvement is slight.

and gives the stoichiometrical ratio of one palrt of Thinner flake scales, such as pipe scale and rod
aluminum to 2.96 parts o f ferric oxide. Ferrous scale, have been found to be more satisfactory than
oxide, FeO, reacts as follows: coarser scales; however, the use o f a slight excess '

5-23
AMCP 706-185

(IIUMI)
(IM-142)

TOTAL WEIGHT- 1600 GRAINS (APPROX.)

Figure 5-10. Typical 20m m H igh Explosive Incendiary Projectile

of aluminum minimizes the effect of particle shape have been tried without appreciable success. The
of the hammer scale. compositions of some of the incendiary mixtures
The use of low-purity aluminum (92.5 per­ . tried are given in Table 5-9.
cent) requires a higher ratio of aluminum to ham­
mer scale (1 to 2.7-2.8) to obtain optimum burning
characteristics. The use of fine-mesh granular 5-4.2.2.2 Liquid Fuel-Based Incendiaries
aluminum results in decreased burning times ap­ Liquid fuel incendiaries depend entirely upon
proaching a minimum limit with decrease in par­ the oxygen of the air for their combustion. The
ticle size. I f the aluminum is too coarse, poor organic- substance with the highest heat of com­
propagation, poor flame, and a longer burning time bustion on a volume basis is anthracene with 11,900
result. calories per milliliter. A wide variety o f natural
During W orld W ar I, binders such as sodium oils and waxes fall in the range of 8,500 to 9,200
silicate, sulfur or celluloid were added in order to calories per milliliter. For hydrocarbons, there is
reduce segregation of the thermite after loading; a definite relationship between the heats of combus­
however, these techniques were only partially suc­ tion and the hydrogen-carbon ratio as shown in
cessful. Thermite has not been used since W orld Table 5-10. The order of heat on a unit-volume
War I for incendiary applications. While the heat basis is the inverse o f the order o f the hydrogen-
released by a thermite mixture is sufficient to heat carbon ratios, while the position is reversed on a
the products of reaction to around 3000°C, the unit-weight basis. While the heat evolution per
incendiary action is confined to a relatively small unit-volume of n-octane is comparatively low, its
area. In order to improve the incendiary effective­ heat evolution per unit-weight is very high ( 1 1 ,­
ness, several other incendiary compositions, in­ 500 calories per gram), being exceeded only by
cluding several modified thermite compositions, ■ boron and beryllium on this basis.

5-24
 AMCP 706-185

TA B LE 5-8 waste, but this method was only fairly satisfactory.

H E A T OF REACTION OF TH ERM lTE-frYPE During World War 11 this idea was revived and,
M IXTU RES CONTAINING MAGNESIUM based on development work, 14 percent cotton
waste saturated with 8 6 percent o f a 50/50 mixture
Mixture Heat of reaction,
of gasoline and fuel oil was tried as a possible fill­
cal/gi
ing for incendiary bombs, but was discontinued as
Mg + SbaS, ...................... 5fft more effective fillers became available.
5Mg + B a(N O s)« .......................... . . . . 1,636
4Mg + BaSO« ........................................ 1,046 5-4.2.2.2.2 Solidified Liquid Incendiaries
4Mg + CaS0 4 ........................................ 1,529
Because of the high degree of dispersion and
3Mg -j- Fe 2 0 2 .............. 1,030
consequent flash burning of liquid incendiaries,
4Mg -f- Fes0 4 ...................... 956
many substances have been proposed for solidify­
2Mg + FeS 2 ............................................ 764
ing liquid incendiaries. These include : - 1
Mg + PbO ............ 378
2 M g + P b 0 2 .......................................... 78^ a. Fatty acid derivatives
4 M g - f P b 8 0 4 .................... 73^ (1) Aluminum, sodium, zinc, and ammo­
5Mg + P b S 0 4 ......................................... 1,054 nium salts
4Mg -f- M gS0 4 . .................. l,6 6 i (2) Lead salts of hydroxy acids
2Mg + M n0 2 ........................................ : 1.24& (3) Sulfonated products .
5Mg + 2K N 0 3 ................................ ■ 79^ (4) Amides
4Mg + KC10 4 ................ ..................... ; 2,442 (5) Fatty acids per se
9Mg - f K 2 S2O g ...................................... i 1,870 ( 6 ) Natural waxes
4 M g -f K 2 S 0 4 .................. I,9l6 (a) Nitrated
4Mg + Na2 S 0 4 .................. 1,066 (b) Sulfonated
(e) Per se
(7) Anilides
5-4.2.2.2.1 Liquid Incendiaries , b. Polyhydroxy derivatives
Liquid incendiaries such as petroleum oils, (1) Glycol compounds: Esters of,fatty acids
carbon disulfide, wood-distillation products, and ( 2 ) Ethanolamine compounds
other flammable liquids, were tested during World (a) Esters of fatty acids
War I. These materials all had the drawback of (b) Compounds of mono-, .di-, an.l tri­
excessive dispersion ; to overcome this, the liquids ethanolamine
were absorbed in some material such as cotton , (3) Glycerol compounds

TABLE 5-9
m o d if ie d t h e r m it e c o m p o s it io n s
Constituents Composition, Percent

i Calcium Sulfate
Therm-8 Therm 8-2 Therm 64-c Barytes Thermite Thermite

Iron Oxide Scale 61 )5.2 44 59.2 , ■ —

Aluminum 2 2 .8 J5 25 25.3 40.9

Barium Nitrate 15 L9.5 29 ' --- . —

Sulfur 0.90 — 2 — 1 .0
Castor Oil 0.30 0.30 — — 0.3
Barium Sulfate --- ' : _____ _ 15.3 _ ___

Calcium Sulfate ' --- — _ _ . '— ' 57.8

5-25
AMCP 706-185

TABLE 5-10
HEATS OF COMBUSTION AND HYDROGEN-CARBON
RATIOS OF SELECTED FUELS

Hydrogen-
Hydrocarbon Carbon Calories Calories Density,
Ratio per ml per g 0 /«

Anthracene 0.72 11,900 9,500 1.25

Naphthalene 0.80 1 1 ,0 0 0 9,600 1.15
Toluene 1.14 8,800 1 0 ,2 0 0 0 .8 6 6

Methylcyclohexane 2 .0 0 8,600 1 1 ,1 0 0 0.769

n-Octane 2.25 8 ,1 0 0 11,500 0.706

(a) Saponified vegetable oil mixes a. Rubber (natural and synthetic)

(b) Nitrated vegetable oils b. Aluminum salts of mixed fatty acids and
(c) Vegetable oils per se naphthenic acid
(4) Polysaccharide compounds <*. Polyacrylates
(a) Lactose anhydride
(b) Dextrins 5-4.2.2.2.2.1 Rubber Thickeners
(c) Pectins
The addition of thiekners—e.g., smoked rub­
(5) Cellulose esters
ber, crepe rubber, and latex— to gasoline produces
(a) Ethyl cellulose (7 to 10 percent)
an incendiary filling resembling sticky rubber ce­
(b) Pulp
ment; Fillings o f this type are reasonably satis­
c. Resinous derivatives
factory; the material sticks to the target and
(1) Natural '
burns slowly enough to allow an effective transfer
(a) Alkali-treated resin
of heat to the target. During World War II, how­
(b) Shellac
ever, rubber was in critically short supply and
(c) Damar
other thickeners had to be developed. Satisfactory
(d ) East India fossil
thickeners can also be made with some synthetic
(e) African fossil
rubbers.
( f ) New Zealand fossil
(2) Synthetic: Saponified polyacrylates
5-4.2.2.2.2.2 Napalm Thickeners
d. Hydrocarbon derivatives !
(1) Paraffin • The napalm thickener finally adopted consisted
of a granular base aluminum soap o f naphthenic,
(2) Synthetic rubber
oleic, and coconut fatty acids. The sodium soap
(3) Natural rubber "
(4) Salts of sulfonated petroleum fractions used for the precipitation of the aluminum soap
contained 0 . 1 0 to 0.15 percent alpha-naphthol. The
(5 ) Salts o f naphthenic acid
recommended formula of the organic acids used in
e. Inorganic derivatives
(1) Organo-silicon compounds: Esters making the napalm thickener was:
(2) Bentonite Parts by weight
(3) Oil shale Coconut fatty acids 50
Naphthenic acid 25
O f these, only a few were ever found practical for
Oleic acid 25
use in thickening incendiary liquids. The most suc­
cessful substances were: The aluminum content of the finished thickener

5-26
 AM CP 706-185

TABLE 5-11
COMPOSITION OE IM -TYPE IN CENDIARY GELS

Code IM IM IM /' ... • .. ■

Type 1 Type 2 Type 3 F-1416 F-1429 F-1431 F-1457

Constituent Composition, Percent

Isobutyl methacrylate
polymer A E (IM ) £.0 5.0 2 .0 3.0 3.0 3.0 3.0
Stearic acid 2.0 — — 1 .0 4.0 3.0 4.5
(Fatty acids) 2.5 3.0 — — — —
Naphthenic acid ‘ 2.5 3.0 3.0 — 1 .0 0.5
Calcium oxide 2 .0 — — 3.1 4.0 3.5 —
Caustic soda (40% solution) 3.0 4.5 — — — —
Ammonium hydroxide (27% solution) — — ■ — — — 2.3
Gasoline ’ 88 .75 87.0 87.5 87.6 86.5 87.3 89.3
Water 1 .25 — — 2.3 2.5 2 .2 __

ranges from 5.4 to 5.8 percent and the mbisturre napalm thickener which may cause 'partial or com­
content from 0.4 to 0.8 percent. Varying tli e com- plete breakdown of-gels formed with gasoline or
position of napalm from the standard to 2 : 1 1 ratio oxidation of the thickener, include excess water,
of coconut to oleic to naphthenic acid indicatj?<d that lime, caustic soda; soaps of sodium, copper, lead,
the viscosity of the gel increased primarily with iron, manganese, and cobalt: powdered or sheet zinc
increased oleic acids and, to a lesser extenjt with and lead; lead nitrate; rust preventatives contain­
increased coconut acid above normal comp osition. ing amines, alcohols, and all acids. Tetraethyl lead,
The acid number of the coconut acid was foi.i:nd im- on the other hand, has, no injurious effects .
portent. Tron was an undesirable impurity when The fundamental reactions may be expressed
found in the alum but not in the acid. Imputiities in as follows (IIU denotes the mixture of fatty and
naphthenic acid ):

6 NaOH + 4HR + A l2(SO 4) 3-> 2A1(0I1) R 2 + 3Na2 S 0 4 + 4H20

6 N a O H -f 2HR + A U O O ,4) ? - » 2 A l(O II)sIt + W a 2 S 0 4 + 2H20

The soaps may hydrolyze:

Because of hydrolysis, A1R3 does not form, and
A1 (O H ) R 2 + H 20 A l(O H )2R -f- IIR
fatty acid in excess of that required remains as
A 1 (0 H )2R + H 2 0 - > A 1 ( 0 H ) 3 + HR
such:

6 NaOH 4 - 6 H R - f A12 (S k ) 3—* [2Al(OH)Rj> 4 - 2HR] 4 - 3Nn2 S 0 4 4- 4H20

Three processes have been used successfully for

the manufacture of napalm. All are based on the 5-4.2.2.2.2.3 Methacrylate Thickeners •
above equations, but the mechanical details for Satisfactory thickened gasoline could be made
combining the materials differ. when 15-20 percent isobutyl methacrylate polymer
Napalm, while a satisfactory thickener, is sus­ (IM ) was added. Some satisfactory IM gels are
ceptible to oxidation by the atmosphere and is summarized in Table 5-11.
hygroscopic, resulting in a th ic k e n e d g a solin e -with Low tpniporaturc »lability is favored by a low
poor characteristics. polymer content, the use of polymer of low meth-

5-27
 AMCP 706-185

TABLE 5-12
COMPOSITION OF PT IN CENDIARY M IXTURES

Code . PT-1 PT-2 PT-3

Constituent Composition, Percent

Goop 49.0 30.0 —

Isobutyl methacrylate
polymer AE 3.0 — . —
Magnesium (coarse) 1 0 .0 1 0 .0 30.0
(50/50 Mg-Al alloy) 1 0 .0

Sodium Nitrate 5.0 8 .0 6.5

Gasoline 30.0 44.0 37.5
Petroleum Oil Extract 3.0 --- ' —
(Bright stock) 1 0 .0

GR-S (Buna-S
synthetic rubber) — 8 .0 6 .0

Sulfur monochloride (S 2 CI2 ) . — 0 .2 (add) 0 .2 (add)

acrylic acid content, a high soap content, a high troops. Because white phosphorus has a low com­
concentration of gelling agent, a low water con­ bustion temperature, it is relatively ineffective
tent, and the use o f gasoline which has a low against any but the most easily ignitible targets.
aniline point. With a reasonably stable basic The alkali metals, especially sodium, have been
formula, the most- important factors appear to be used as incendiaries but the results have not been
the nature of the gasoline and the strength and con­ satisfactory. .
centration of the gelling agent. High tempe;ra.ture
stability is favored by a high polymer content, a
5-4.2J Typical Incendiary Devices
high stearic acid content, and the use of con­
centrated solutions of the gelling agent, i.e., a low The principal military characteristic of an in­
water content. The presence of oxygenated solvents i cendiary device is its ability to initiate combustion
destroys high temperature stability. !j. of material with which it comes in contact, and to
In order to increase the effectiveness o f the in­ provide the energy to maintain the combustion
cendiary filling in starting fires in targets more process and assist in enlarging the area over which
difficult to ignite, a complex filling was developed combustion takes place. This characteristic is
having as its main constituent “ goop” , a mixture . called fire raising power. Other military character­
of magnesium particles and asphalt. To this was istics covering tactical use, provision of fire-fight­
added gasoline, thickened with IM oxidizing agents ing deterrents, and design details are also speci­
and magnesium scraps. PT-1 composition, and the fied.
substitutes PT-2 and PT-3, used synthetic rubber The four-pound magnesium alloy bomb, shown
instead of IM and an aluminum-magnesium alloy in Figure 5-11, was used during W orld W ar II in
in place of “ goop” . (See Table 5-12.) tremendous quantities. Its hexagonal shape adapted
it to assembly in clusters for shipping and loading
5-4.2.2.3 Other Incendiaries on planes. After dropping from the planes the
Phosphorus and its compounds have been used bombs were separated from the clusters and widely
as an incendiary against personnel and readily- dispersed in random manner. The explosive charge .
lgnitiole materials. Burning phosphorus produces in the h »ee w ns e x p lo d e d by the heat, providing a
serious skin burns and tends to demoralize attacked deterrent to fighting the fire. Only a portion of

5-28

\
\
 AMCP 706-185

the bombs had the high explosive charge; the ofhers

were constructed as shown in Figure 5-12.
A “ fire bomb” using napalm-thickened gaso­
line as the incendiary filling is illustrated in Figure
5-13. An incendiary grenade, suitable either for
combat use or for destruction of materiel,. is
illustrated in Figure 5-14. It is loaded with a
S H EE T STEEL
thermate, and is provided with an igniting charge, TAIL SECTION

specified as first fire mixture. FIRING PIN

FIRING PIN HOLOER

5-5 D ELAY COMPOSITIONS AND HEAT
POW DERS
Gasless pyrotechnic mixtures are used for pro­
ducing a icon trolled amount of heat and for time
delays in a number of military applications. These
compositions, which are physical mixtures of cer­
tain metals with one or more powdered oxidizing
agents, react at a predetermined rate when igiited
by the application of heat or flame. Their com­
bustion is characterized by high reaction tem pera­
tures and the formation of mainly solid products,
Both the burning rate and calorific output can be
varied over fairly wide ranges by controlling the
properties and proportions of the ingredients. TH ERM ATE
Since little gas is produced by the combustion of
these mixtures, atmospheric oxygen is not required
for combustion, and the reaction rate is not greatly
influenced by pressure; .“ gasless” compositions
are particularly valuable for use in armament,
e.g., in short delay.bomb fuzes. IR O N NOSE

5-5.1 PYROTECHNIC D ELAYS

Some ordnance items are more effective if
functioning is delayed for an interval of time
Figure 5-11. Four-Pound M agnesium A llo y Incendiary
the initiating, stimulus. While a variety of me­
Bomb
chanical and electrical devices29 have beed em­
ployed for this purpose, a time delay caln be
obtained; by incorporating a pyrotechnic Idelay device consisting of an initiator, delay column,
element into an explosive train. The time delay, and an output terminal charge or relay; all as­
in this case, depends on the length and raite of sembled into a specially designed inert housing.
burning of the delay composition. Time delays In some designs, one or more o f these components
can also be obtained by controlling the rate of heat may be omitted. In some cases, depending on the
flow through a thermal barrier , 30 or by the rupture application and delay composition, the delay ele- *
o f a barrier by the build-up o f gas pressure.3 1 ment may also include baffles, a housing, and pro­
•» . vision for an internal free volume. Based on their
5-5.1.1 I)elay Elements i construction, pyrotechnic delays can be subdivided
A delay element is a self-contained pyrotechnic into two general types, obturated or vented.29

5-29
 AMCP 706-185

5-5.1.1.2 Vented Delay Elements80,82

Vented delay elements have openings through
which the gases produced by the functioning may
escape. Vented delays are used when large quan­
tities of gas are produced by the burning of the
delay powder and may even be necessary for “ gas­
less” mixtures when long delay times are required
in order to eliminate pressure buildup within the
delay element. Venting exposes the burning delay
composition to ambient pressure. As a conse­
quence, the burning rate of the delay mixture is sen­
sitive to changes in altitude. In addition, these
vents require sealing up to the time of functioning
in order to protect the delay composition from
humidity. Two methods for sealing vented delays
are illustrated in Figure 5-16.
Another vented delay is the time ring which
consists, as shown in Figure 5-17, o f a column of
fuze powder which is pressed into the fuze cavity.
Because of its construction, the ring delay occu­
pies a large part of the total fuze volume. With a
ring delay the delay time can be set to any desired
value within its time range by rotating a calibrated
ring which varies the length of the delay train that
must be burned before the terminal charge func­
tions.

5-5.1.2 Delay Compositions

The delay compositions, being a critical part
of the delay element, should ideally have certain
characteristics which may be summarized as fol­
lows :
5-5.1.1.1 Obturated Delay Elements a. The ingredients should be stable and non­
An obturated delay element, as shown in Figure hygroscopic; should have the highest purity con­
5-15, is constructed to contain all of the gases pro­ sistent with requirements; should be readily avail­
duced by the functioning o f the initiator and delay able and inexpensive; and should be compatible
composition before the functioning of the terminal with each other.
charge. Delays in which the gases produced are b. The compositions should be capable o f being
internally vented into a closed chamber in the ex­ blended, loaded, and assembled into an item with
plosive device are considered to be obturated. minimum risk from impact, friction, moisture, heat,
Because they are sealed, obturated delays are not and electrical discharge.
influenced by the effects o f the ambient pressure c. They should be readily ignitible, and should
or humidity. The combustion products are con­ change little in performance characteristics with
tained which prevents possible harm to other com­ small changes in percentages of ingredients. Their
ponents of the device. Short time delays are often burning rates should be reproducible within each
obturated as obturation tends to increase the aver­ batch and from batch to batch with a minimum
age burning rate of the delay composition. of variation.

5-30
 AMCP 706-185

Figure 5-73. Typical N apalm Bomb

d. They should be compatible with their con uted largely to its good dry surveillance character­
tainer fas well as with other contacting composi istics, its ease of ignition, its wide availability in
tions. Performance characteristics shoqld not. reproducible quality and granulation, its ease of
change appreciably with long term storage loading, and its versatility from the standpoint of
e. They should be relatively insensitive to delay times obtainable.
changes in pressure and temperature. As already indicated, black powder produces
f. They should be capable of withstanding the gases on burning, and the burning rate is affected
vibration and shock of transportation, setback, ro­ by pressure. Hence, the disposition of the gases is
tation, and impact, and should be resistant to a primary consideration in design; delay elements
physical abuse inherent in the loading, an d firing using black powder are generally vented. The
of ammunition. ' burning rate of black powder is affected by the ro­
tational si>eed of the projectile and by the ambient
5-5.1.2.1 Black Powder Delays t pressure1. A major shortcoming of black powder
Black powder has been long and widely used has been and still is its marked hygroscopicity.
as a delay material in spite o f the fact that it does As has been indicated earlier, because of these un­
not meet many o f the ideal characteristics for a desirables, gasless delay compositions were de­
delay composition. This popularity may be attrib­ veloped.

5-31
 !

AMCP 706-185

Figure 5-15. O b tu ra te d D elay Element

5-5.1.3 Factors Affecting Performance88

5-5.1.2.2 Typical Gasless Compositions The propagative burning o f a pressed column
The gasless pyrotechnic mixtures which have of a gasless delay composition is a combustion re­
been reasonably satisfactory for delays are given action in which the fuel and oxidizer react to give
in Table 5-13. Different burning rates can be ob­ essentially solid products. The gases formed con­
tained by selecting a specific composition or by sist mainly of hydrogen, water, nitrogen, carbon
varying the proportions of ingredients in a ,com­ monoxide, carbon dioxide, and traces of organic
position. materials. 37 These gaseous products are produced
The burning rates obtained with these com­ as a result of the presence of impurities or for
positions are given in Table 5-14. Under controlled other reasons not directly related to the primary
laboratory conditions, the coefficient of variation reaction. The observed velocities of the reaction
o f most o f the compositions listed is three percent -have been justified; however, quantitative agree­
or less. Lot-to-lot variability may be compensated ment was purely on the basis of thermal flow. 88'89
by adjusting the length o f the delay column for Questions have been raised concerning the de­
each new lot of delay composition or by adding tails o f burning of gasless delay compositions.
appropriate ingredients and remixing to speed up For some compositions, there is evidence that the
or slow down the mixture. Variation may be con­ formation of a, gaseous phase plays an important
trolled by use of standardized raw materials and part in the overall reaction mechanism while con­
preparation procedures. densed phase reactions are important in the pre-

i -
5-32

v ■
X
 METHOD A METHOD B
Figure 5-16. Sealing o f Vented D elay Element

ignition reactions. 8 8 4 0 -4 1 4 2 ,4 8 D TA and TGA 5-5.1.3.1 Composition

studies of the ingredients in barium chromate- There are a large number of exothermal reac­
boron delay compositions do not, however, indicate tions between inorganic solids which yield little or
the formation of a gaseous phase before ignition no gaseous products. However, most of the reac­
o f the composition, 44 and that a gaseous phase may tions are not satisfactory for one or more o f the
not be important, at least in this particular reac­ following reasons:
tion. a. Erratic burning rates
In some cases the effectiveness of an explosive b. Large column diameter required for reliable
train depends greatly on the accuracy of the time propagation
delay produced by the burning of a delay column. c. Large temperature coefficient o f burning rate
While it is possible under controlled laboiatory d. Failure at low temperatures
conditions to obtain coefficients of variation (Para­ e. Hygroscopicity
graph 5-5.1.2.2), less than three percent for many f. Rapid deterioration
delay mixtures, the effect of ambient conditions g. Unavailability of reproducible supply of raw
and manufacturing variation in many canes is materials
somewhat less than desirable. Factors which may h. Large pressure coefficient of burning rate
influence the accuracy o f a gasless pyrotechnic i. Failure at low pressure
include:
Reactions which were studied are summarized
a. Composition and Quantity o f Charge in Table 5-15.24 Under the standardized conditions
b. External Pressure for these tests, it was found that for each oxidiz­
c. External Temperature ing agent used, very fast burning times were ob­
d. Terminal Charge tained with magnesium, aluminum, zirconium, and
e. Particle Size . titanium. Slower burning times were obtained with
f. Ignition silicon, manganese, and chromium; while still slow­
g. Column Diameter er ones occurred with iron, tungsten, and others.
h. Loading Pressure Metals which gave fast burning times with silver
i. Housing Material oxide, silver chromate, barium peroxide, and lead
j. Acceleration chromate gave slower burning times with cuprous
k. Storage oxide, barium chromate, and iron oxide.
l. Processing ' The variation in burning rate for the barium

5-33
 AMCP 706-185

TABLE 5-13
GASLESS D ELAY COMPOSITIONS IN CURRENT USE 88-8*-88-80-8 1

Fuel, % Oxidants, % Inert, %

Manganese Barium Chromate Lead Chromate None

30 to 45 0 to 40 26 to 55

Boron Barium Chromate Chromic Oxide None

4 to 11 89 to 96 —
13 to 15 40 to 44 41 to 46

Nickel-Zirconium Barium Chromate Potassium Perchlorate None

Alloy 26 60 n 14

Nickel-Zirconium Barium Chromate Potassium Perchlorate None

Mix
5/31 22 42
5/17 70 8

Tungsten Barium Chromate Potassium Perchlorate Diatomaceous earth

27 to 39 59 to 46 9.6 5 to 12
39 to 87 46 to 5 4.8 3 to . 1 0
20 to 50 70 to 40 10

Molybdenum Barium Chromate Potassium Perchlorate

20 to 30 70 to 60 10

Silicon Red Lead Diatomaceous earth

20 80 Max 8 parts
by weight
Zirconium Lead Dioxide
28 , 72

chromate-boron system as the percentage of boron 5-18,88 indicates that compositions with less than
in the composition was increased to 50 percent is 1 1 percent boron burn slower than those contain­

summarized in Table 5-16.88 As indicated by the ing more than 13 percent boron when the amount
data presented in this table, a sharp drop in burn­ of heat evolved is the same.
ing time is obtained initially as the percentage of
boron is increased. A t approximately 10 percent 5-5.1.3. 2 External Pressure
boron, the burning rate levels off and remains near­
As shown in Figure 5-19 for a 95.4% barium
ly constant to approximately 25 percent boron,
chromate-4.6% boron composition, an increase in
when it begins to decrease quite rapidly. The
the external pressure resulted in a decrease in
heat o f reaction reaches a maximum at approxi­
burning times (an increase in burning rate). The
mately 13 percent boron, which is a somewhat lower
relationship is hyperbolic and can be represented
percentage than that composition (19 percent)
by an equation of the form :
producing the maximum burning rate. A plot of
total heat evolved against burning times, Figure t = ap* (5-11)

5 -3 4
 AMCP 706-185

TABLE 5-14
BURNING RATES OF G ASLESS D ELAY COMPOSITIONS 88’ 86-8 1 8 2

Inverse Burning Bate,

Composition ■ sec/in.

BaCrO i/B (amorphous) 0.5-3 5

95/5 1.5
90/10 0.6
BaCr 0 4 /B (crystalline) 9-12.5
BaCr O4 /KCIO 4 /Zr-N i (70-30) /Zr-Ni (30-70) 3- 11
60/14/9 (7 0-30)/17 (30-70) 6
60/14/3 (70-30)/23 (30-70) 11 .
BaCr 0 4 /P bC r 0 4/M n i 2.5-12.5
30/37/33 9.45
35/33/42 12.5
Red Lead/Si/Celite 4- 11
80/20/3 to 7 added
Z r/N i/B a C r 0 4 /K C 1 0 4
5/31/42 /22 6.5
5 /1 7 /7 0 /8 17.5
BaOz/Se/Talc
84/16/0.5 added 2.3 (approx)
PbOa/Zr
28/72 < 0 .5
BaCr 0 2 /CraOa/B 4.5-8.5
44/41/15 4.5 (approx)
44/42/14 6.5 (approx)
BaCr 0 4 /K C 1 0 4/W
40/10/50 12.5 (approx)
60/10/30 31 (approx)
32/5/58 1

41/5/49 ' 10
58/10/27 40

where t is the burning time in seconds, p is pres­ slightly with increasing pressure above atmospher­
sure in pounds per square inch, and a and. n are ic. Results with mixtures which contained man-
constants. The numerical values o f the constants ganese, cobalt and a nickel-zirconium mixture as
are n = 0.13 and a = 2.52 for the 95.4/4.6 barium the fuel indicated that a change in composition
chromate-boron composition. : * of the atmosphere did not have a significant effect
No significant change was found, see Figure on the burning rate. 48 ■ “ .
5-19, in the burning times for a 90/10 and 81/19
barium chromate-boron composition for pressures 5-5.1.3.3 External Temperature
less than atmospheric. f As shown in Figure 5-20, the burning times for
Results obtained with other delay mixtures also delay compositions were found to decrease with
indicated that the burning rate would increase increasing temperature. For 90/10 barium chro­
* 8 rounds not ignited. mate-boron, a plot of burning rate against the

5-85
AMCP 706-185
!|

I TABLE 5-15
H EATS OF REACTION OF INORGANIC MIXTURES
CONSIDERED FOR DELAYS

Silver O xid e Silrer Ih rov w te Barium P eroxid e Lea d Chrom ate C u p rou s O xide Barium C hrom ate Iron Oir
M eta ls - A / / 0 - A H ° / n - A H° -A H ° /n - A H ° - A W 7 n - A H 0 —A H ° /n - A H 0 —AH °/n - A H° —A H °/n - A H 0 —A.

MAGNESIUM 139.1 69.6(1) 688.5 68.9(1) 126.7 63.4(1) 560.7 56.1(1) 103.6 61.8(5) 292.9 48.8(6) 239.8 40.0
ALUMINUM 378.0 63.0 1869.0 62.3 340.6 56.8(1) 1485.6 49.5 271.5 45.3 253.6 42.3(N) 200.6 33.4
ZIRCONIUM 244.1 61.0 1206.5 60.3 219.7 54.9fI) 950.9 47.5 173.1 43.3 483.5 40.3 377.3 31.4
TITANIUM 211.0 52.8 1041.0 52.1 186.2 46.6(1) 785.4 39.3(5) 140,0 35.0 384.2 32.0 278.0 23.2
SILCON 187.0 46.6 921 46.1(N) 164.8 41.2(1) 665.4 33.3 116.0 29.0(N) 312.2 26.0(12) 206.0 17.2(N)
MANGANESE 89.5 44.8 440.5 44.1 77.1 38.6(4) 312.7 31.3 54.0 27.0(10) 144.1 24.0(23) 91.0 16.2(N)
CHROMIUM 252 42.0(N) 1239 41.3(N) 214.8 35.8(5) 855.6 28.6 146.5 24.3 63.8 21.3 74.5 12.4
ZINC 76.5 38.3 374.5 37.5 63.9 32.0 247.7 24.8 41.0 20.5 104.6 17.4 52.0 8.7
TIN 124.1 31.0 606.5 30.3 99.3 24.8 350.9 17.5 53.1 18.3 123.5 10.3 17.8 1.4
IRON 177.5 29.6(8) 866.5 28.9(8) 140.3 23.4 483.1 16.1(11) 71.0 U.8(N) 53.1 8.9(N) 0 0
CADMIUM 58.2 29.1 284 28.4 45.8 22.9 156.2 15.6 22.7 11.4 60.2 8.4 -2 .9 -0.6
TUNGSTEN 174.7 29.1 852.5 28.4 137.5 22.9 469.1 15.6 68.2 11.4 60.3 8.4
MOLYBDENUM 155.5 25.9 759 25.2 118.3 19.7 373.1 12.4(17) 49.0 8.2 31.1 6.2
NICKEL 50.5 25.3 250.0 25.0 39.0 19.5 122.2 12.2 15.9 8.0 29.8 5.0
COBALT 51.4 25.7 245.5 24.6,. 38.1 19.1 117.7 11.8 15.0 7.5 27.1 4.5
ANTIMONY 145 24.2 704.0 23.5(10) 107.8 18.0(6) 320.6 10.7 38.5 6.4 20.6 3.4
BISMUTH 116.1 19.4 544.0 18.1 78.9 13.2 176.1 6.9 9.6 1.6 -8.8 -1 .4
COPPER 31.5 15.8 150.5 15.1 16.4 8.2 22.7 2.3 -29.9 -5.0

NONM ETALS
PHOSPHORUS 195 39(1) 192.4 38.5(1) 487.6 48.8(1) 128.4 25.7(2) 213 21.3 652.8 18.4(6) 36.3 7.1(16)
SULFUR 142.1 23.7 682.5 22.8(4) 158.2 26.4(4) 101.2 16.9(9) 95.9 4.8 28.8 4.8 -15.1 -0.6
SELENIUM 67.6 11.3 311.5 10.4 86.6 14.4 31.3 5.2 -0.2 -0.3

- A H " HEAT OF REACTION'.

—AH °/n EQUIVALENT HEAT OF REACTION (HEAT OF REACTION PER ELECTRON CHARGE).
(N) NO REACTION OBSERVED. ,
(I) VERY FAST BURNING RATE.
( ) BURNING TIME, SECONDS

logarithm of the absolute temperature results in a The magnitude of this reduction in burning time
straight line. For the 95.4/4.6 compositions, this for several barium chromate-boron compositions
is also true for most of the temperature range; ' is a function of the burning rate of the composi­
however, for some 95.4/4.6 compositions, there is tion. (See Table 5-17.) As shown in Table 5-18 the
a departure from this type of relationship at the reduction in burning rate is less for the more
lower temperatures. Over the narrower tempera­ rapid burning compositions. Obturation of the
ture range ( —60°F to 160°F), the burning rate is delay column substantially increases the magni­
essentially a linear function o f the logJ0 tempera- tude of the anticipatory effect. The anticipatory
effect is reduced by barriers, between the delay
column and the thermally-sensitive terminal
5-5.1,3.4 Terminal Charge, Anticipatory Effect46 charge, which would reduce the flow of gases. The
The burning characteristics of pressed delay importance of gas permeation in the burning of
compositions are different when loaded above a pressed delay compositions is indicated.
thermally-sensitive terminal charge. The overall
burning time and the reproducibility are both de­ 5-5.1.3.5 Particle Size
creased under these conditions. This anticipatory The effect of particle size on the inverse burn­
effect has been observed with a variety of thermal­ ing rates of delay compositions follow a nearly
ly-sensitive terminal charges for both gaseous and direct proportionality. In addition to increasing
nongaseous delay compositions. The effect has also the. burning rate, reduction of the particle size
been observed for typical end item delay elements tends to reduce the effects of temperature and
having a lead styphnate-lead azide relay. pressure. This effect is shown to a marked degree
The extent of the reduction in burning time by tungsten delay compositions, as is shown in
that occurs with delay elements having thermally- Table 5-19. Although the percentage compositions
sensitive terminal charges, compared with similarly are not identical, they are close enough that little
pressed delay columns without a terminal charge, difference in burning time would be observed if the
approaches a constant value as the length of the tungsten fuel had' the same surface area. • The
delay column above the terminal charge increases. weight, average diameter, and the surface area

5-36
 AMCP 706-185

TABLE 5-16
E FFE C T OF PERCENT COMPOSITION ON BURNING TIME,
H EAT OF REACTION, AND IM PACT VALUES
. OF TH E BARIUM |CHROMATE-BORON SYSTEM

N o. H eat o f Reaction
Results Total Im pact
Charge A vg and Burning Range, Volume Cal in Test
W t, Range Tim e, Range, sec/sec gas Loaded PA,
% B oron mg Based on |sec - sec B .T . Cal/g rrd/g Fuze Cal/sec inches

3 .0 % 2130 5 ■jf.56 0.469 0.620 Incomplete reaction ' 40+

3 .5 % 2150 4 3.54 0 070 0.020 278 5.0 597 169 40+
4 .0 % 2140 4-; 1.72 0.031 0.018 354 5.0 768 446 40+
4 .6 % 2125 5' 1.44 0.040 0.028 400 4.0 850 590 39
5 .0 % 2130 6v 1.09 0:035 0.032 420 8.0 895 821 40+
6 .0 % 2110 5 0.767 0.021 0.027 231 8.4 909 1186 37 ,
7 .0 % 2000 4| 0.653 0.010 0.015 453 6.4 906 1387 38
8 .0 % 2000 4 0.560 0.001 0.002 462 7.9 924 1650 28
9 .0 % 2000 4 6.539 0.002 0.004 474 7,5 948 1758 29
10.0% 1975 4, 0.465 0.015 0.032 515 7.3 - 1017 2187 21
11.0% 1925 4; 0.432 0.020 0.046 536 6.9 1032 2388 18
13.0% : 1900 4i 6.397 0.006 0.015 556 8.9 1056 2661 20
1 5.0% 1875 4! 0.382 0:027 0.071 551 7.0 1033 2704 16
17.0% ! 1800 4i 6.375 0.027 0.072 543 11.6 977 2606 13
19.0% i 1750 ' -4 i 0.366 0.021 0.057 535 8.8 936 2558 16
21.0% ‘ 1685 .4 0.375 0.007 0.019 526 8.6 886 2363 34
23.0% 1650 • 4; 0.407 0.023 0.057. 503 4.2 830 2703 40
2 5 .0 % 1625 4 0.433 0.025 0.058 497 10.2 808 1865 40+
30.0% ; .1611 4; 0.574 0.025 0.044 473 10.4 762 1328 40+
35.0% I 1500 4; 0.965 0.115 0.119 446 12.7 669 693 40+
4 0.0% 1430 4'. ll9 0.110 0.050 399 14.1 571 261 40 +
4 5 .0 % i 1360 3 6.25* 0.210 0.040 364 15.0 495 94 40 f
5 0 .0 % 1290 2 14.5* 1.000 0.069 Incomplete reaction ' 40+
1
•2 rouada not ignited

were determined on the micromerograph. Under charge of an igniter composition on top o f the
these experimental conditions, a fuel with about delay column, which is easy to ignite and is cap­
twice the surface area will have a linear burning able, in minimum quantities, of igniting the delay
time of about one-fifth o f the former. column. The complex interactions between initiat­
For the 90/10 barium chromate-boroh composi­ ing source and igniter and, in turn, igniter and
tion, the use of boron of -1, 13.5, and 53 mijjron main charge are yet to be determined. F or the
average particle size resulted in an increase in the most part, igniters have been and still are selected
inverse burning rate o f 0.45, 6.61 and 9.53 seconds on an arbitrary basis. Compositions of some of
per inch, respectively. Similar results were ob­ the ignition powders which have proved relatively
served for manganese delays.85 „ satisfactory are given; in Table 5-20. These mix­
In addition to the average particle size, the tures are also gasless.
particle size distribution and blending o f delay
mixtures is important if reproducible burning 5-5.1.3.7 Column Diameter
rates are to be obtained.47 For the barium chro­ Radial losses of heat can retard or extinguish
mate-boron composition, there appears to be little the reaction in a delay column. Such losses be­
difference ‘ between delay mixtures produced by come more serious as the column diameter, burn­
wet and dry blending methods. W et blending is ing rate, and ambient temperature are reduced.
preferred for safety reasons. These effects combine to result in a failure diam­
eter associated with a given delay mix for a given
5-5.1.3.6 Ignition Compositions ambient condition. For manganese delay compo­
Some gasless delay compositions are difficult sitions at —65°F, the failure diameter for a three-
to ignite. It is the usual practice to press a small second per inch composition is less than 0.109 inch;

5-37
AMCP 706-185

TABLE 5-17
E X TE N T OF ANTICIPATORY EFFECT AS A FUNCTION OF
BURNING R A TE OF VARIOUS BARIUM CHROMATE-BORON

Average Burning Time, msec

95/5 90/10 86/14

Delay composition alone 464 167 132

Delay composition above terminally
pressed 100-mg increment o f SI-98 158 124 116
Burning time reduction, msec 306" ~ "1 5 "

SI-98 squibs were empolyed for initiation of columns. Oomposition loaded in M112 fuze
housings at 36,000 psi.
SI-98 Composition:
Mo08— 26%
KC104— 21%
Zr— 53%

STAB PRIMER AND

BLACK POWDER
STARTING CHARGE

BLACK POWDER
TRANSFER PELLETS

BLACK POWDER
RING OR TRAIN

FELT WASHERS

BLACK POWDER
BOOSTER (LOOSE
LOADED)

Figure 5-78. T o ta l Heat Evolved Versus Burning Time o f

Binary Barium C hrom ate-Boron Compositions Loaded to a
H eight o f 0.79 Inch in M112 Fuze Housing a t 3 6 ,0 0 0 psi

that of a ten-second per inch mix is between 0.125

and 0.156 inch, while for a 12.5-second per inch
composition, the failure diameter is between 0.156
and 0.203 inch. As shown in Table 5-21, the effect
o f column diameter, was found to be significant for
all 95/5 barium chromate-boron delay systems and
for obturated 90/10 barium chromate-boron de­
SECTION X - X lays.48

Oohy Typo: Hint ** Irein/ Vontod/ Without Bofflo, ; 5-5.1.3.8 Loading Pressure
Tlmt Sohttioo/ 1 to 81 .
Loodlny: Burning rates o f delay mixtures will decrease
Upper J.18S Gromt.
Lower fttaf— J.640 Gtomt. as the consolidation pressure increases. The rather
A-? Block Powder, looded In Woct M Staff* Increment of 68*000 ptl.
small and systematic changes with loading pres­
Figure 5-77. Time D elay Ring o r Train, Vented sure for barium chromate-boron composition are

5-38
 AM CP 706-185

TABLE 5-18
EXTENT OF ANTICIPATORY EFFECT AS A FUNCTION OF
COLUMN LENGTH 55/35/10 TUNGSTEN-BARIUM CHROMATE-
POTASSIUM CHROMATE COMPOSITION*

' ’ Average Burning

Burning Time Length of
Time,*** Range, Percent A Burning % Column Column
msec msec Range Time By-passed By-passed, in

One 1000-mg increment

Without terminal charge 2348 411 ■ 18
W ith terminal charge** 1473 462 31 875 37 0.07

Two 1000-mg increments

Without terminal charge 4291 259 6 .
With terminal charge 3404 583 17 887 21 0.09

Three lOCjO-mg increments •

Without terminal charge 6082 328 5 15

With terminal charge 5192 1042 20 890 0.09

Four 860-mg increments

Without terminal charge 6914 337 5
With terminal charge 6173 990 16 741 11 0.08

*81-98 squibs were employed for litiation of columns. The compositions was loaded in .
M112 fuze housings at 36,000 psi.
** SI-98 terminal charges were used
*** Average burning time values ha1 ve beett reduced by 6 msec in order to take into ac-
count the burning time of the terminal charge itself.

summarized in Table 5-22.40 These effects might

be used to compensate fo r the differences in burn­
ing rate from lot to lot. However, this method has
1.40
not been used due to the established practice of
I.SO loading delays at pressures between 30,000 and
40,000 psi in order to withstand the forces to
Bumune tint, scconos

1.00
which it is subjected in use. Yielding of the delay
• OS.4% 0 « C * V 4 . 4 % i - 04-404 element while pressing the delay composition will
040 * • 5 .4 % B © C e ^ -4 B % B -0 P -4 * *
• M .4% B#CrQ,-4.6%B-OP-4BO cause erratic delay times.
• t0 % S«C»Q,- 1 0 % B -O P -4 7 *
0.00
• • !% 6 * 0 ^ - It% B -O P -B O *

040
5-5.1.3.9 Housing Material
o-to . The body into which a delay composition is
loaded serves as a heat sink, as metals in general
0.00
SO 40 SO *0 70 are much better conductors o f heat than delay
m m u K C , cm, MtftcuitY
compositions. Delay columns close to their low-
temperature failure diameters tend to have larger
F igure 5-19. Burning Time o f M i l 2 Fuze Versus External temperature coefficients as the surrounding wall
F re ttu re thickness is increased. For materials well above

5-89
AM CP 706-185

< TABLE 5-19

E F F E C T OF SPECIFIC SURFACE ON BURNING
TIM E OF TUNGSTEN D E LA Y COMPOSITIONS

Type of
Tungsten Composition M10 ND 3499

‘ Surface Area
cm2/g 1377 709
Fuel
Characteristics
Weight Average
_ Diameter, microns 2.3 4.9

Delay ' Tungsten . . . 40 38.0

Composition,
% , BaCrO* 51.8 52.0

KC10« 4.8 4.8

_ Diatomaceous E arth. 3.4 5.2

Burning Time,
sec/inch n! ' ■
' ' • 4.17 21.5

.|{<

■ ... TABLE 5-20 ,

IGNITION POW DERS FO R GASLESS D E L A Y ELEMENTS

Fuel, % Oxidants, % , Inert, %

Zirconium s Ferric Oxide Diatomaceous Earth

65 25 , 10

Boron Barium Chromate .

10 . 90 ' ' ,

Zirconium Ferric Oxide

33 50 •
Titanium
17

Zirconium Ferric Oxide Diatomaceous Earth

51 : 39 : - . ' 10

Boron : Lead Peroxide

30 70
 rw

TABLE 5-21
EFFECT OF FUZE HOUSING M ATE R IA L AND DIMENSIONS ON BURNING TIME
OF BARIUM CHROMATE-BORON COMPOSITIONS

Parameters Effect

1 . Metal Housings
a. A luminum, Brass and Stainless Steel a. No effect on burning times over test temperatures, internal
diameter, wall thickness and fo r either vented or obturated
columns.
. - . • . b. No interaction between metal and composition.
2. Internal Diameter, inch
a. OJS50 95/5 vented vs obturated a. Results for vented columns significantly different at 95% con-
< fidence level.*
. b. 0.j 75 95/5 ventedjvs obturated
--------------------------:--------b.—Resultsfoi^obturated—columnssignifieantly- differentat~ 9 5 %^
confidence level. ■ ■
c. 0.250 90/10 vented vs obturated c. No significant difference for either column at this diameter.
d. 0.375 90/10 vented vs obturated • d. Results for obturated column significantly different at 95%
confidence level.
3. Temperature, °C ”
a — 54, Room Temperature, and 76 a. The effect' o f temperature was significantly different at the
* / ■ 95% confidence level for all metals, internal diameters, wall
; , . . - thickness and for Vented and obturated columns.
4... 'Wall Thickness; in c h '(0 M , 0.15, 0.30, ' 0 . 5 0 , .
0.75, and 1.00) ' . . . ‘ : ' ■’ "
a. 95/5 vented and obturated columns a. Results for different wall thickness were significantly different,
although no apparent trend was observed.
b. 90/10 vented and obturated’ columns - b. No significant differences or trends in results due to wall thick­
......... ness for either type o f column.

AMCP 706-185
5-41

\
 AMCP 706-185
T A 3 L E 5-22
E F F E C T OF LOADING PRESSURE ON BARIUM CHROMATE-BORON COMPOSITIONS

. • -■•- - -' “ 95/3 BaCrOr B --

Loading Pressure (IQ8 psi) 36 18 9 3.6 1.3 0.5
Mean BR, sec/inch* 1.69 1.60 1.49 1.39 1.29 1 .2 1

Mean BR, sec/gram 0.648 0.655 0.645 0.642 0.646 0.693

% Coefficient o f Variation 1 .2 0 .6 0.7 0.7 0 .8 0 .8

90/10 BaCrO,»-B
.Mean BR, sec/inch 0.670 0.653 0.619 0.586 0.558 0.544
Mean BR, sec/gram 0.272 0.276 0.280 0.287 0.297 2.309
% Coefficient o f Variation 1.5 0.9 •1 . 1 . 1 .6 2 .0 1 .8

* BE = burning rate.
 AMCP 706-185

T, *K
tion or a subsequent charge and extinguish the
reaction. Quantitative data regarding the resis­
tance of delay compositions to this type o f failure
are not available. “ Slag retention,’ ’ i.e., the
fraction of the weight o f the original charge re­
maining in an open ‘ended delay column after
functioning, has been used as a possible qualitative
indication of the resistance o f a delay element
to acceleration forces. Slag retention for some
delay compositions is as follows: manganese,
> 9 5 % ; red lead, 9 0 % -9 5 % ; tungsten, > 9 5 % ;
nickel-zirconium, 80%-90% ; boron, 59%-90%.84
2.9 4 0 2.440 2 .940 2 .640 Introduction o f a binder will improve perfor­
LOO.o T, -K
mance under high acceleration conditions; how­
Figure 5 -2 0 . Burning Time o f M i l 2 Fuze C ontaining 90% ever, binders tend to produce sufficiently large
Barium fh ro m a te -1 0 % Boron C om position. Versus og- amounts of gaseous products so that the system
arithm o f Absolute Temperature could no longer be considered gaseless. Mechanical
support of the delay column at both ends tends
their failure diameters, the effect of wall thtiick- to reduce variation in burning times by minimizing
ness becomes less important. 82 As shown in Tnble slag flow. ;
5-21 for the 95/5 barium chromate-boron composi
tion, the wall thickness had a significant effect for
5-5.1.3.11 Storage
both vented and obturated items; however, the
differences observed were small and had ho ap­ The effectiveness of an item of ammunition
may depend greatly on accuracy of the delay. Be­
parent trend. No significant difference due to
cause it is necessary to store ammunition for a
wall thickness was noted for the 90/10 barium
long time, it is important to know the effect of
chromate-boron compositions. 48 :
storage on the burning times of delay compositions.
As also shown in Table 5-21, the material used
for the housing did not appreciably affect the In general, dry storage for relatively long periods
of time results in little change in burning time.
burning rate of barium chromate-boron composi­
tions. 48 . . ' ' For example, barium chromate-boron composi­
tions loaded and stored over a desiccant show little
Delay compositions have been loaded and o n -
change after time intervals up to two years, as il­
solidated into lead tubing by a swaging technique.
lustrated in Table 5-23. For loose powders stored
The accuracy of delays prepared by the lead-thbe
up to two years in unheated magazines and then
method depends on many factors associated with
loaded, a slight increase in burning time has been
the composition, application* etc. However, it
observed. Storage under dry conditions prevents
may be said that in some applications it is more
further increase in burning time and may reverse
accurate and in others less accurate than the
the trend as shown in Table 5-24.
conventional method o f filling. 48
When manganese delay mixtures are kept dry,
their burning times will not increase more than five
5-5.1.3.10 Acceleration percent during eight weeks’ storage at + 165°F .
Some mixtures containing manganese did not
Delay elements are often subjected to very high change their burning times when stored without
accelerations while the delay composition is burn­ sealing at 1 0 0 percent relative humidity and
ing, as in skip bombing. I f the structure of the 4-165°F. Other manganese mixtures deteriorate
material at or behind the reaction front is too rapidly under the same conditions. This wide
weak, the accelerations may cause the hot products variation in storage stability is due to differences
to lose contact with the unburned delay composi­ in the manganese powder used in preparing them,

5 -4 3
AM CP 706-185

TABLE 5-23
E FFE C T OF STORAGE ON FUZES LOADED W ITH
BARIUM CHROMATE-BORON COMPOSITIONS

Zero Time Stored 19 months

Mean Mean
Comp., B. T.,* % Coef. B. T .* % Coef.
% B See. Std. Dev. Var. Sec. Std. Dev. Var.

1 0 .0 0.514 0.013 • 2.5 0.515 0.025 4.9

1 0 .0 0.590 0 .0 1 2 2 .0 0.579 0 .0 1 2 2 .2

1 0 .0 0.519 0.015 3.0 0.476 - 0 .0 1 0 2 .2

1 0 .0 0.574 0.004 0 .8 0.522 0 .0 1 2 2 .2

5.0 1.590 0.015 0.9 1.587 0 .0 2 0 1.3

5.0 1.075 0.016 1.5 1.059 0.015 1.4
5.0 1.294 0.026 2 .0 2.264 0.019 1.5
5.0 0.818 0.016 2 .0 0.785 0.016 2 .0

5.0 1.192 0.036 3.0 1.277 0.016 1.3

5.0 0.986 0.033 3.4 " 0.955 0.014 1.4
M112 Fuzes loaded at 36,000 psi, stored over desiccant

* B. T. = burning time.

TABLE 5-24
BURNING TIMES OF FUZES LOADED W ITH 93/7 BARIUM
CHROMATE-BORON COMPOSITIONS STORED LOOSE
UNDER VARIOUS CONDITIONS

Initial Conditions Storage Conditions

Mean B. T.,m % Coef. Mean B. T.,* % Coef.
Sec. Var. Temp. Time Sec. Var.

150°C 4 hours 0.707 1 .1

8 hours 0.722 1 .0

0.694 2.7 105°C 1 week 0.723 1 .8

50% RH 1 week 0.720 1.5

Desiccated 1 week 0.685 1.7
0.647 2.3 150°C 4 hours 0.685 2.5
Compositions loaded in M112 Fuze Housings at 36,000 psi.

• B. T. = burning time.

and, apparently, is associated with the manganese For zirconium-nickel delays, four weeks’ dry
crystallite size and surface oxidation. Protective surveillance increases burning times up to 16 per­
treatment o f the manganese fuel against corrosion cent. Wet surveillance for four weeks results in
— oxidation o f surface by dichromation and coat­ unreliable performance. Delay compositions of
ing with a thin film of stearic acid— did not im­ silicon and red lead exhibited increased burning
prove the dry surveillance properties of manganese times of up to 1 0 percent after four weeks’ dry
delay powders but did improve the wet surveil­ surveillance and were unreliable after four weeks’
lance characteristics. ' ■ wet surveillance.

5-44
 AMCP 706-185

In general, results o f tests indicate that gasless compositions are relatively difficult to ignite, an
delays will exhibit changes of up to 15 percent in explosive train similar to that used in other ex­
burning times after four weeks of dry surveillance. plosively loaded items is used to produce the ig­
Wet surveillance appreciably affects per f on nance nition stimulus required to initiate the main pyro­
of most delay mixtures, in some cases sufficiently to technic composition. Such a train can be con­
make the mixture unreliable. sidered as divided into three parts. The first
part contains a sensitive initiating composition
5-5.2 HEAT POWDERS80 that can be initiated by a relatively small, me­
chanical, electrical, or chemical stimulus. This
The majority of pyrotechnic heat powders have
initiating composition, on burning, produces suffi­
been developed for thermal battery applications
cient heat to initiate intermediate explosive or
to melt the solid electrolyte and activate the electro­
pyrotechnic composition (s) in the second part
chemical system. In general, the heat powder—
of the explosive train. The output o f this second
which generates between 350 and 500 calories per
part will initiate the main charge in the third part
gram— is mixed with inorganic fibers and made
o f the explosive train . 29 -8 1 '8 2 In many cases, a de­
into heat paper using conventional paper miking
lay train (see Paragraph 5-5.1) can be included
techniques. The heat paper can be stamped into
in the second part of an explosive train. Emphasis
required shapes and easily assembled with the other
in the following paragraphs will be on initiator,
battery components. Other uses include warming
first fire, and starter compositions used in pyro­
of battery electrolytes, melting o f soldered joints
technic items.
to activate spring loaded mechanisms, and furnish­
Work on the development of initiators, first
ing heat for thermal delays. Many gasless heat
fires and starters for military pyrotechnics has in­
powders and gasless delay compositions can be
dicated that ignition is a complex phenomenon.
used interchangeably; however, the electrical con­
Ignition failures of pyrotechnic items emphasized
ductivity o f the products formed during burning
the need for more research and the need for more
is important in the ability of heat powders to satis­
understanding of the ignition and combustion
factorily perform their function.
processes. The available compositions, with de­
The heat output of a heat powder is of prime
scriptions of their applications, are discussed in the
significance and the burning rate is important only
paragraphs which follow.
to the extent of its influence on the heat output of
the mixture. Other important characteristics; in­
clude : 5-6.1 PRIME IGNITION80

a. Heat of reaction. Basically determines the Prime ignition is the starting of a fire without
heat output per unit weight of heat powder. the use of another fire and includes methods based
b. Gas evolution. The gases evolved mus ; be on friction, percussion, concentration of the sun’s
controlled because it is possible they will affect rays by mirrors or lenses, and an electric impulse.
the behavior of the heat battery. Many materials and mixtures o f materials
c. Burning rate. Basically determines the rate have been found which produce heat as a result
o f heat release by the heat mixture powder. (The of chemical reaction and which require relatively
burning rate o f heat paper has been suggested as little physical effort for initiation. Chemicals, such
a means of obtaining a controlled delay time.) as white phosphorus and phosphorus-containing
compounds, burst into flame on exposure to air.
Other materials, including many metals which com­
5-6 INITIATORS, FIRST FIRES, AND monly will not ignite in air, become pyrophoric
STARTERS when finely ground; while other materials are acti­
The initiation of combustion o f a pyrotechnic vated by exposure to water or acid, to a spark
composition requires that a portion of the comp osi­ with a small energy content, or to very slight im­
tion be raised to its ignition temperature. (See pact. Still other mixtures require only a small and
also Paragraph 3-3.6.1.) Since some pyrotechnic predictable amount o f energy to be initiated. This

5-45
 AM CF 705-183

last group, which includes mutches, is of im­ airplane flare contains 14 parts potassium chlorate
portance as initiators for ordnance items. and 1.6 parts charcoal hardened with 0.3 part
Development of modern matches made fire­ dextrin. Ignition is effected by pulling a loop of
making a commonplace act. A safety match head is, braided wire coated with red phosphorus and
essentially, potassium chlorate in a matrix of shellac through a pellet o f the composition.5 1 Modi­
animal glue. The striking strip is composed of red fied scratch sensitive mixtures containing some
phosphorus in a similar binder. 1 'se of additives thermite produces very high temperatures and can
and adjustments in the manufacturing process ignite some smoke mixtures without an intermedi­
results in a safety match which ignites easily when ate starter. 8
. rubbed on the striking surface. The friction and In addition to matches and other scratch sensi­
contact of potassium chlorate crystals with red tive materials, prime ignition of pyrotechnic muni­
phosphorus results in the ignition of the match tions, like other munitions, is accomplished w ith:
head which, in turn, causes the ignition of paraffin a. Percussion (or stab) primer which contains
impregnated in the match splint. A typical match a mixture that is relatively sensitive to impact and
head formula, and that for the striker, are given friction, or ^
in Tables 5-25 and 5-26.50 b. Electrically ignited primer (or squib) in
which the heat produced by the flow of electric
TABLE 5-25 current in a bridgewire ignites a heat sensitive
COMMERCIAL explosive. For certain applications, especially
S A F E T Y MATCH COMPOSITION* those involving initiation of high explosives, a
bridgewire may be exploded by application of a
Ingredient Percent•
high current pulse causing direct initiation of some
Animal (H ide) Glue.................................. 9-11 less-sensitive explosives.2 0 ,8 1 '8 2 '52
Extender (Starch, D extrin ). . ..................... 2-3 Certain chemical reactions have been used for
Sulfur (R o sin )................................................ 3-5 ignition of explosive trains. As has been indicated
Potassium. Chlorate........................ . *5' 55 earlier, some materials bum when exposed to air.
Neutralizer (Zinc Oxide, An example is white phosphorus. It has been used
Calcium Carbonate)............................... 45-05 in bursters for jelled gasoline incendiaries where
Infusorial (Diatomaceous) Earth................. 5-6 it serves the dual purpose o f igniting the incendi­
Other Siliceous F ille r .................................. 15-32 ary, and the reigniting jelled gasoline which has
been extinguished. Diethyl zinc, or triethyl alu­
""Fractional percentages o f a soluble burning rate
minum, contained in a glass vial, has been used
catalyst, such as potassium dichromate, are added, also
soluble dye stuffs. Lead thiosulfate or zinc ferrocyanide to ignite a match mix in a silent igniter. Some
can be used i f the match head is to be white. materials, notably the alkali metals, react very
Present “ strike-anywhere ” (S A W ) matches vigorously with water, liberating hydrogen which
have a small, easily ignitible tip composed of is ignited by the heat of reaction. Bursters filled
tetraphosphorus trisulfide (phosphorus sesquisul- with sodium have been considered for igniting oil
fide) affixed to a larger bulb composed of a rather slicks on water. 8 The vigorous chemical reaction
resulting from bringing iron powder, potassium
insensitive modified, safety match head composi­
tion. Table 5-27 gives the formulation for two such permanganate, and sulfuric acid together is an­
other method of prime ignition.
compositions. 50
„ The match mixtures used in munitions are gen­
erally much less complicated in composition and 5-6.2 CHARACTERISTICS OF ID EAL
manufacture than the commercial match mixtures IGNITER, FIRST FIR E , AND
which require a special striking surface. Com- ' STARTER COMPOSITIONS
positions which have been widely used in friction The compositions used to ignite any burning-
primers for artillery are given in Table 5-28. A type pyrotechnic should have the following char­
composition used in the friction primer for an acteristics :5S •

5-46
 AM CP 706-185

t a b :LE 5-26
S A F E T Y MATCH STR IK E R COMPOSITION

formula 1, t Formula 2, t Formula 3, t

Ingredient % % %

Binder • 20 16
Red Phosphorus 53 50 50
Antimony Sulfide 42 — —

Charcoal 5 _ ■ --- '

Carbon Black ■'--- — 4
Neutralizer (ZnO, CaCOs) — — -5
Sand --- ■
30 —
Powdered Glass :--- — 25

* In NC laquer, Dextrin, Casein, Animal Glue, plus hardener o f TJ.S. Pat. 2,722,484 129.
i Formulas 1 and 2 are 1‘ one-strike ’ ' military or firework strikers. Formula 3 is a
commercial formula. Antimony sulfide and charcoal act as extenders to the phosphorus,
Antimony sulfide also seems to fulfill the role Q i a neutralizer and preservative for red
phosphorus.

TAB LE 5-27
SA W ( “ STR IK E -A N Y W H E :*E” ) MATCH COMPOSITION

Formula 1 * Formula 2*
Ingredient % %
Animal Glue 1 1 12
Extender 4 5
Paraffin — 2

Potassium Chlorate 32 37
Phosphorus Sesquisulfide (P 4 S3 ] 10 3
Sulfur — 6
Rosin 4 6
Dammar Gum — 3
Infusorial Earth — 3
Powdered Glass and Other Filljer 33 2 1 y2
Potassium Dichromate ■
— m
Zinc Oxide 6 1

• Formula 1 represents the tip formula which ignites on any hard surface. Formula 2 is
the match composition’s base, loaded with combustibles for strong billowing flame but o f low
friction sensitivity.

a. Be ignited* by the primer, fuze, or match The specific nature of the ignition composition
employed in the munition. is primarily determined by the particular ignition
b. Ignite the main pyrotechnic composition. problem since it involves the nature of the filling
c. Be sufficiently insensitive for safe handling to be ignited and the method by which the ignition
in manufacturing and loading operations. composition is ignited. The wide variety of fillings
d. Be resistant to the effect o f moisture. used in burning-type munitions makes it impossible

5-47
AM CP 706-185

TA B LE 5-28 be ignited appears to be the most practical basis

FRICTIO N PR IM E R COMPOSITIONS for differentiation of the various compositions.
Ignition compositions may be classified as those:
a. For munitions containing thermite-type fill­
Ingredient Parts by Weight
ings or illuminating compositions, the reaction
Potassium Chlorate........ ................ 56.2 44.6 should be very hot yet evolve little gas.
Antimony Sulfide............ ................ 24.6 44.6 b. For munitions containing HC smoke fillings,
Sulfur .............................. ................ 9.0 3.6 the reaction should be hot and preferably produce
Meal P ow d er.................... 3.6 some slag; some evolution o f gas is acceptable.
Ground G lass................... ................ 10.2 3.6 c. F or munitions containing colored smoke mix­
tures and toxic smoke mixtures, the reaction prod­
uct may vary from gaseous slag to highly gaseous
to develop one composition for all purposes. A
with no slag.
composition producing a slag and a high tempera­
Ignition compositions which are used as rocket
ture would be desirable for ignition of a thermite-
motor igniters are usually ignited by the output
type incendiary or most illuminating compositions,
of a black powder which was commonly used for
but would be unsatisfactory for ignition of a
this purpose, has been replaced by igniter com­
colored smoke since the high temperature would
positions composed o f a powdered metal and in­
cause flaming of the dye.
organic oxidizer.
Requirements for ignition compositions, there­
fore, must be varied depending on their use. Ig ­
nition mixtures can be classified as slag-producing 5-6.3 TY PIC A L COMPOSITIONS
or gas-producing mixtures. As some compositions The compositions of typical igniter, first fire,
produce both slag and gas, the type o f filling to and starter mixtures are given in Table 5-29.

REFERENCES

1. The Thermochemistry o f Incendiaries, NDRC 6. G. H. Custard, G. Francis, W . Schnackenberg,

Unnumbered, 2 Aug. 1943, Available at Tech­ Small Arms Incendiary Ammunition, JL Re­
nical Library, Edgewood Arsenal, as NDRC view o f the History and Development, Frank-
Mise. Pub. 308, Report of Division 11, Na­ ford Arsenal Report R -1407-3, December 1956.
tional Defense Research Committee, Office o f 7. L. Finkelstein, A. E. Gaul, Incendiaries, Vol.
Scientific Research and Development, Wash­ 18, Part I I o f History o f Research and Devel­
ington, D. C. opment o f the Chemical- Warfare Service in
2. A. T. Wilson, Development o f M O X E xplo­ World W ar II, Edgewood Arsenal, Maryland.
sives: Various Oxidants in M OX, NFOC-6, 8. S. J. Magram, Starters, Vol. 16 o f History o f
National Northern Corporation, West Han­ Research and Development o f the Chemical
over, Mass., December 1952. Warfare Service in World W ar II, Edgewood
3. R. W. Evans, Experimental Investigation of Arsenal, Maryland.
Infrared Radiating Sources, TN-9, Denver Re­ 9. W. Jost, Explosion and Combustion Processes
search Institute, Denver, Colorado, July 1961 in Oases, McGraw-Hill Book Co., Inc., N. Y .,
(D D C-AD 324 807). 1946.
4. S. Gordon, C. Campbell, “ Differential Ther­ 10. B. Lewis and G. Von Elbe, Combustion Flames
mal Analysis o f Inorganic Compounds,” An­ and Explosions o f Oases, 2nd Ed., Academic
alytical Chemistry 27, 1102 (1955). Press, Inc., N. Y., 1961.
5. A. M. Prentiss, Chemicals in War, McGraw- 11. H. F. Coward and G. W . Jones, Limits of
H ill Book Co., Inc., N. Y ., 1937. Flammability of Oases and Vapors, Bulletin
 AMCP 706-185

TABLE 5-29
SOME F IR S T F IR E , STARTER, AND IG N ITER COMPOSITIONS

Composition (Percent by weight)

A lnw iirnim 13
Boron 10
Charcoal 4
Magnesium 25
Silicon 20 25 26
Titanium 25
Zirconium 20
Zirconium Hydride 15

Barium Chromate
Barium Nitrate 50 90 75
Iron Oxide (FesO«) 25
Iron Oxide (FexOs) 25
Iron Oxide (Scale) 22
Lead Oxide (PbOa) 80
Lead Oxide (PbjOe) 35
Potassium Nitrate
Tetranitracarbizole 5
Laminae Binder 5*

•Laminae binder: Laminae 9 9 % ; liupersol 1%.

••Most of these compositions can b<i used as a loose powder mixture or with binders sueh
as celluloid, nitrocellulose or NC lacquer.

REFERENCES (cont’d)

503, Bureau o f Mines, Washington, D. C., 16. Ounfire Tests to Determine the Vulnerability
1952. of Jet-Propelled Aircraft Fuels, Report F-27-1,
12. A. G. White, “ Limits for the Propagation of Naval Proving Ground, Bureau o f Naval
Flame in Inflammable Limits,” Journal of Weapons, Washington, D. C., December 1945.
the American Chemical Society 127 (19! 55). 17. A. Stein, M. J. Torsch, Effectiveness of In­
13. G. Von Elbe, B. Lewis, Papers presentee l at cendiary Ammunition Against Aircraft Fuel
Third Symposium on Combustion and Flim e ■■Tanks, BRL Memorandum Report 484, Aber­
and Explosion Phenomena, held at University deen Proving Ground, Md., 1948 (D D C-ATI
o f Wisconsin, Sept. 7-11,1947, with Bureau of 42 383).
Mines, Pittsburgh, Pa. 18. A. J. Metzler, Minimum Spark Ignition Ener­
14. G. W . Jones, Research on Flammability Char­ gies of 12 Pure Fuels at Atmospheric and Re­
acteristics of Aircraft Fuels, Progress Report duced Pressure, NACA-RME53H31, National
No. 5, Bureau o f Mines, Pittsburgh, Pa., Advisory Committee for Aeronautics, Wash­
March 1951 ington, D. C., 1953.
15. Science of Petroleum, IV , Oxford Unviersity 19. G . W . Bauserman, An Instrument for De­
Press, 19$8. termination of Transient Flame Temperatures,

5-49
AMCP 706-185

REFERENCES (cont’ d)
Phase Report No. 4, Denver Research Insti­ 33. B. Werbel, S. Lopatin, Development of Delay
tute, Denver, Colorado, 1952. Powders, Picatinny Arsenal Technical Report
20. Thermite, Plain, Incendiary, CWS Formula 2477, Picatinny Arsenal, Dover, N. J., 1958.
No. D-l-1, 19 August 1944 (CW S Formulary, 34. M. F. Murphy, A Comparative Study of Five
Technical Command, Edgewood Arsenal, 1 Pyrotechnic Delay Compositions, NAVORD-
September 1945), Edgewood Arsenal, Mary­ 5671, Naval Ordnance Laboratory, Bureau of
land. Naval Weapons, Washington, D. C., 1958.
21. A Solidified Oil Incendiary, ETF-182-1, Massa­ 35. M.'F. Murphy, Current Topics in Gasless Heat
chusetts Institute o f Technology, Cambridge, Powder Work at NOL, Speech before NOL
Massachusetts. Pyrotechnic Symposium, Naval Ordnance Lab­
22. D. Hart, Oasless Powders for Delay Elements oratory, Bureau o f Naval Weapons, Washing­
o f Fuzes, Picatinny Arsenal Technical Report ton, D. C., 1959.
1239, Picatinny Arsenal, Dover, N. J., 1943. 36. R. H. Comyn, Pyrotechnic Research at DOFL.
23. S. Sage, Manufacture of Barium Chromate Part II. Pyrotechnic Delays, TR-1015, Harry
Delay Powder on a Semi-Plant Scale, Pica­ Diamond Laboratories, Washington, D. C.
tinny Arsenal Technical Report 1432, Pica- 37. P. Rochlin, Mass Spectrometric Analysis of
,tinny Arsenal, Dover, N. J., 1944. Gaseous Combustion Products from Delay
24. D. Hart, Delay Compositions, Research and Powders, Picatinny Arsenal Technical Report
Development Lecture 27, Picatinny Arsenal, 2006, Picatinny Arsenal, Dover, N. J., 1954.
Dover, N. J., 1956. 38. R. A. W. Hill, T. L. Cottrell, “ Studies of
25. C. A. Poppendieck, Research on Heat-Pro­ Combustion Waves in Solids,” Fourth Sym­
ducing Compositions, First Quarterly Report, posium (International) on Combustion, The
Contract DA-36-039-SC-75071, Catalyst Re­ Williams and Wilkins Company, Baltimore,
search Corporation, Baltimore, Md., 1958. Md., 1963.
26. L. Apostolos, Powder Plate Development, Cat­ 39. J. E. Spice, L. A. K. Staveley, “ The Propaga­
alyst Research Corporation, Baltimore, Md., tion of Exothermic Reactions in Solid Systems,
1953. Part I. Preignition Reactions. Part II. Heats
27. Apparatus for Testing Pulp and Paper, Bulle­ of Reaction and Rates of Burning,” Journal
tin V II, Williams Apparatus Company, Wa­ of the Society of Chemical Industry 68, 313­
tertown, N. Y. 19, 348-55 (1949).
28. R. H. Comyn, Pyrotechnic Research at DOFL. 40. S. Nakahara, “ Studies on Delay Powders, I.
* Part I. Heat Source Materials, Technical Re­ Measurement of Temperature o f Combustion
port 884, Harry Diamond Laboratories, Wash­ of Delay Powders, ’ ’ Industrial Explosives So­
ington, D. C., 1960 (DDC-AD 321 045). ciety Journal, 1958.
29. AMCP 706-210, Engineering Design Hand­ 41. S. Nakahara, T. Hikita, “ Studies on Delay
book, Fuzes, General and Mechanical. Powders, II. The Combustion Pressure of De­
30. R. H. Comyn, The Use of Gasless Mixtures for lay Powders,” Industrial Explosives Society
Producing Controlled Time Delays in Ord­ Journal, 1958.
nance Devices, D O FL Report 22-576, Harry 42. S. Nakahara, T. Hikita, “ Studies on Delay
Diamond Laboratories, Washington, D. C., Powders, III. On Mechanism o f Delay Pow­
1957. ders,” Industrial Explosives Society Journal,
31. Ordnance Explosive Train Designers Hand­ 1958.
book, R - l l l l , Naval Ordnance Laboratory, 43. S. Nakahara, “ Studies on Delay Powders,
Bureau of Naval Weapons, Washington, D. C., IV. Theory o f Combustion Propagation Ve­
1952. locity o f Delay Powders,” Industrial Explo­
32. AMCP 706-179, Engineering Design Hand­ sives Society Journal, 1958.
book, Explosive Trains. 44. S. ‘ Gordon, E. D. Crane, Compilation and

5-50
 AMCP 706-185

REFER ENCES (cont’ d)

Evaluation of the Ignition Temperature Pa­ Sands Proving Ground, November 17, 1959,
rameters and Differential Thermal Analysis Picatinny Arsenal, Dover, N. J.
for Pyrotechnic Systems. 1. Barium Chromate 49. The Application of Lead Tubing to the Filling
Boron,' Picatinny Arsenal Technical ’ Note 24, of Pyrotechnic Delays, Branch Memo X 4 /3 /5 8 ,
Picatinny Arsenal, Dover, N. J. ■ Armament Research and Development Estab­
45. R. Comyn, R. Skelton, Effect of Pressure on lishment, Ministry of Supply, Great Britain.
the Burning Rate of Gasless Delays, NAVOIJD- 50. H. Ellern, Modern Pyrotechnics, Chemical
1787, Naval Ordnance Laboratory, Bureau of Publishing Co., 1961.
Naval Weapons, Washington, D. C. 51. K. L. Davis, Chemistry of Powder and E x ­
46. M. Gilford, B. Werbel, G. Weingarten, L. Key, plosives, John W iley & Sons, N. Y., 1943.
The Anticipating Effect. A Study of the Burn­ 52. R. C. Maninger, Background of Exploding
ing Mechanism of Delay-Relay Columns, Pisa- Bridgewire and Conventional Systems, Pre­
tinny Arsenal Technical Report 3047, Pisa- sented at American Ordnance Association
tinny Arsenal, Dover, N. J., 1964. Joint Technical Meeting on Exploding Bridge-
47. R. E. McIntyre, Factors Affecting the Blend­ wire Systems, Los Angeles, California, Febru­
ing of Gasless Mixtures, TP-648, Harry Dia­ ary 10-11, 1964.
mond Laboratories, Washington, D. C., 1959. 53. S. J. Magram, A Survey of Starters for Burn­
48. B. Werbel, Recent Advances in Pyrotechnic ing Type Munitions, TDMR-655, Edgewood
Delay Compositions, Speech presented at White Arsenal, Maryland.
i
 m
AMCP 706-185

CHAPTER 6

PRODUCTION OF LIGHT

6-1 HISTORICAL SUMMARY prepared in 1786 and first mentioned as an in­

Military pyrotechnic items used for illumina­ gredient in a pyrotechnic composition in 1823.®
tion and signaling by the military share a com­ By 1830 several formulas containing potassium
mon origin with the spectacular white and colored chlorate had been developed for firework display,
flames produced by fireworks. Tracing the de­ military signaling and signaling at sea. While
velopment o f these compositions is relatively easy most colors could be produced in a more or less
since there was little progress made in the develop­ satisfactory manner by 1850, it was several years
ment o f flame producing compositions until the later before a satisfactory blue flame was pro­
introduction o f potassium chlorate pyrotechnic duced. This was accomplished by adding copper
mixtures near the end of the 18th century.1 salts to compositions containing potassium chlorate.
The color was enriched by the use o f calomel,
6-1.1 CONSOLIDATED ILLUM1NANTS Hg2Cl2. During this period colored flames pro­
duced by adding color-emitting salts to potas­
6-1.1.1 Flares and Signals sium chlorate and sulfur compositions were found
Modern fireworks, with a few exceptions, can to be very satisfactory. In spite of their good color
be dividied into two types, those designed t!o pro-, quality, these compositions were abandoned be­
duce force and sparks, and those producing a cause o f their sensitivity to impact and friction.
flame.1,2 Early efforts were directed toward the Sulfur was replaced first by powdered shellac and
development o f spark and force producing com­ later by other gums and resins.
positions. A t that time, there was no known way Magnesium was first produced on a commercial
o f imparting color to a flame. As a result there scale in 1860 and was used by European pyrotech-
was little difference to the eye between a flame nicians several years later. In the United States,
produced by a pyrotechnic mixture and one result­ possibly because of its cost, magnesium was not
ing from the burning o f pitch, petroleum, or used in military pyrotechnic mixtures until around
resinous wood. Sparks could be varied in form and 1926. Aluminum was not used appreciably in pyro­
brightness, although not in color, so that spark technic compositions until near the end o f the 19th
compositions became, and remained for cen turies, century when it became commercially available.
the main consideration o f the fireworks maker. Illuminating compositions for military appli­
The few flame compositions available in the cations were, basically, the same as those used in
17th century usually included a flammable liquid firework displays over two hundred years earlier.
in order to ensure combustion of the rest o f the A primitive type o f light producing item— whose
mixture consisting of gunpowder, antimony sul­ composition consisted of saltpeter, sulfur, resin,
fide, and arsenic sulfide. Appier1,2 was far in and linseed oil— was included in British military
advance o f his time when he suggested the use of stores until at least 1870. Most important of the
acetate o f copper to give a green tint to a flame. few inventions in military pyrotechnics during the
By the early part of the 19th century, a pyro­ latter part of the 19th century was the parachute
technist, Claude-Fortunl Ruggieri,1,4,5 suggested liight which appears to have originated about 1820
the use o f metal salts and ammonium chloride in in Denmark much in advance of its widespread use
the production o f a colored flame. in the W orld Wars of the 20th century. Another
The modern era in pyrotechnics began with the invention, the Very Pistol which was patented in
introduction of potassium chlorate which was first 1878, originated as a civil signaling device. Ini­
 AM CP 706-185

tially, the pistol had a one-inch bore; this was The range of the crude guns introduced after
later increased to one and one-half inches during the invention of gunpowder was so short that the
W orld W ar I. Improved illuminating and sig­ point of impact of the projectile could be noted
naling devices were developed in the 1914-1918 by the eye. However, this was no longer possible
period because they were required in the trench after the introduction of weapons which fired
warfare of W orld War I to a much greater extent small-caliber, high-velocity bullets over ranges of
than in prior wars. The growing importance of more than a thousand yards. During World War I,
air warfare opened a whole new field for the use the. need for tracers was intensified by the wide use
of illuminants and signals. Simulators and decoys of machine guns. The need for tracers became
were developed for the purpose o f misleading enemy acute, coincident with the enormous expenditure
observers. of ammunition by infantry and air service. At
Most of the illuminating and signaling "devices long range, in the air and on the ground, it was
produced in the period between W orld Wars were almost impossible to estimate range and correct
developed by empirical methods. The limited aim by observing the point of impact of bullets
amount o f work performed in this period necessi­
which did not incorporate tracers.
tated a hurried attempt to put the pyrotechnic
During W orld War I, the air services of both
field on a scientific basis at the start of W orld War
the Allied and Central Powers urgently demanded
II. This attempt was hampered by the necessity
an efficient, accurate tracer bullet and, as the re­
o f producing items for immediate use on the battle­
sult, tracer ammunition was soon developed by all
field. Most o f the research and development con­
of the belligerents. A German tracer composition
tinued to rely upon empiricism. However, a lim­
— containing a mixture o f magnesium, strontium
ited amount o f basic and applied research, much
nitrate, calcium hydroxide and rosin—was not
of it directed toward the development o f better
very satisfactory because it was difficult to ignite
light producing compositions, was started at sev­
and produced a very dim and indistinct trace.
eral o f the Government installations and continued
The French tried several tracer mixtures which
after the war. Results o f the work done after the
contained a small amount o f linseed oil as a
war were extremely rewarding. A t the end of
binder. These tracers were quite brilliant and de­
W orld W ar II Borne opinion was expressed that
pendable but were unstable in storage and became
little improvement could be made in flare and
practically useless soon after manufacture. As a
photoflash compositions.7 Contrary to this opinion, result, French tracers were made immediately be­
major improvements were made, some of them in
hind the lines so that the ammunition could be
time to be of great service in the Korean Conflict.8 placed in the hands of the troops as promptly as
Current research and development effort is possible. I f the ammunition could not be used
being directed toward the development o f advanced within two or three weeks, it was scrapped and
flare compositions, for both illuminating and sig­
replaced.
naling purposes, to functibn at altitudes where After the United States entered the War, a pro­
little or no atmospheric oxygen is available. gram of developing better tracer ammunition for
the American Expeditionary Forces was activated.
6-1.1.2 Tracers The result of this work was the development of
Before the invention o f gunpowder and the use M1917 tracer ammunition, which consisted o f a
o f bullets, there was no need fo r tracers. The jacket of cupronickel surrounding a container of
projectiles used, namely spears and arrows, were gilding metal and a lead shot. The tracer composi­
large in size, and traveled at a low velocity, so that tion was a mixture o f barium peroxide and mag­
their line o f flight could be readily followed. A r­ nesium in grain alcohol, which was dried and
rows tipped with burning grass might be con­ pressed into the container at 48,000 pounds per
sidered the first tracers. Though the prime reason square inch. This tracer was quite satisfactory
fo r using these burning arrows was to start fires, and produced a trace— which was not especially
the course o f the arrow could be followed at night. brilliant— for about 500 yards. Another tracer

6-2
 AMCP 706*185

was developed in cooperation with - the , British, vestigated as a means o f improving color jof the
using a mixture of barium nitrate, barium perox­ flame - and buring. During this period, calcium
ide, and magnesium loaded in a hollow brass bul­ resinate was introduced aa an improved composi-;
let, An igniter mix of barium peroxide and mag­ tion binder. - By 1929, there was concern as to'the
nesium was required with this tracer mixtur;. effects of-incorporating mercury compounds such
The using services were not satisfied with the as,calomel in tracer bullets because, under certain
status of tracer ammunition at the end of the War, conditions, it was observed that the jackets split
and again studies directed toward the! production in storage,. probably due ;to the liberation o f the
of a better tracer bullet were resumed. Many mercury from the calomel.^ Investigation ; proved
mixturesiwere tried during this period:and it was that-the cracking of the jacket was due to the pres­
found that calomel would increase the ^brilliance ence, .of..free mercury, and elimination o f tracer
and luminosity o f the trace produced; this resulted compositions followed. , , ' ,
in the\ introduction of the. M1923 tracer bullet, In,addition to this work, a limited amount.of
caliber .30, and the design of an M1924 protlotype. research and development effort directed toward
During ithis period, tracers Were *developed for the development o f red tracer, compositions for
caliber .50 and also for caliber .45 weapons; these ammunition larger than caliber .50 was initiated.
Were used primarily as red, green, and white sig­ During this same period, the Navy had developed
nal rounds. It is also interesting to note that the and adopted, satisfactory compositions for [.red,
M1923 tracer was evaluated as-a small arms in­ white, green, and orange tracers. .
cendiary bullet •and found to be superior to the . .A bout,1934, study, of test records showed that
then-available small arms incendiary ammunition; Army ^tracers , became ^unsatisfactory after , five
for some time thereafter,this tracer also served as years’ .storage. _ The tracer composition had been
a small arms incendiary. B y December 1926, mili­ wet-processedLto obtain good storage stability;.i.e.,
tary requirements, brought,,about standardization the calcium resinate was dissolved in carbon,tetra­
o f the red, tracer as the only one approved for chloride, mixed to a paste with the , other ingred­
general-military use. The designation was “ Bul­ ients, baked dry, and pulverized tto a powder to
let, Tracer, Caliber .30,,M l.” The tracer.composi­ render .all ingredients moisture-repellent._ Poor
tion contained strontium peroxide made by the storage stability was apparently due, not to the
dry process and a higher-density calomel, . tracer composition, but rather to the dry-blended
The igniter composition contained: barium per­ barium peroxide-magnesium-red lead igniter com­
oxide and fine magnesium. * Tracer M l wks also position.’ Red lead, although aiding bonding and
loaded with a subigniter consisting o f thret parts identification o f the igniter composition, was found
igniter and one part tracer composition to insure to be chemically., incompatible w ith; barium >per­
ignition o f the tracer composition. These changes oxide and, therefore, was removed from the fonnu-
resulted in an increased length o f trace to 1300 la. The magnesium .was pre-treated with jwater to
yards for caliber .30 tracers, and to 2200 yards form a protective oxide ^coating and one percent
for caliber .50 tracers. Research and ,development zinc, stearate was added as a water repellent. This
concerned with small arms^ ammunition continued igniter blend proved to be more stable-under high-
at a very limited rate resulting in changes1such as humidity, testing and was adopted for use in 1937.
the development o f a gilding metal bullet jacket - ' During the period from 1935 to 1941, develop­
to replace the cupronickel jacket.1 The bullet de­ ment, work on delay action and dim igniters for
sign o f the caliber '.30 M l tracer was; standardized small arms tracers was active.9'10 Two composi­
in 1929, based upon the,M 1924’prototype round; tions ^were developed which were standardized.
however, , the ’ pyrotechnic compositionc were .These- compositions form the basis for all delay
changed significantly during the period between action'and dim igniters used in small arms am­
W orld W ar I and 1929. For example many munition. The basic composition is designated.I-.
strontium compounds such as strontium peroxide, .136 Delay Action and is composed o f 90 percent
strontium oxalate, and strontium nitrate were in- strontium,peroxide and 10 percent calciUm resi-
 AMCP 706-185

order to increase the number o f photographs ob­ the requirement1that it should be no'more sensitive
tainable on a mission. ' It contained'about seven to projectile fragments and bullet impact than a
pounds o f dash powder in a cylindrical paper­ general purpose bomb.
board case. Later it was placed in a streamlined' Work on photoflash compositions continued
'steel outer case to improve its operational char­ with considerable' emphasis directed toward the
acteristics. Development " o f the M46 Photoflash development o f flash mixtures containing calcium,
Bomb was started just1before the United States which were more effective at higher altitudes than
entered W orld W ar II. This bomb contained up other photoflash mixtures. ’ -
to 25 pounds o f photoflash mixture in a stream­
lined metal case and was widely used in W orld
6-1.2.1.1.2 Dust Type14
W ar II for photography from intermediate alti­
, The need.for night illuminant safer than the
tudes. ‘
standard flash powder bomb (which was easily
In an attempt to increase the intensity o f the
detonated, by bullet impact) led to a requirement
light from pyrotechnics, scientists under National
for a less-sensitive powder composition. This ap­
Defense Research Committee auspices at Wesleyan
proach was-considered to be preferable to armor­
University and at the California Institute o f Tech­
ing the bomb.\ By 1943, British reports o f the de­
nology conducted a more fundamental study of
velopment o f a safe metal dust bomb, using either
photoflash powder. Both groups reached the con­
aluminum or magnesium powder detonated by a
clusion that no real improvement in flash output
tetryl burster, jhad been received. Initial tests
could be gained by changing the standard mag­
made in this country of.the metal dust type were
nesium-aluminum-potassium perchlorate mixture
not encouraging. It was found that the “ safe”
then in use. Consideration 'was then given to pos­
powder produced only about 20 percent as much
sible methods o f ^obtaining a more- efficient dis­
light as the <standard photoflash bomb. Further
tribution o f the light from the flash. Further
work resulted in the T8 bomb, which was a com­
study, however, indicated that a larger bomb was
plete failure. Instead of dispersing as a dust to
an easier way to obtain higher levels of illumina­
explode in a short bright flash, the milled mag­
tion. Because o f shortages o f aluminum and mag­
nesium powder used in the bomb apparently com-
nesium powdera at the start o f W orld W ar II, a
.pacted into large adhering masses which burned
mixture using a magnesium-aluminum alloy as a (progressively. . 1 •.,
fu e l' instead o f a mixture o f magnesium and The T8E1 bomb, containing 70 pounds o f flake
aluminum, known as Type II, Class A, photoflash aluminum and weighing over 200 pounds, reached
powder was developed. Later, barium nitrate was a peak intensity of one billion candlepower in
adopted as the oxidizer. This mixture was known about' 12 milliseconds. This was little more than
as Type II, Class B, photoflash powder. Later, the peak candlepower of the 50-pound M46 bomb.
a new standard photoflash powder, Type III, Class A ring-shaped flash with, a characteristic non­
A , consisting o f 40 percent aluminum, 30 percent luminous ‘core was produced, presumably caused
barium nitrate, and 30 percent potassium per­ by gaseous decomposition o f the.high explosive
chlorate . was adopted.1
•.
3 It was
* - .. ^
found
f t r■ *. that*.the
.
lat­
- burster. The same dark center was also noted in
ter mixture, when confined,in a heavy-walled cas­ the British dust bombs, Mark III and Mark IV.
ing, would produce more light output from a •By the end of the War, small scale tests o f a
smaller
. -
and
'
safer photoflash r
bomb."
‘ f ■* ..
These results variety of metal dusts, bursters, and casings showed
led t. to the cancellation
- S' o f further
^ l
work on thin-^ that a conical burster eliminated the dark core.
walled photoflash bombs for high altitude, night Continuing research on metal dust bombs
aerial photography, and led to the development showed that a satisfactory bomb was unattainable
o f the safer heavy-walled bombs. These bombs with magnesium dust. The smaller the burster, in
were in production in late 1951 and were used in proportion to weight o f dust, the greater the effi­
the Korean Conflict in 1952. While much safer ciency in terms o f candlepower-seconds per gram,
than the M46, this type of bomb still did not meet but the slower the flash'. No satisfactory point of

6-6
 AMCP 706-185

compromise could be found. The use of atomized 6-1.1.2.2 Photofiash Cartridges16

magnesium-aluminum alloy was then suggested While most of the night aerial photographs
because of its nonhygroscopic nature. It provided during the early phases o f W orld W ar II were
twice the peak candlepower o f magnesium dust obtained at relatively high altitudes, the need
accompanied by relatively little change in total for low level night aerial photographs during the
light output. latter phases of the war was anticipated. There­
A separate development project was started in fore, development of suitable photofiash mixtures,
1948 and led to the standardization of the M122 as well as cartridges and ejectors for this purpose,
dust bomb in 1952.18 The M122 was eight inches was started but the work progressed slowly because
in diameter by 54 inches in length, with a total of low' priority.
weight of 110 pounds. The bomb achieved a peak In 1943 when the need. became acute, the
of 0.82 billion candlepower, although the Average United States’ designs were not complete and a
of several tests was about 0.70, and in the best 40 photofiash cartridge designed and developed by the
millisecond period it produced 31.9 million candle- British was used. This cartridge was based on
power-seconds. It was slow to peak, requiring
the case used for the Very parachute flare. By
about 42 milliseconds. The flash was so long in
1945, the first low altitude photofiash cartridge
duration that on one occasion two photographs
developed in the United States was based on a
Were taken with a single camera using the light
standard signal flare case and contained about
o f a single bomb. Under ideal conditions of dear
five ounces of Type II, Class B flash powder.
atmosphere and high reflectance terrain, it was
Its light output characteristics were poor and,
possible to obtain usable photographs at altitudes
hence, it was not standardized or used during
of 16,000 to 20,000 feet. Good photos under! normal
conditions were possible at altitudes of 5000 to World War II.
12,00 feet. The bomb was stable from an Airspeed The first United States standardized photofiash
o f 185 to 400 miles per hour. The RB-26 (aircraft cartridge was developed by 1949. It contained the
carried a load of ten M122 bombs; the RB-45C then new Type III photofiash powder and could be
carried twenty-five; and the RB-50 carried fifty- used to obtain satisfactory aerial photographs up
two. Procurement was initiated too late for use to an altitude of 4000 feet. These cartridges were
in the Korean action. used extensively in the Korean Conflict for low
altitude night reconnaissance photography. As the
tactical situation in Korea often required night
6-1.2.1.1.3 Segregated Oxidant Type photographs at higher altitudes, the M46 bomb
In 1950, the development o f a segregated oxi­ was also widely used. However, due to the greater
dant type photoflash bomb was begun in an at­ weight o f the M46 bomb, fewer units could be
tempt to obtain both the safety from impact carried, resulting in a demand for smaller units
initiation associated with the dust type bomb and having adequate candlepower. This requirement
the high peak light intensity associated with the had been anticipated and tests using the Type III,
photofiash powder type bomb. In addition, this 30/40/30 formula (potassium perchlorate 30%,
type bomb— in which the burster, oxidant, and aluminum 40%, and barium nitrate 30% ) had been
metal dust are loaded separately in coaxial cylin- made as early as 1947, using charges ranging in
ders— also should be relatively insensitive to alti­ size from 1.7 to 7 pounds. The 1.7-pound charge
tude as compared to the dust which de pend en­ was found to be entirely adequate up to 8000 feet
tirely on atmospheric oxygen. Considerable effort and was loaded as the M123 cartridge with an ob­
was directed toward the development of a bomb turated delay fuze of two, four, or six seconds.
o f this type; however, the results obtained did not Work on photofiash cartridges continued after
prove to be markedly superior to those obtained the Korean Conflict.
with the newer nonsegregated types. As a result, In 1951 an atempt was made to obtain an in­
the segregated oxidant photofiash bomb was not creased light output together with safe charac­
developed into a standardized item. teristics for use in photofiash cartridges. A high
AMCP 706-185

metal content mixture (70 percent aluminum signals of differing intensities which allowed more
and 30 percent potassium perchlorate) was used flexibility in programing of flashes along the tra­
with massive bursters o f RDX. This mixture gave jectory of the missile. Flash signals also have been
twice the total light o f the Type III 30/40/30 developed to evaluate the functioning of the mis­
formula and was relatively insensitive to both fric­ sile warhead frequency system.
tion and flame initiation. Since that time, a limited Further information and references on non­
amount of work has been continued on photodash consolidated illuminants may be found in compre­
cartridges and associated high rate ejection systems hensive reports available.17,18,19
for night aerial photography and other purposes.
6-2 THEORY OF LIGHT AND COLOR

6-1.2.2 Spotting Charges 6-2.1 BEH AVIO R OF LIGHT

For many years, the flash and smoke produced In a strict physical sense, light is that, electro­
by the functioning of a small explosive charge, magnetic radiation which affects the eye and pro­
usually black powder, was used as an aid in spot­ duces vision. The wavelength range of visible
ting the point of impact of practice ammunition. radiation extends from approximately 3800A to
Occasionally, these charges were also used in con­ 7000A; the angstrom unit, A, is equal to 10” 8 centi­
nection with certain items of service ammunition. meters. Other units used for indicating the wave­
During and after W orld War II, the develop­ length of electromagnetic radiation include the
ment of large caliber weapons for use in tanks micron, |x, which is equal to 104 angstrom units.
created a need for simple and reliable target ac­ In a less strict sense, the term light is also applied
quisition for these weapons. One of the more satis­ to electromagnetic radiation whose wavelengths
factory systems developed employed a subcaliber are longer (infrared) or shorter (ultraviolet)
spotting rifle aligned with the major weapon. This than those for visible light.
rifle fired a projectile having a trajectory closely All forms of electromagnetic radiation, in­
matching, in the critical range, that of the major cluding light, are absorbed and emitted as integral
weapon so the location of the flash and smoke pro­ numbers of energy quanta and are transmitted by
duced by the pyrotechnic charge in the subcaliber particles known as photons. The amount o f energy,
round indicated where the major round would hit. E, associated with each photon is:
High precision tracking data is necessary in
E = hi (6-1)
the development of intermediate- and long-range
missile Systems. To obtain this data, brilliant light where v is the frequency of the radiation, and h
flashes must be produced o f sufficient intensity to is Planck’s constant. This equation is often ex­
be recorded by a tracking camera and also be of pressed in other ways, such as:
a short enough duration to provide accurate posi­
E = ~= h < X (6-2)
tion information. Early sources of light used
for this purpose were of the gas discharge type.
where c is the velocity of light in centimeters per
To obtain sufficient light intensity without the
second; X is the wavelength in centimeters; v is
weight penalty associated with electronic flash
the wave number, the reciprocal of the wavelength
systems, pyrotechnic light sources were developed
in centimeters; and h is Planck’s constant.
for this purpose. While the first pyrotechnic sys­
All electromagnetic radiations, including light,
tem developed, the Daisy Photoflash Cartridge, was
have both particle and wave properties. This
a satisfactory light source for a tracking aid, it
dualistic nature is also applicable to matter. A c­
created other problems, the most serious of which
cording to the deBroglie equation, the wavelength
was the production of metal fragments and at­
associated with a particle of mass m moving at a
tenuation of radio signals, which resulted from the
velocity v is given by:
functioning of the flash signal.
In addition to minimizing these problems,
further development resulted in a series of flash
 AMCP 706-185

Many of the effects of light may be sihiply sist, in the optical region, of colored lines, colored
explained by assuming that light, in a uniform bands, and colored regions on a dark background.
medium, will travel in straight lines at measurable Absorption spectra are produced by white light
velocity. This assumption, which is the basis for which has been passed through gases, liquids, or
geometric optics, is very nearly true in most cases other light-absorbing materials on a brightly col­
of interest in pyrotechnics. The direction, or path ored background. Both types of spectra can be
of light, is often represented by a straight line observed in wavelength regions outside the visible
called a ray. Other effects, which cannot be ex­ by special techniques.
plained by geometric optics, must be discussed in Depending on the appearance of the spectra
terms of the wave nature of light, while still others produced in a given wavelength interval, both
must be explained in terms of the particular nature emission and absorption spectra can be further
of light. classified as discrete or continuous spectra. The
A knowledge of the properties of light is im­ spectral distribution of the light produced by
portant in pyrotechnics due to the need for mea­ pyrotechnic light sources for, both illumination
surements and instrumentation required for eval­ and signaling is important; therefore emphasis in
uation, and to carry out the necessary research the following paragraphs will be on emission
aimed at improving light and color sources. Some spectra.
of these properties include reflection, transmission,
absorption, refraction, and the optical character­ 6-2.2.1 Discrete Spectra
istics associated with mirrors and lenses. These
Luminous gases and vapors under moderate or
subjects will' not be discussed in detail as standard low pressures yield emission spectra which consist
physics texts cover them and may be consulted of definitely placed bright lines or closely placed
when required.20 One of the most important) char­ groups of bright lines called bands. The energy,
acteristics associated with the electromagnetic spec­ E, associated with a quantum of light having the
trum o f radiation is spectral distribution; analysis same frequency, v— i.e., a spectral line— is:
o f this distribution provides an excellent tool for
determining the emitting species in flames and E — /iv — E 2 — Ei (6-4)
other light sources. For this reason, several of where h is Planck’s constant. This energy is the
the subsequent paragraphs are devoted to this area. difference between two quantized energy levels in
the atom or molecule, designated above as E\ and
6-2.2 SPECTRAL DISTRIBUTION ; . E 2, s o that the wavelengths of the spectral lines
are characteristic of the radiating source. The
I f a narrow beam of white light is passed
number of lines and their relative intensities in
through a prism, each wavelength is deviated in
an emission spectra also depend on the method of
direction by a different amount and the light beam
excitation.
is spread out into an array of colors. The array
A line observed in an emission spectrum re­
of colors is called the visible spectrum, and extends
sults from the transition of the atom or molecule
from about 0.4-micron to about 0.7-micror. This
from a higher, E 2, to lower, E u energy level ;21 i.e.,
visible portion of the spectrum represents a very
the, transfer of quanta of energy is evolved. I f
small fraction of the electromagnetic radiation
the line is observed in an aborption spectrum, the
commonly emitted by radiation sources, and lies
atom or molecule is raised from a lower to higher
between the longer wavelength (infrared) and the
quantized energy level by the absorption of a light
shorter wavelength (ultraviolet) portions of the
quantum of the proper frequency.
electromagnetic radiation spectrum to which the
eye is insensitive.
Spectra of two general types are observed, 6-2.2.1.1 Line Spectra22
emission spectra and absorption spectra. Emission Line spectra— consisting of a series o f sharp,
spectra are produced by light which is emitted brightly colored lines on a dark background— are
from luminous and incandescent bodies and con­ produced by single or chemically uncombined
AMCP 706-185

o t

£
i 1 1 i § constant; and and Zc2 are integers. The Lyman
M2: n m m — * _r xt
series found in the ultraviolet, and for which
1
I floniiofkm ki = 1 and k2 = 2, 3, 4, —, is caused by transi­
1 \ \ towl
' i j tions from excited atomic states to the ground state
rL _-------------------
______________ :_____ I______ It
l I :------ :-----1---------»—rn
c 1'! k - i 1! 1 SO* - £ or lowest atomic energy state, as is also illustrated
S||! 304 * £
Sn i 1 5 1 300*9 |9 in Figure 6-1. The Balmer series found in the vis­
£l * ______________! 293 If
I 1 ible spectra for which fci = 2 and k2 = 3, 4, 5, —, is
i .. _____ ___ ___ ___ ___ t______i 278 £r
Is caused by transitions from excited atomic states
23* ? S to the first excited state. Other series— includ­
: s
*? ing the Paschen series, Brackett series, and
o Si Pfund series— are found in the infrared. The
f 5
spectral lines for materials of higher atomic num­
Figure 6-1. Emission Spectrum and Energy Levels of ber rapidly become so complex that they cannot
Hydrogen Atom be represented by a single simple equation.

atoms and, therefore, are often called atomic spec­

tra to distinguish them from the band spectra char­ 6-2.2.1.2 Band Spectra28
acteristic of molecules (Paragraph 6-2.2.1.2). The The emission spectra in the visible or ultra­
complexity of the line spectra produced by emis­ violet region, due to molecules, consist o f a rela­
sion depends on the particular atom involved and tively large number o f regularly arranged, but
the method of excitation. Normally, more lines complicated, groups of lines called bands. These
appear in a spark spectrum than in an arc spec­ line sequences are called bands because they ap­
trum and both exhibit more lines than a spectrum pear as structureless bands in low dispersion
produced by thermal excitation in a flame. spectrographs. Each band spectrum shows, in gen­
The term "lin e spectra" 'can also be con­ eral, a threefold structure. It consists o f a num­
sidered a collective term including both atomic and ber of similar but separated groups of bands mak­
ionic spectra. In this context, atomic spectra are ing up the band systems. Each band system is
produced only by neutral atoms while ionic spec­ made up of a number of bands, sometimes ar­
tra refers to spectra produced by ionized atoms. ranged in sequence, consisting o f a number of
Less energy is required to excite an atomic line than regularly arranged lines.
is required to ionize an atom and excite an ionic This threefold structure is due to the partition­
line. In general, therefore, only atomic lines are ing of the total internal energy of the molecule into
found in the spectra excited by arcs and flames. three parts resulting from : the electron configura­
Lines due to ionized atoms are found in spark- tion, the vibration of the atoms in the molecule
excited spectra where excitation is due to high with respect to each other, and the rotation o f the
velocity electrons and the energy is sufficient to molecule. Therefore, the location of the band sys­
excite spectra corresponding to large differences tem in the visible or ultraviolet region of the spec­
in energy. trum is determined by the magnitude o f the energy
Because the energy levels in an atom are re­ changes associated with these transitions. A ll
lated to the configuration of the extra-nuclear bands of a band system are associated with the
electrons, the simplest line spectra are produced change in electron configuration. The position of
by atomic hydrogen (note that the spectra for band in a band system is associated with a change
ionized helium will be similar) where the observed in vibrational energy; changes in the rotational
spectra (Figure 6-1) can be represented b y : energy determine the location o f the different lines.
Changes in energy o f a molecule due to a
change in rotational energy are an order o f mag­
V= B (~ k f~ v ) (6_5)
nitude smaller than those due to vibrational
where v is the wave number, the reciprocal of changes which, in turn, are an order o f magni­
the wavelength in centimeters; R is the Rydberg tude smaller than the energy changes due to a

6-10
 AMCP 706-185

6-2.3 R AD IATIO N SOURCES

Radiation sources can be classified in terms of
the spectral distributions of their radiation and
in terms of the manner in which this radiation is
C o lo riM
(IOOO*l excited. Continuous radiation is generally pro­
duced by hot solids (Paragraph 6-2.2.2). Although
a$\!o o r b or© cSfo or© light produced by certain lasers is very nearly
monochromatic, there is no source o f strictly mono­
Figure 6 -2 . Various Types o f S pectra and Corresponding
chromatic radiation. A narrow range o f wave­
Electronic, V ib ra tio n a l a n d R otational M o tio n
lengths can be obtained by isolating, with a
monochromator or filters, one o f the bright lines
change in electronic configuration of the mDlecUle
produced in emission by certain elements. A wider
( Figure 6-2). The relatively small amounts of
range of wavelengths (however manifest in the
energy corresponding to emission or absorption in
visible spectrum to give the sensation of a color)
the far infrared and microwave regions alre due
can be isolated by similar methods from sources
to changes in rotational energy of the molecule.
producing band or continuous spectra.27
The spectrum associated with these changes is
called the rotation spectrum. The energy Ranges
corresponding to the spectrum found in the near 6-2,3.1 Thermal Radiation Sources
infrared are associated with changes in vibra­ Many radiation sources are based, at least in
tional energy. The superimposition of the effects part, on the emission from a material heated to a
due to rotation, on those due to changes in vibra­ high temperature. The radiation produced is con­
tional level, result in the more complex vibration- tinuous in nature, resembling that of a blackbody.
rotation spectrum. As already indicated, the band
system found in the visible and ultraviolet is due 6-2.3.1.1 Blackbody
to the superimposition of energy changes due to
A “ blackbody” is an idealized body which will
changes in electron and configuration in vibration
absorb all the radiant energy falling upon it. A
and rotation.
blackbody can be approximated experimentally by
an enclosure having a very small opening in one
6-2.2.2 Continuous Spectra21,24,25 > wall through which radiation may enter or leave.
A continuous emission spectrum in the visible According to the Stefan-Boltzmann Law, the total
region is a continuous brightly colored band ex­ radiation E emitted by a blackbody at an abso­
tending from color to color. Incandescent solids, lute temperature T is :
liquids, and gases, under high pressures, produce
E = <
jT4 (6-6)
a more or less continuous spectrum which may
extend without interruption from; the extreme where a is a constant equal to 7.56 X 10-B erg
ultraviolet through the extreme infrared. The cm-3 deg-4 . The intensity of radiation from a
energy in any range, X to (X -f- d k), of wavelengths blackbody at a given temperature varies with the
o f a continuous spectrum is a continuous function wavelength according to Planck’s Equation:
of the wavelength so that the radiation is char­
acterized by a continuum of wavelengths. p 2%c2h nx
X h e/k\ T (b -l)
While continuous spectra are generally pro­
duced by incandescent solids, liquids, and gases;
regions o f continuous emission or absorption may where Ex is the radiance of wavelength X, e is the
result in gases at low pressure when at least one velocity o f light, k is Boltzmann’s constant, and h
o f the energy states involved in the transition is is Planck’s constant. This equation, which is
unquantized, possessing free kinetic energy. These plotted at various constant temperatures in Figure
continue, therefore, correspond to processes such as 6-3, gives calculated values which are in extremely
ionization, recombination and association.!5,26 good agreement with the intensity values deter­
 AMCP 706-185

Figure 6-3. Planck’s Law: Radiance as a Function o f

W ave le n gth fo r Various Temperatures Figure 6 -4 . R adiant Energy in D iffe re n t W ave le n gth
Sonde as a Function o f Temperature

mined experimentally. The function has a single­ for maximum efficiency decreases as does the value
valued maximum, for each temperature, which for the maximum efficiency.28
varies with temperature along curve AB in Figure
6-3. The wavelength of the maximum is given by 6-2.3.1.2 Graybody
the equation:
A graybody, or nonselective radiator, radiates
at every wavelength an amount o f energy bearing
Xmat= - -1 - ( 6-8 ) a constant ratio to the amount radiated by a black-
body at the same absolute temperature. This ratio
and the radiance at XmM is given b y : is called the emissivity and is less than one for all
solid radiators, but may closely approach unity in
E > W = 1178 X 1 0 - T2"> (6-9)
some cases for an extended wavelength region.
As shown in Figure 6-4, the amount o f energy Thus, the spectral distribution is exactly the same
radiated in any given wavelength region by a con­ as that for a blackbody but the total energy radi­
stant temperature blackbody radiator increases ated is less. Several solid materials, including
continuously but at different rates relative to the platinum, iron, tungsten, and carbon, are very
increase in the total amount of radiation, with nearly nonselective radiators over a fairly wide
temperature. Therefore, as shown in Figure 6-5, range of wavelengths.
the efficiency o f conversion o f thermal energy into
radiation in a particular band varies with the 6-2.3.1.3 Incandescent Sources
temperature and exhibits a maximum. As the Actual solid radiators are not “ bla ck " and
wavelength of the band increases, the temperature their total emission is less than that o f a black- m

6-12
 AMCP 706-185
EFFICIENCY, %

Figure 6 - 6 . " O p tic a l" Temperatures o f a Tungsten Filament

cerium oxides, have a low emissivity in the infrared.

When heated by a relatively nonluminous flame,
a larger proportion of energy is radiated in the
visible region. The efficiency o f a Welsbach
mantle as a light source is also due, in part, to
the catalytic activity of the oxides so that the
TEMPERATURE,•« chemical reaction is faster and, therefore, the heat
production greater near the mantle.
Figure 6 -5 . Isotherm al Efficiencies: Fraction o fl Energy Temperatures of incandescent sources can be
Em itted b y an Isotherm al R adiator in Various W avelength
estimated from their total radiation by use of
Bands as a Function O f Temperature I
Stefan’s Law, according to which the total radia­
body. In addition, their emissivity varies with the tion == 5.67 X 10“ B T* ergs per second per square
wavelength and actual radiators are not gray- centimeter. Temperatures determined in this way
bodies. The radiation is thermal if Kirchoff’s Law are called radiation temperatures. I f temperatures
applies, and the ratio of emissive to absorptive are estimated from the visible brightness at a par­
powers is a constant for each wavelength wad tem­ ticular wavelength, they are called brightness tem­
perature. Application of this law distinguishes peratures. I f temperatures are estimated on the
between incandescence or thermal radiation, and basis of the best fit of their emission curve to a
luminescence or radiation excited by other blackbody in the visible region, they are called
methods.28 color temperatures. While it is possible that tem­
While there are materials, such as carbon, peratures determined by these methods may differ
whose emissivity is nearly constant with wave­ widely, in extreme cases, from the true tempera­
length, the emissivity of certain other materials ture, the difference is usually less than a hundred
is strongly wavelength-dependent. I f tne emis­ degrees for incandescent solids such as furnaces
sivity is high in the visible region and relatively and lamp filaments (Figure 6-6).
low in other spectral regions (especially infrared),
a larger portion o f the total radiation will be in 6-2.3.2 Luminescence
the visible and the heat-to-light conversion effi­ Luminescence results when a process leads
ciency is improved. As an example, Welsbach directly to an atom or molecule in an excited state,
mantles, which are impregnated with thorium and from which it can return to a lower energy state
 AMGP 706-185, Cl

by th'e emission of radiation. Under these circ imstances, The ra d ia tio n from any system in complete
the radiation produced at certain wavelengths may be thermodynamic equilibrium will be continuous and the
mucll greater than the amount expected due ;o thermal same as a blackbody at that temperature;however, flame
radiation. Broadly speaking, luminescence refers to the systems, do not fit in this category due to their
emission of light for any reason other than high nonequiiibrium nature. In most small flames, the
temperature. ■. : emission of radiation by the emitting molecules and
particles is not balanced by the absorption of radiation
6-2.3j.2.1 Chemiluminescence resulting in a steady deactivation o f excited molecules
If; the excited atom or molecule is formed directly as and radiation cooling of solid particles. This energy loss
the result of a chemical reaction, the phenomenon is must be made up by collision processes in the.flame and,
knoy'n as chem ilum inescence. The emission of if not efficient enough, the distribution of energy
formaldehyde bands from the “cool flames” of ether between the excited molecules or solid particles may
aldehydes and certain hydrocarbons, at temperatures differ from equilibrium conditions. In addition, chemical
b e t w ee ii 2 0 0 ° a n d 4 0 0 ° C , a r e due t o equilibrium may not be obtained.
chemiluminescence. Radiation from the react on zone of The small particles that are formed in many flames,
a Bunsen burner, the inner cone, is stronger .hail can be including most pyrotechnic flames, definitely influence
a c c o u n t e d f o r t h e r m a l l y , and is due to the radiation produced by these flames. The continuous
l ■ ■
chcihilumincscencc. The amount of radiatioh produced background is emphasized and, in many cases, most of
by j a p y r o t e c h n i c flam e w hich ii due to the radiation produced is continuous. This continuum
chemiluminescence is difficult to determine and, under produced by particles in a flame differs from that
certain circumstances, the amount may be significant. produced by a graybody or blackbody because:
(1) The emissivity o f the material which makes up
6-2.J3.2.2 Phosphorescence and Fluorescence the particles varies with the wavelength.
Certain substances, including the sulfides of calcium (2) The scattering of light: by the particles changes
andl barium, when exposed to radiation, will continue to with wavelength even if the! material making up the
glo|v after the radiation source - is removed. This particle is black or gray.
phenomenon is known as phosphorescence. In other While most of the radiation produced by flames is
materials, the glow persists only for a fraction o f a thermal, in origin, some of the radiation is due to
second: In the latter case, the phenomenon is known as chemiluminescence where the amount of light emission
fluorescence. In general, the radiation emitted, by a is much greater than that expected from thermal
phosphorescent or fluorescent material is of a longer emission. For, premixed flames o f the “Bunsen” type,
wavelength than the exciting radiation. In all these cases, the emission from intercanal gases is thermal in origin.
absorption of the exciting radiation causes ti e formation For the reaction zone (the inner cone) there is more
of an escited molecule or atom. The longei wavelength radiation than can be accounted for thermally.
o f jthe emitted light is attributed to the r( turn of the The characteristics of the radiation produced by all
excited particle to the original nonexcited state in two flames, whether they contain small particles or not, will
or more steps, rather than by a single transition change as the flame size increases. Self-absorption
becomes more important and the radiation will approach
6-2.3.3 Flame Sources25>26 more nearly that o f a blackbody . . ■ ’ V
jThe chief distinction between combustion and other
chemical reactions is the appearance o f flame and the 6-2.4 PHOTOMETRY
emission of light. Most flames produce an emission Photometry is the science of measuring light. Since
spectra of discrete bands which may, especially for the eye is very sensitive and nonlinear in its response to
l umi nous flam es c ont a i ni ng Solid particles, be radiation, an arbitrary unit, the lumen, is used to
superimposed on a continuous background. evaluate radiant electro m a g n etic ' flux in
 AMCP 706-185

terms of its visual effect. The lumen has the by collision can be utilized to increase the number
same dimensions as power. It has been found by of electrons reaching the anode for a given amount
experiment that, for the so-called normal observer, of incident light. Still more sensitive photocells,
one lumen is equivalent to 0.00161 watt of mono­ known as photomultipliers, use the phenomenon of
chromatic green light of a wavelength correspond­ secondary electron emission to produce an internal
ing to the maximum in the visibility cur ire, 555 amplification of the order o f one million. In all
millimicrons. The number of lumens produced cases, the response of the photocathode surface is
by one watt of radiant power is called the luminous spectrally selective and is determined by the basic
efficiency of the source. For a monochromatic material and its preparation. Another type of
source, the luminous efficiency is obtained by mul­ light-sensitive cells is the photoconductive cell, in
tiplying the relative visibility for the wavelength in which the action of light causes an increase in the
question by 680 lumens/watt.2" electrical conductivity of the device. The selenium
cell is an example. A third type of detection uti­
lizes the photovoltaic effect in which a voltage is
6-2.4.1 Instruments for Measuring Light Intensity produced across the interface separating a semi­
Instruments used for the measurement of light conductor from a conductor by light incident on
intensity can be divided into two general cate­ the interface. A common example o f this type of
gories: (1) those which use the heating effect of detector is the copper-cuprous oxide cell. All of
the radiation, and (2) those which make use of these detectors— photoemissive, photoconductive, or
quantum effects o f the radiation. photovoltaic— have a selective spectral response, as
In'the first category, the radiation absorbed by do photochemical reactions, including photography.
the receiver raises its temperature which il sensed The spectral response of photochemical reactions is
by some appropriate means. The thermocouple selective because only the light which is absorbed
uses the thermoelectric effect while the bolometer will produce a photochemical effect. Actiometers
uses the change in resistance of a resistance ele­ use photochemical reactions in which the quantum
ment, which may be a semiconductor, to sense this yield, which is equal to the number of induced re­
temperature rise. Generally, both of these de­ actions divided by the number of quanta absorbed,
tectors are spectrally nonselective in their response has been accurately determined,
to radiation, i.e., they absorb like graybodies. In
another type of thermal detector, which may be
selective in its response, the radiation is absorbed 6-2.4.2 Measurement of the Light Output of Flares
by a gas. The temperature change produced in the Flare output measurements are usually made
gas, which is confined to a very small volume, is in a photometric tunnel. This tunnel is a light­
sensed as a pressure rise. tight structure with a fan to remove smoke and
The second category of detectors are the photo­ with instruments to measure the brightness, color,
detectors which, in principle, count the number of and burning time o f a flare. The inside o f the
quanta o f radiation. An example of a common tunnel is usually flat black and baffled to eliminate
detector in the second category is the photocell reflections. The tunnel is usually built in three
which is a photoemissive detector. It depends for parts: a burning room, which contains the burning
its operation on the ejection of electron) from a table, ignition apparatus, and exhaust fa n ; a long
specially prepared surface by the incident quanta tube section from 50 to 100 feet long which houses
of radiation. In a vacuum photocell the response the photometric transducers; and an instrument
to incident radiation is a linear function o f the room, which houses the recording instruments and
light intensity. The electrons emitted are drawn provides a place for the personnel to work. More
to the anode from the sensitized cathode by a rela- complete measurement capability for a tunnel
tively small voltage applied to the electro ies. Gas- would include the ability to determine the visible
filled photocells are nonlinear in their response spectral output of flares, ultraviolet and infrared
to incident light intensity, but are more sensitive outputs, and flame temperatures. The tunnel must
than the vacuum type because ionization of the gas have calibrating lights and color filters for calibra-

6-16
 AMCP 706-185

tion of the instruments. Luminous intensity mea­ steradians. A unit point source, emitting light uni­
surements in terms of candlepower are often de­ formly in all directions, radiates 4x lumens. The
termined by an instrument which consists of a unit of luminous intensity— adopted by the Inter­
barrier layer photocell, filters, and a microammeter. national Commission on Illumination in 1948— is
This illuminometer is placed at an accurately the candela. It is o f such a magnitude that a black-
known distance from the point at which the candle body radiator at the temperature at which pure
or assembly is to be burned and is then calibrated platinum solidifies has a luminance of 60 candela
by means of a standard incandescent white light per square centimeter.30 An earlier unit o f lumi­
source. During the burning of the .item, illumi­ nous intensity, the candle, is equal to 1.02 candela.
nometer readings are taken at predetermined time Another unit, candlepower, also has been widely
intervals throughout the burning period and the used to express the luminous intensity of a light
average of these readings is calculated. In many source. While the use of these units should be
cases the output of the detector is displayed on a discouraged, they have been widely used by many
graphic recorder. In this case, the output of the pyrotechnic investigators. Therefore, the terms
photocell is fed into the recorder which has been candela (preferred), candle, and candlepower will
calibrated so that the anticipated light output will be used interchangeably in this handbook.
produce a nearly full scale reading. A graphic
record is superior to readings taken with an illumi- 6-2.4.4 Brightness
nometer because all variations during burnings are The concept o f brightness is required because
recorded and thus are available for future study. most sources are not points and the concept of in­
The area under the curve thus obtained represents tensity is not readily applicable to extended
the candlesecond value of the tested item. An inte­ sources. The brightness of an extended source is
grator, which gives the candlesecond value of the expressed in candela per square centimeter of
composition directly, is coupled with the photo­ emitting surface.
cell, thus avoiding the time consuming and less
accurate method of estimating or planimetering 6-2.4.5 Illumination
the graphic record. The illumination of a surface is the amount of
The state of the science in photometry is not light flux (lumens) incident upon a unit area of
yet precise, and measurement errors within ± 10% surface. An illumination of a lumen per square
on flares are as good as can now be attained. Speci­ foot is called a foot-candela. The illumination E
fication MIL-C-18762 covers general requirements of a spherical surface of radius r, enveloping a
although later refinements have been made at each
point source of intensity 7, is given by:
military installation. Representative facilities for
these measurements are to be found at Picatinny _ _P_ _ 4x7 7 lumens
( 6- 11)
Arsenal, Dover, New Jersey; Naval Ammunition ~ A ~~ 4xrs r2 unit area
Depot, Crane, Indiana; Naval Ordnance Test Sta­
for a plane surface at a distance x from a point
tion, China Lake, California; and Naval Ord­
source of intensity I :
nance Laboratory, White Oak, Silver Spring,
Maryland. E = - 4 - cos 0 (6-12)
ar
6-2.4.3 Intensity where 6 is the angle between the source vector and
The intensity of a point source, in any direc­ the normal to the surface.
tion, is defined as the light flux in lumens per unit,
solid angle (per steradian) in that direction, or
6-2.4.6 Photometric Units .
The units employed in photometry are a con­
tinuing source of difficulty, especially for the
where 1 is the intensity in candela and dF is the novice. A strong effort is being made to secure
lumens o f flux within a small solid angle of d<a greater uniformity, reduce the number, and pro-

6-16
 AMCP 706-185

TABLE 6-1
CONVERSION FACT ORS FOR PHOTOMETRIC UNITS

Physical Phycho Physical

Radiator-source of Radiant Energy Luminator-source of Luminous Energy

Radiometry Symbol mks units Photometry Symbol mks units

Radiant Luminous
energy joule energy Q talbot
density joule/m s density q talbot/m 3
flux watt flux F lumen
emittance W watt/m 2 emittance L lumen/m 2
intensity watt/sterad intensity I lumen/sterad
radiance N watt/sterad-ci n2 radiance B lumen/sterad-m 2
irradiance H watt/m 2 illuminance E lumen/m 2
Spectral Luminous
reflectance reflectance r
Spectral Ijurriinous
transmittance • transmittance t

/Rumination
1 lumen/ft2 = 1 foot-candle = 10.764 1umen/meter2 = 10.764 lux
1 lumen/meter2 = 1 meter-candle = 1 lu x — 10—4 phot
Brightness ;
. 1 foot-lambert = 1 equivalent foot-candlc
1 lambert = 3183 candle meter- 2 = 296 candle f t - 2 = : 2.054 candle inch"
E xp osu re
1 meter-candle-second = 1 lumen-second meter- 2

vide more logic in photometric units.7 -8 Some of tent of white lig h t; only monochromatic colors are
the more common photometric units arei sum­ completely saturated. Brightness or lightness is a
marized in Table 6-1. The units of photometry are measure of the amount of light being emitted or
often applied, incorrectly, to measurements! of in­ reflected from the colored light sources or colored
frared or ultraviolet radiation, or to describe the object. Brightness applies to luminous sources
sensitivity of photographic emulsions to radiation. while the term lightness refers to color seen be­
Such usage should be avoided and radiometric cause of reflected light. These three aspects of
units used for these spectral regions. color can be represented on a color solid (Figure
6-7) where hue changes around the circle, light­
6-2.5 COLOR 8 1 -88 t ness increases upward, and saturation increases
In a physical sense, color is determined by the outward from the axis.
wavelength (s) or spectral energy distribution con­
tained in a light beam. Physiologically, color is the 6-2.5.1 Additive Color
sensation produced as the result of the excitation In principle, it is possible to produce any hue
of the retina of the eye by these waves. Colors by a suitable combination o f three primary colors,
are compared in terms of hue, saturation or purity, one from the middle of the visible spectrum, green,
and brightness; all of which influence the color and one from either end, blue-violet and red. As
sensation produced. Hue refers to the color, i.e., indicated by the additive color circles in Figure
red, green, or blue. Not all hues are observed in 6 -8 , proper proportions o f red and green light will
the spectrum of sunlight. The purples are notably produce yellow. I f the proper amount o f blue-
absent. The sensation is a measure of the con­ purple light is added, white light is produced.

6-17
AMCP 706-185

White

Figure 6 -8 . A d d itiv e M ix tu re o f P rim ary C olors

Figure 6 -7 . Dimensions o f the Psychological C o lo r Solid
type. It was found that only the mutual ratios
Colors such as yellow and blue-purple, that pro­ o f three primary colors are of importance in de­
duce white light when added together, are called termining the "color according to the eye” of a
complementary colors. The complementary color given light type. These ratios may be described by
for red is a blue-green (cyan), for green is a red- ,s expressing each primary as a part of the total
purple (magenta), and for blue-purple; is, as indi­ impression of the light type obtained by the eye..
cated earlier, yellow .7 ■ f Thus, for red, green, and blue, respectively, the
ratios are:
6-2.S.2 Subtractive Color
■ r ’ . 9 . b
The light incident on a nonluminous object may r+ 0 + b ’ r + ff + b ’ » \+ 0 + b
be partly reflected, partly absorbed, and partly
which necessarily total one, and, as a result, only
transmitted. I f the incident light is white, the
two need be designated to determine the light
transmitted light will be the color which is com­
type. A particular color or color point, therefore,
plementary to the color which is selectively ab­
may be displayed on an x-y plane, and, due to the
sorbed. For example, the light transmitted will be
mutuality Of the components, will fall within an
red if blue-green is selectively absorbed. Opaque
area bounded by a , 45-degree triangle. However,
bodies, which are seen because light is diffusely
the actual area containing color points varies with
reflected from them, also appear colored because of
the particular set of color sensitivities used to
selective absorption o f light which penetrates a
determine the color points o f the various light
short distance beneath the surface before it is re­
types. Each set produces a "co lo r triangle” with
fleeted. .
its own shape.
In order to effect a standardization, the Inter­
6-2.5.3 Chrojnatidty Coordinates national Commission on Illumination (I.C .I.),* in
The tridimensional color stimulus required by 1931, recommended that all subsequent color data
the eye has been studied in detail and has led to a
* Now known as O.I.E., Commission Internationale de
precise method for expressing a particular light ! ’Eclairage. ■ .

6-18
 AM CP 706-185
. ri.
%

(A

%
m
3

0>
K

Figure 6-10. C .I.E . C hro m a ticity D ia g ra m

400 • 900 600 TOO

W A V E L E N G T H , M ILLIM IC R O N S Since, as indicated earlier, only two coordinates

are required to describe the light type, the values
F ig u re 6 -9 . Tristimulus Values o f the Spectrum C olors o f X and Y are plotted on a chromaticity diagram
According to the 1931 I.C .I. S ta n d a rd Observer
(Figure 6 - 1 0 ) and form a loci of monochromatic
spectrum colors. The line drawn between 380
be expressed in terms o f the same tristiraulus sys­
millimicrons and 700 millimicrons forming the
tem so that the results would be immediately com­
“ base” o f the triangle is called the “ purple line”
parable. The Standard Colorimetric Cciordinate
along which no perceptible colors exist. The
System (X , Y, Z color triangle) was introduced
center o f the triangle (C ) is the equal energy or
which is based on the color sensitivity curves shown
“ white point” and has been designated by the
in Figure 6-9. These curves are the result o f color
I.C.I. (or C .I.E .; used interchangeably) as the
comparison tests conducted on many observers and
light produced by “ Illuminant C ” which corre­
compiled to produce those for the “ standard ob­
sponds very closely to average daylight. Comple­
server. ’ ’ The primary colors were selected so as to
mentary colors will fall on a straight line passing
produce no tristimulus value less than zero (avoid­
through Illuminant C. Also, any color can be con­
ing the use o f negative values in computations).
sidered as a mixture o f Illuminant C and spec­
Further, the curve for the Y-factor is identified
trum light having a wavelength given by the in­
with the eye-sensitivity curve for light, which forms
tersection o f a straight line through Illuminant
the basis of photometry. The values of X , Y, Z are
C and the given color G, with the Chromaticity
the amounts o f the three I.C.I. primaries required
Curve D (Figure 6-10). This wavelength D is
to color match a unit amount o f energy having
called the dominant wavelength. In addition, a
the indicated wavelength. The chromaticity co­
mixture o f two color points anywhere on the
ordinates for each wavelength are obtained from
diagram will produce a color which is located on a
the values of X , ¥ , and Z by means o f the ratios:
line between the two initial colors. Other useful
x — aspects o f the Chromaticity Diagram can be found
in the references. 82
y — z=
X + Y + Z\’ X + Y + Z XU- Y + Z The assignment o f chromaticity coordinates to

6-19
AM CP 706-185

a particular light source is not an easy task. Theo­ 6-2.5.5 Color Value
retically, this can be accomplished for the T value A commonly used designation for describing the
by multiplying the ordinate of the Y curve in color of a pyrotechnic composition is the color
Figure 6-10 at each wavelength by the radiant value. This is defined as the ratio o f the apparent
flux o f the light source at the wavelength and sum­ light intensity (through specific filters) to the total
ming over the visible spectrum. The X and Z (or unfiltered) intensity. This is usually accom­
values may be found by a like process and the plished through the use of two photocells, one of
chromaticity coordinates x, y and z can be cal­ which is equipped with a glass filter. The ratio
culated. In practice, it is difficult to match ex­ obtained is a measure of the visual depth of color
actly the I.C.I. tristimulus curves; however, sev­ of the flame.
eral methods have been suggested8 1 which give
fairly good results. The more widely used methods 6- 2.6 ATMOSPHERIC EFFECTS
incorporate barrier layer photocells and correction Absorption and scattering can change the en­
Alters. ergy distribution of light passing through the at­
mosphere. While the absorption in parts o f the
6-2.5.4 Munsell Color System8 1 . ultraviolet and infrared regions may be very
large, the more important effects in the visible
The Munsell color system specifies a surface
region are due to scattering. A light beam passing
color by giving, for usual viewing conditions, its
through a length x of the atmosphere is attenuated
position on a more or less arbitrary hue (Munsell
from the initial flux F 0, to a flux F, by an amount
hue), lightness (Munsell value), and saturation
which depends mainly on the scattering coefficient
(Munsell chroma) scales having nearly percep­
a, even though individual layers may absorb light.
tually uniform steps. The Munsell value varies
from zero for an ideal black surface having a F = F 0e~ ” (6-13)
luminous reflectance equal to zero, to ten for an For particles whose radii are less than approxi­
ideal white diffusing surface having a luminous mately Yi o the wavelength of the light X, the
reflectance equal to one. Munsell chroma is ex­ scattering coefficient a can be approximated b y :
pressed in arbitrary units intended to be percep-
. <x= AX« (6-14)
tuaily of the same size regardless o f value and hue.
The strongest known pigment colors have chromas where A is effectively a constant. The theory for
o f about 16 neutral grays ; black and white have a spherical particles comparable in size to the wave­
zero chroma value. Munsell hue is expressed on a length of light results in extremely complicated ex­
scale intended to divide the hue circle (red, yellow, pressions for the scattering coefficient. ,
green, blue, purple, and black to red) into 1 0 0 As discussed in greater detail in Paragraph
perceptually equal steps. 7- 2.1.1, smaller droplets preferentially scatter the
The pocket edition of the Munsell Book o f Color shorter wavelengths so that the color o f the trans­
has been widely used as a color standard. It con­ mitted light will shift toward the red. The pref­
sists o f forty constant hue charts where all color erential scattering of the shorter wavelengths de­
samples making up a chart have the same hue. The creases with ( increasing particle size until the
color samples making up the chart are arranged in particle radii become slightly greater than that
rows and columns, the rows .being chroma at con­ corresponding to the maximum for red light. A t
stant Munsell value and the columns being value this time the transmitted light appears blue or
scales at constant Munsell chroma. Comparison green. There is little preferential scattering for
o f an unknown color with these two families of particles whose radii are greater than one to two
scales gives, by interpolation, the Munsell value microns. Little or no variation in transmission
and Munsell chroma o f the unknown color. Inter­ with wavelength is observed for fogs or thin clouds
polation between the constant hue charts gives the because their drop size distribution is broad. I f
Munsell hue. ' the scattering particles are polydispersed, but

6-20
 AMCP 706-185

smaller than optimum size, the transmitted light TABLE 6-2

will be more red than the incident light, acc junt- CANDLEPOWER REQUIREMENTS VERSUS
ing for the deep red of the transmitted light from HEIGHT OF ILLUMINATING SOURCE
the setting sun.
Ground Brightness,
6-3 CONSOLIDATED ILLUMINATING Height Above Ground 0.1 1.0
DEVICES
10 0 ft 1 ,0 0 0 * 1 0 ,0 0 0 *
A consolidated illuminating composition is
500 ft 25,000 250,000
formed by mechanically pressing, extruding, or
1 0 0 0 ft 1 0 0 ,0 0 0 1 ,0 0 0 , 0 0 0
casting finely divided illuminating composition
into some solid shape which often has a candle-like
* Candlepewer requirements necessary to provide speci­
form. When such an item burns in a propagative fied illumination (0.1 and 1.0 fl) on the ground from given
fashion, the flame radiates energy in the ultraviolet, heights above the ground.
visible, and infrared region of the spectrum.. In
most cases, less than 1 0 percent o f the radiant above 1 . 0 foot-lambert will generally require an
energy is in the visible region. The distribution unreasonable amount o f illuminant.) Although it
and relative intensity characteristics of the radia­ is often difficult to, produce, white light provides
tion produced, in any given region o f the spec­ the best illumination for the greatest range of pos­
trum, are determined basically by the products of sible conditions in the field. Since illuminating
the burning reaction which emit in that region and flares are used under field conditions where the
the temperature reached by the emitting species. location and recognition of unfamiliar objects are
Light-producing pyrotechnic devices are char­ important, sufficient duration and intensity are
acterized for military purposes by luminous in­ required to complete the visual observation and-to
tensity, color value (hue and saturation) of the distinguish objects in the field from their b: ‘.k-
flame, and burning rate. Sensitivity o f the com­ ground. Candlepower requirements necessary or
position to impact, static electricity, and friction adequate illumination, 0 . 1 to 1 . 0 foot-lambert, fl,
should be a minimum for safety. The ignition tem­ when the flare is suspended above the ground, are
perature, ignitibility, stability, and hygroscopicity given in Table 6 -2 . 83
are important in determining the certainty o f A diagram o f a parachute suspended flare is
functioning. shown in Figure 6 - 1 1 indicating the manner in
which ground illumination W may be approximated
6-3.1 ILLUMINATING FLARES from values of h, the height of the source; r, the
radius of the desired illumination; and I, the
An illuminating flare produces a single source
intensity of the source. Intensity curves for
of illumination which is generally of high candle-
various heights to produce a minimum value for
power and substantial duration. Flares may be
E of .025 foot-candle are shown in Figure 6-12.
parachute-supported, towed, or stationary. While
their primary function is illumination, they n ay be
used fo r identification, ignition, location of 6-3.1.1 Aircraft Flares
tion, or warning. Flares for aircraft provide illumination for
In general, a pyrotechnic illuminating flare reconnaissance, observation, bombardment, land­
should:8® ( 1 ) produce essentially white lighi., ( 2 ) ing, and also targets for practice firing of anti­
have an intensity in foot candles adequate to pro­ aircraft guns. While details o f flares vary with
duce a brightness level from 0 . 1 to 1 . 0 foot-lambert their purpose, flares for illumination have cer­
on areas or targets with minimum reflectivity, and tain characteristics in common in that they all
(3) burn at peak intensity for a minimum o f thirty produce high-intensity white or colored light for
seconds and, preferably, in excess o f one minute an appreciable length o f time. Most aircraft flares
(These values are desirable; however, where neces­ are parachute-supported to retard their speed of
sary, lower levels may be adequate. Illumination fall and thus provide illumination over a given
 AMCP 706-185

TABLE 6-3
CH ARACTERISTICS OF VARIOUS ILLUMINATING FLARES

T im e lapse
from M a x speed
actuation o f airplane
to full Burning Candle- M ax at tim e o f
function, time, power, Fall, M a x L, dia, Weight, release,
Item Method o j actuation sec sec 10* fp s in. in. lb mph

F L A R E , A IR C R A F T :
guide, 1 min
T6E1 (white) 650
T7E1 (red) Electricity 6 to 7 45 to 60 700 5.4 5.46
T8E1 (green) 90

F L A R E , A IR C R A F T :
paraohute
M8A1 (w/o suspension
bands) (emergency night Release from 3.0 to 5 .0 165 to 195 350 8.0 25.42 4.25 17 6 200
landing) airplane
M8A1 (training) (w/o
suspension bands)

M9A1 Fired from PIS­ 2.5 60 to 70 60 7.0 15.05 2.0 2.11 200
TOL, pyro­
technic, AN-M8

M26A1 (AN-M26) or 150

M26 (M26)
M26A1 (AN-M26) or 5 to 92 195 ±15 800 11.6 50.0 8.0 52.5 350
M26 (w/blue band) 575 (fuzed) (M26A1)
Released
M138 (T10E4) from 360 1,500
M139 (T10E6) airplane 5 to 92 180 3,000 10 45.6 6.25 62 440

Mk 5 and Mods variable 180 600 27.0 4.76 18.0

Mk 6 Mod 6
Mk 6 Mod 6 variable 180 1,000 35.76 5.37 30.0
AN-Mk 8 Mod 1 90
AN-Mk 8 Mod 2 120 180 500 8.0 25.12 4.75 18 250

3. minute, electrically 1H 180 200 9.1 28 4.5 22

operated
3 minute, Wiley SA 8

F L A R E , A IR C R A F T :
tow-target, M50 0 360 65 22.8 2.62 7.13 120

F L A R E , A I R C R A F T : towed Tow cable

Red, M77 (T18) attached to air­ 0 360 ±30 225 23.34 4.65 21 200
Amber, M78 (T19) plane. 70
Green, M79 (T20) 90

FLARE, SURFACE:
Airport, M76 Hand or 0 300 to 420 600 to 850 31.33 4.26 27.6
electrie squib

Parachute, trip, M48 Pressure or trip 3 20 110 3 9.76 5.5 5.0

wire

TOp, M49 Tripwire 0 55 40 6.75 3.0 1.5

■ l
area for a greater time interval. Aircraft flares for bombing purposes, are provided with shades
also have some form of delayed ignition so that to shield air-crew members from glare. Data for
they will clear the aircraft and function at a de­ several aircraft flares are presented in Table 6-3.
sired altitude below it. Certain flares designed A typical aircraft parachute flare for night bom­
for use below the aircraft, such as those intended bardment is shown in Figure 6-13, and its opera-

6-22
 A MCP 706-185

single parachute-supported star or from one to

five freely falling stars, with or without colored
tracers. To be effective, any signal must be recog­
nized in addition to being detected. Characteris­
tics of illuminating signals which are important
in determining their effectiveness include intensity,
duration, and the hue and saturation of the color . 38
Illumination signals are used during the day
as well as night. The brightness of the daylight
sky requires a signal of increased intensity to pro­
vide adequate contrast. Depending on the location
of the signal relative to the clouds and sun,.and the
brightness of the sky; the intensity o f a signal
adequate for night use must be increased by a
factor of ten (twilight) to over 1 0 0 , 0 0 0 (bright
daylight). Relatively little is known concerning
the effects o f flame duration on tie detection and
recognition of pyrotechnic illuminating signals.
However, the burning time should be of sufficient
duration that the signal can be detected, and the
color should be of sufficient saturation so as to be
recognized in a relatively short period of time.
; Since color differences are often the basis for
Figure 6-11. Illum ination D iagram fo r Parachute communication by signal flares, the relative ef­
Suspended Flare ; fectiveness of the various color hues and their
saturation is important. Since a signal used
tion is shown diagrammatically in Figure 6-14. during daylight must often be observed against
typical tow-target flare is illustrated in Figure a sky (blue) background, red signals,''even though
6-15. '■ f : . V. ; . ' " requiring slightly more intensity at night, are most
visible and most easily recognized in general
usage. 38 Of the other methods, such as multiplicity,
6-3.1.2 Surface Flares ^
different shapes, sizes, patterns, or flashing of the
Flame-type surface flares are used for illumi­ -which could be used for communications
nation during airplane landings in case o f power only multiplicity appears to be flexible enough
failure at airports, or to outline boundaries of for normal combat use.
emergency landing fields. Mine- or grenade-jtype
surface flares are u s e d to illuminate targets and
objectives, to aid in detection o f infiltration or 6-3.2.1 Aircraft Illumination Signals
surprise attacks by enemy troops, and for recog­ Aircraft signals used directly in connection
nition and signaling purposes. Data On several of . with,-combat - operations were originally intended
tln.se flares are presented in Table 6-3. A surface for signaling from air to air or air to surface.
flare which is primarily used to give warninjg of Since the introduction of the pyrotechnic pistol
infiltration by enemy troops is shown in Figure and hand pyrotechnic projector, aircraft signals
6-16. have also been used by ground troops for ground-
to-ground and ground-to-air signaling. The sig­
nals are generally of one piece, rimmed case con­
6-3.2 ILLUMINATION SIGNALS struction with a steel closing Cap. Aircraft sig­
Light-producing signals are much smaller and nals are fired from the pyrotechnic pistol or hand
faster burning than flares and may consist o f a pyrotechnic projector.

6-23
AMCP 706-185

RADIUS fl£ ILLUMINATION. IN F£EI

Figure 6-12. Intensity Curves fo r V arious Parachute Flare Heights

Single-star aircraft signals, double-star signals, ing fire. In some small arms tracers the gilding
and tracer double-star signals contain red, green, metal or steel bullet jacket has, as shown in Figure
or yellow light-producing candles of pyrotechnic 6-18, a cavity into which the tracer and its asso­
composition. Stars can be distinguished ait dis­ ciated igniter compositions are loaded and com­
tances up to five miles ai night and two to three pressed at 80,000 to 125,000 psi. Armor-piercing
miles in daylight. tracer ammunition contains a steel core which is
Data on aircraft signals are presented in Table inserted into the bullet jacket, as shown in Figure
6-4(A ). . 6-19. The steel core has a cavity into which the
tracer compositions are loaded. Some artillery
6-3.2.2 Ground Illumination Signals projectiles have a cavity in the base into which
These signals consist of devices which produce the tracer and igniter compositions are pressed,
a signal when fired vertically into the air. The as shown in Figure 6-20, at a pressure of over
height of projection is from 600 to 700 feet. Data 100,000 psi. Other artillery projectiles use a sepa­
for some ground illumination signals are given in rately-loaded tracer assembly which is fitted into
Table 6-4 (B ). A typical hand-held device is shown the base of the projectile as illustrated in Figure
in Figure 6-17. 6-21. In some ammunition, the tracer composition
initiates a charge which destroys the projectile
6-3.3 TRACERS after a definite time interval. In specific cases,
Tracer ammunition for both small arms and this may be the only function performed by the
artillery is used for determining range and direet- composition loaded in the tracer cavity.
 AMCP 706-185

ENLARGED SECTIONAL

ABC D E F 6*

JKLMNOP QRSTU V W

ASSEMBLED WITH FUZE AND

ARMING WIRE

A Shipping plug I Flare charge Q Releasing cup disk

B Shad* retainer support J Relay charge R Cover releasing cup
C Rib retainer K Delay element S Cover
0 Stem L base block assembly T Stabilising sleeve
E Lower spacer M Shock absorber assembly (J Hangwire
F Ribs N Shrouds V Handle assembly
C Shade 0 Thrust spocer , W Fin stiffener
H Oulckmatch P Parachute

F ig u r e 6-13. Typical A irc ra ft Parachute Flare

Since tracer compositions are relatively diffi­ protect the tracer composition from the effects of
cult to ignite, a more easily-ignitible ignition com­ moisture. I f the brilliant light from the igniter
position is loaded on top o f the tracer composition. composition dazzles the gunner and betrays the
The ignition composition, which usually contains location of the weapon, a so-called “ dim igniter ” 10
a binder, along with a thin metal seal, serves to composition may be used.

6-25
 AMCP 706-185

A — A R M IN G WIRE J— P U LL-O U T CORD

B— HANGW IRE K— RELEASING CUP DISK
C— COVER L— THRUST SPACER
D— TEAR WIRE M — SHADE RETAINER SUPPORT
E— SLEEVE N— SAFETY DISK
F— DETACHABLE COVER LOCK P— SHOCK ABSORBER
G—COVER RELEASING CUP 0 — fR IC T IO N WIRES OF IGNITER
H— DETACHABLE COVER R— LOWER SPACER A N D RIB RETAINER

Figure 6-14. O p e ra tio n o f Typical A irc ra ft Parachute Flare

The pyrotechnic behavior of tracer composi­ tions should, in general: ( 1 ) produce maximum
tions is similar to that exhibited by other con­ light output and saturated color for maximum
solidated compositions and the same characteris­ visibility, ( 2 ) burn long enough to permit the
tics are important. Tracer pyrotechnic composi­ projectile to be followed to the target, and (3)

6-26

\
1
 £4.''-

AMCP 706-185

H 6 F E DCB A
b.

A-CABLE RING G - RETAINER N - I G NI TER S

B - P U L L COVER H - B A S E BLOCK P - FIRE C L A Y TOP S E A L
C - SLEEVE J - QUICKMATCH Q - F L A R E CASE
0 - SAFETY DISK K - ILLUMINANT CHARGE R - CLOSING COVER (TOP)
E - SHOCK A B S O R B E R S L - F I R ^ T - F I R E . CHARGE S- SE ALI NG STRIP
F- FRICTION WIRE P UL L WI RES M - PRIMING COMPOSI TI ON T- CLOS I NG CO VE R ( BO T T O M)

Figure 6-15. Typical Aircraft Tow Target Flare

ignite easily from the igniter composition but re­ (2) Binders which include resins, waxes, elas­
sist ignition by any propellant gas which may tomers, plastics, and oils.
penetrate to the tracer composition. Most tracers (3) Waterproofing agents which usually are
are made to produce red light because red light resins, waxes, plastics, oils, and dichromating solu­
# is the most visible color under daylight conditions;
however, wide use of white tracers had also been
tions. (They are used as protective coatings on
metals such as magnesium to reduce the amount of
made by the Germans and Japanese. At limes reaction with atmospheric moisture.)
there may be requirements for several different (4) Retardants which are usually inorganic
colors to indicate origin of the projectiles. salts, plasties, resins, waxes, and oils. (They are
Smoke tracers (Paragraph 7-1.3) have been used to decrease the rate of the reaction between
proposed and developed to provide a more visible the fuel and the oxidant so as to obtain the desired
trace in daylight; however, the advantages do not overall burning rate.) Some retardants behave
justify providing two types of ammunition with merely as inert diluents while, others participate
different tracers. in the reaction at much slower rates than the main
constituents.
6-3.4 TY P IC A L COMPOSITIONS Typical illuminating, signaling, and tracer
Pyrotechnic illuminating compositions, like compositions are given in Tables 6-5(A ) and
other pyrotechnic compositions, are basically a 6-5 (B ).
mixture of an oxidizing agent and a metal fuel.
Other materials are added to this mixtuie to 6-3,5 FACTORS AFFECTIN G PERFORMANCE
modify the burning rate, color, and radiant out­ As indicated in Figure 6-22, three zones are
put, as well as to increase handling safety. Im­ established when a consolidated illuminating com­
portant additives include: position is ignited and burns propagatively. In
(1) Color intensifies which are mainly highly Zone A, essentially the burning surface, both exo­
chlorinated organic compounds, e.g., hexacliloro- thermal and endothermal reactions take place re­
ethane (CaClg), hexachlorobenzene (C 6 Cle), De- sulting in the formation of gaseous fuel and oxi­
chlorane (C 1 0 CI1 2 ), and polyvinylchloride (C H 2- dizer intermediates. These intermediates react exo­
CHC1). thermally in the flame zone. Usually, the pyro-

Ms* 'M3 6-27

 AMCP 706-185

TABLE 6-4(A )
CHARACTERISTICS OF VARIOUS A IRCRAFT SIGNAL FLARES
time lapse
from
actuation
tofull Burning
function, time, Candlepower, Fall, Max L, Max dia, Weight,
Item Method of actuation sec sec 10* fpe in. in. 16

SIGNAL ILLUMINATION,
AIRCRAFT: Fired
Double star: from
Red-red, AN-M37 PISTOL, 5 1.54
Red-red, AN-M37A1 pyrotechnic, 10±3 26 (ea star) Free 3.85 1.67 0.35
Red-red, AN-M37A2 AN-M8 5 1.57
or
Yellow-yellow, AN-M38 PROJECTOR, 12 (ea star) 1.54 0.42
Yellow-yellow, AN-M38A1 pyrotechnic, hand, 10±3 20 (ea star) Free 3.85 1.67 0.35
Yellow-yellow, ANM 38A2 M9 5 .20 (ea star) 1.57 0.35

Green-green, AN-M39 1.54 0.35

Green-green, AN-M39A1 10±3 20 (ea star) Free 3.85 1.57 0.39
Green-green, AN-M39A2 5 1.57 0.39

Red-yellow, AN-M40 25 (Rsiar) 1.54 0.39

12 (Y star)
Red-yellow, AN-M40A1 Fired 10±3 25 (R star) Free 3.85 1.57 0.35
from 20 (Y star)
Red-yellow, AN-M40A2 PISTOL, 5 25 (R star) 1.57 0.35
pyrotechnic, 20 (Y star)
AN-M8
Red-green, AN-M41 or 25 (R star) 1.54 0.35
Red-green, AN-M41A1 PROJECTOR, 10±3 20 (G star) Free 3.85 1.57 0.39
Red-green, AN-M41A2 pyrotechnic, 5 1.57 0,39
hand,
Single star: M9
Red, AN-M43 1.54
Red, AN-M43A1 10±3 25 Free 3.85 1.57 0.27
Red, AN-M43A2 5 1.57

Yellow, AN-M44 0 15 1.54

Yellow, AN-M44A1 10 ±3* 25 Free 3.85 1.57 0.26
Yellow, AN-M44A2 5 25 1.57

Green, AN-M46 30 1.54

Green, AN-M45A1 10±3 25 Free 3.85 1.57 0.32
Green, AN-M46A2 5 25 1.57

Tracer, double star:

Yellow tracer, red-yellow star,
AN-M63
Yellow tracer, red-yellow star, 0 T, 2.5 to 4 T, 30
AN-MS3A1 Star, 3 to 4.5 RBtar, 48 Free 3.85 1.67 0.40
Y star, 36
Yellow tracer, red-yellow star, 5 3 to 4.5 R star, 48
AN-M63A2 Y star, 36
Green tracer, red-red star,
AN-M54 T, 2 .5 to 4 T, 25
Green tracer, red-red star, 0 Star, 3 to 4,5 Star, ea 48 Free 3.86 1.67 0.38
AN-M54A1 5 3 to Star, ea 48
Green tracer, red-red star, 5 3 to 4.5
AN-M64A2

Green tracer, green-red star,

AN-M55
£8389
HOPJOrt

Green tracer, green-red star, T, 2.5 to 4

Free 3.86 1.57 0.38
t i l l

AN-M55A1 0 Star, 3 to 4 .5
Green tracer, green-red star,
AN-M55A2 5 3 to 4.5

6-28
 AMCP 706-185

TAB] >£ 6-4(A ) (coat’ d)

Tt«ne lapse
from
actuation
to full Burning
function, time, Candlepower, Pall, Max L, Max <Ha, Weight,
Item Method of actuation sec sec 10* fv* in. in. lb
Red tracer, green-green star,
AN-M66
Red tracer, green-green star, Fired 0 T, 2 .5 to 4 T, 30
AN-M66A1 from 5 Star, 3 to 4.5 Star, ea 20 Free 3.85 1.57 0.38
Red tracer, green-green star, PISTOL, 3 to 4.5 Star, ea 20
AN-M56A2 pyrotechnic,
AN-M8
Red tracer, red-red star, or
AN-M57 PROJECTOR,
Red tracer, red-red star, pyrotechnic, 0
AN-M67A1 hand, 5 3 to 4 .5 Star, ea 48 Free 3.85 1.57 0.39
Red tracer, red-red star, M9
AN-M67A2

Red tracer, green-red star,

AN-M68
Red tracer, green-red star,
AN-M68A1 0 Free 3.86 1.57 0.39
Red tracer, green-red star,
AN-M68A2 5 3 to 4.5 G star, 28
R star, 48

technic composition is fuel rich and the excess by these emitting species. The rate at which a
fuel* reacts with oxygen from the atmosphere. pyrotechnic mixture burns depends on the amount
Some o f the energy required to form these gaseous and rate at which heat is evolved. Sufficient heat
intermediates results from the energy released in must be produced to raise the temperature o f the
exothermic reactions on the burning surface (Zone ingredients to a point at which an exothermal
A ) and some from the flame zone. Energy from reaction will be initiated, and the reaction rate
Zone A is also transferred to Zone B which may must be sufficient to more than compensate for heat
be considered the pre-ignition zone. Directly below losses in order for the composition to burn propa­
Zone B is the remainder of the unreacted pyro­ gatively. As are common to all combustion pro­
technic composition, or Zone C. cesses, the rate o f burning, the products formed,
Figure 6-23 shows a typical isothermal dia­ and the flame temperature are affected markedly
gram o f the temperature distribution o f a pyro­ by the composition o f the mixture, as well as by
technic flame. 8 The temperature is not co:ostant the physical condition o f the materials and the
throughout the flame, the hottest portion occurring ambient conditions under which it is burned. Some
approximately two inches above the burning sur­ o f the more important factors which affect the per­
face in the middle o f the flame. formance o f light-producing pyrotechnic items
The flame produced by most pyrotechnic com­ include: ( 1 ) heat o f reaction, ( 2 ) composition,
positions is heterogeneous in nature, containing (3) emitters, (4) color intensifiers, (5) binders,
solid, liquid, and gaseous products of combustion. ( 6 ) particle size and distribution, (7) consolida­
As most o f the radiation produced is o f thermal tion, ( 8 ) flare diameter, (9) case materials and
origin , 8 the distribution o f radiation in any spec­ coating, ( 1 0 ) temperature and pressure, ( 1 1 ) ro­
tral region is determined, basically, by the chemical tational spin, and (12) moisture. In addition to
nature and physical state o f the products which the above factors, the igniter or first fire used may
emit in that region and the temperature reached also influence the output o f a pyrotechnic device.
* See example Paragraph 3-2.5. Any changes in the pyrotechnic composition, the

6-29
 AMCP 706-185

TABLE 6-4(B )
CHARACTERISTICS OF VARIOUS GROUND SIGNAL FLARES
j
Tim e lapse
from
actuation
to fu ll Burning
function, time. Candlepower, Fall, M a x L, M a x dia Weight,
Item M ethod o f actuation sec sec 10s fp s in. lb in.
S IG N A L , I L L U M I N A T I O N ,
GROUND:
White star, cluster, M18A1 18 (for ea
White star, cluster, M18A2 ■ ‘ 5.5 4 to 10 of 5 stars) Free 10.14 1.88 1.09
Green star, cluster, M20A1 Fired from 7 (for ea of
Green star, cluster, M20A2 LAUNCHER, 5.5 4 to 10 5 stars) Free 10.14 1.88 1.09
grenade,
Amber star, cluster, M22A1 M7 series 2 (for ea of
Amber star, cluster, M22A2 5.5 4 to 10 5 stars) Free 10.14 1.88 1.06
Bed star, cluster, M52A1
5.5 4 to 10 35 (for ea Free 10.14 1.88 1.09
Bed star, cluster, M52A2 of 5 stars)

Green star, cluster, M125 (T71) Hand-held rocket- 5.0 4 to 8 9 (for ea of 4.5 10.14 1.64 1.3
propelled launching 5 stars)
mechanism

White star, parachute, M17A1 Fired from 5.5

LAUNCHER, 20 to 30 20 7 10.40 1.88 1.04
White star, parachute, M17A2 grenade,
M7 series
Green star, parachute, M19A1 5.5
20 to 30 20 7 10.40 1.88 1.02
Green star, parachute, M19A2

Amber star, parachute, M21A1 5.5

20 to 30 4 7 10.40 1.88 1.00
Amber star, parachute, M21A2

Bed star, parachute, M51A1 5.5

20 to 30 20 7 10.40 1.88 1.02
Bed star, parachute, M51A2

Red star, parachute, M126 (T72) Hand-held rocket- 50 5 8 9.04 1.64

White star, parachute, M127 propelled type
(T73) launching 5.0 25 50 10-16 9.64 1.64 1.3
Bed star, parachute, M131 mechanism
(T66E1) 30 10 10.0 1.63 1.21

igniter, the container, etc.— which might be caused combustion should be high and products formed
by storage conditions— may also markedly affect must be stable at the high temperatures necessary
the output o f light-producing pyrotechnics. to produce the luminous intensity required for il­
luminating and signaling purposes.
6-3.5.1 Heat o f Reaction The heats of reaction for the stoichiometric
One o f the important factors in determining reaction between several oxidizers, and aluminum
the luminous intensity of a light-producing pyro­ or magnesium as the fuel, are summarized in Tables
technic device is the temperature reached by the 6 - 6 and 6-7. In general, for both fuels, the per­

emitting species in the flame and produced by the chlorate oxidizers are the best solid energy pro­
burning of the pyrotechnic mixture. The tempera­ ducers on either a weight.or volume basis; how­
ture reached depends, in turn, on the amount and ever, some o f the nitrates are almost as good.
rate at which energy is released by the reaction. Physical data and burning characteristics of
In general, therefore, the energy released during stoichiometric mixtures of the alkali and alkaline-

6-30
 AMCP 706-185

PARACMUU

P U LL RING
SUSPENSION
C- A BI E

FELT PAD STRIKER

IlLlM iN A N T
COMPOUND

PERCUSSION
CAP
LAMINA TED
P A P E R C AS E

IGNITION
Ig n ite r
CHANGE

F t I T PAD

PROP*'11<NC
f H A HOI

DELAY n ,7 (

PROPELLING CHARGE

Figure 6-16. Typical Surface Trip Flare

6-31
 AMCP 706-185

S te M L -
CBCnO N C M M fi£ ,

Figure 6-17. Typical Hand-Held Illum inating S ignal r

Figure 6-18. Sm all Arm s Tracer

earth nitrates and potassium perchlorate are sum­ lower molecular weight oxidants in each group
marized in Table 6 -8 (A ). The nitrates have been should be preferred over those of higher molecular
arranged in accordance with their molecular weight. Unfortunately, the lower weight oxidants
weight and the periodic group of the metallic tend to be extremely hygroscopic, which complicates
element. It is evident from this arrangement that, their use in pyrotechnic compositions, and the
in each group, as the molecular weight of the oxi­ shelf-life or the stability of mixtures containing
dant increases, the proportion of fuel in the them is markedly reduced in the presence of traces
stoichiometric mixture decreases. Consequently, of atmospheric moisture. Greater care is therefore
the heat of reaction decreases. This is reflected in required in sealing the container and a higher
a decreasing luminous intensity, burnng rate, and probability exists for inadequate performance after
efficiency. On this basis, it would appear that the long storage.

6-32
 AMCP 706-185

HARDENED ALLOY
INCENDIARY MIXTURE IM -II-
GILDING METAL JACKET-

Figure 6 •19. A rm or-P iercing Tracer

6-3.5.2 Composition oxidizer used, ranging from about 1 0 , 0 0 0 candles

The luminous intensities of flares containing per square inch for potassium nitrate to around
binary mixtures of magnesium and the oxdizers 800,000 candles per square inch with sodium ni­
listed in Table 6 -8 (B ), change with increasing trate as the oxidizer. The difference is due to
magnesium as shown in Figure 6-24. For a given several factors, one of the more important of
oxidizer, the luminous intensity increases with the which is the metal in the oxidant. Sodium is a
amount of magnesium until a maximum is reached strong emitter in the visible region while potas­
at 70 to 80 percent magnesium. A further increase sium is not.
in the amount of magnesium results in a reduction The elements used to color pyrotechnic flames
in luminous intensity. The burning rate also is for military uses are strontium, producing red;
a maximum at 70 to 80 percent magnesium, as is barium, producing green; and sodium, producing
illustrated in Figure 6-25. yellow. Copper (blue or green) has also been
As seen in Example 5, Paragraph 3-2 5, the used.2 2 Lithium (red), boron (green), thallium
amount of magnesium which will produce the maxi­ (green), rubidium (red), and cesium (blue), are
mum luminous intensity can be estimated if it is also strong color producers, but their use is not
assumed that only that amount of magnesium, in practical because o f cost, toxicity, or nature of
excess of the stoichiometric amount, which |can be their compounds. 39
vaporized by the stoichiometric reaction will react The chromaticity coordinates for a large num­
with the oxygen in the air. It requires about 1.5 ber of yellow (sodium containing), green (barium
kilocalories to vaporize one gram of magnesium; containing), and red (strontium containing)
therefore, the amount of energy released iby one flares, when plotted on a chromaticity diagram,
gram of a stoichiometric mixture of magnesium form three straight lines which converge toward a
and sodium nitrate will vaporize about 1.3| grams common point, as shown in Figure 6-26.8T
of magnesium. This corresponds to a mixture con­ The dominant wavelength for the yellow flares
taining about 75 percent magnesium. (indicated by the intersection of the straight line
with the perimeter of the chromaticity diagram)
6-3.5.3 Emitters is around 590 millimicrons. Results of some yel­
.As shown in Figure 6-24, the light inteinsity at low flares did not, as indicated in Figure 6-26,
the optimum magnesium content varies w th the fall on the straight line. This is believed to be due

6-33
AMCP 706-185

H E PROJECTILE

IGNITER CHARGE

ALUMINUM1 HOUSING 'Tr'& a f 1 v ' . '.: ; .

CtQSING DISC

*•'^-rt . . »
^E A U N G WASHER
-i ‘

aOSING WASHER
' *;•&;•.r.•«.»'•.
"’,r., ' ' .
-i;

I^ S IN G DISC
-~ 'i
r. ' ...-.'I--
...... - -■*:■,‘?.<i
**»• - ■. . ■■ - '4 £ t

^ , >- .-

•v rs a a r»* r%

Figure 6-20. Artillery tracer Element in Projectile

to measurement error as later measurements of 'liatomic. ■a n d -possibly triatouiie emitters which

Hares with essentially the same composition foil ..■■n exist at Hr*, high temperatures in a pyro­
close to the straight line. For the red flare and technic flame.1’’ - Secondary emitters, including
green flare, both of which contain a source of particulate matter, will influence the dominant
chlorine, the dominant .wavelengths are approxi­ • ;i'.('length, the colorimetric- purity, ihe saturation,
mately 640 millimicrons and approximately 524 and the relative intensity of the !'>.'ht produced.
millimicrons, respectively. Typical spectra obtained These spectroscopic 'studies iudicateu that the red
for a red, yellow, and green signal flare are given light produced bv flares containing -nrojitinm and
in Figure 6-27. a source of .chlorine is due to the diatomic mole­
Spectroscopic studies indicate that most of cule SrfU which emits strongly near 640 radii-,
the light produced by illumination and signal microns. For flares which did not contain chlorine,
flares is due to a limited number of monatomic, but produce a red light, it was concluded that
 AU CP 706-185

the red light was, most likely, due to strontium emission o f cuprous chloride (CuCl), much of
oxide (rirO). which is radiated in the 420- to 460-millimicron
Green flames are produced by the band System region of the spectrum. The blue-green and green
of barium chloride (BaCl) in the 505- tc> 535- systems which are also produced are usually much
millimicron region of the spectrum. Most green weaker.
flames show, in addition to the band emission from Yellow light is primarily due to the D lines of
barium chloride, emission in the orange and red sodium and associated continuum. A t high sodium
region, band emission from calcium chloride ( CaCl) concentrations, there is strong continuous emission
and strontium chloride (SrCl) formed from stron­ in a region which extends from 500 to 700 milli­
tium and calcium impurities in the barium. In microns.
addition, there are contributions from an extensive As shown in Figure 6-28, which is the spectral
barium oxide (BaO) band system (400 l!o 800 distribution of energy from a green flare,88 the
millimicrons). specific emission, approximately 525 millimicrons,
Other studies indicate that the triatomic mole­ is superimposed on a continuous background . 40
cule Sr (O H ) (strong emission near 640 milli­ This results in a less saturated green. An increase
microns) may contribute to the production of red in magnesium content, as shown in Figure 6-29 for
light and that barium hydroxide B a (O H ) (strong a yellow flare, 87 results in a decreased saturation
emission from 487 to 527 millimicrons) may con­ of the colored light produced. The continuous
tribute to the production o f green light. There is background may be due, in part, to incandescent
some evidence that part of the radiation from the carbon (from binder) as a binary mixture of mag­
emitter may be due to chemiluminescence.^ 2 nesium and an oxidizer show' somewhat less con­
Blue flames are normally produced by the tinuous background. It is .also due. in part, in

6-35
AMCP 706-185

TABLE 6-5
T Y PIC A L ILLUMINATING, SIGNALING, AND TRACER COMPOSITIONS

FUEL OXIDIZERS Binder

Stron­ Oil
Mag* Alumi­ Barium Sodium Sodium tium Linseed Wax
SOURCE COLOR netium num Miec. Nitrate Oxalate Nitrate Nitrate Mite. /Cottar Paraffin Mite.
A White 26.9 38.3 25.2(d) 2.9 6.7
A White 28.6 6.5 67.0 8.0
A White 36 4 43 12.6 1 2.6
1
A White 48 21 5 21 1 8
1
C Yellow 52 36 13(j)
C Yellow 68 37 600
0.6(1)
C Green 23 63 ' 2(m)
20m)
2m)
C Bed 40 18 22(e) 6(n)
7(o)
C 21 68 6 2 4(p)
D 68.0 37.6 4.5(e)
(29) (k)

A. Naval Ammunition Depot, Crane, Indiana >

B. Frankford Arsenal
C. Picatinny Arsenal
I). NOL White Oak, Maryland
a. Pyrotechnic compositions .
b. Manganese
e. Silicon
d. Potassium Nitrate
e. Potassium Perchlorate
f. Strontium Peroxide
. Strontium Oxalate
f . Barium Chromate
i. Lead Chromate
j. Thiokol
k« laminae
1. Pluronio
m. Copper Powder
n. Hexaehlorobencene .
o. Asphaltum
p. Sulphur
q. Calcium Reainate . '
r. Polyvinyl Chloride
s. Binder Composition .
t. Zirconium Hydride ' •
u. Tetranitrocarbaeole
Note: Details of preparation aud material specifications should be obtained from source installations.

6-36
 AMCP 706-185

TABLE 6 - 6
H E A TS OF REACTION OF ALUMINUM W ITH
STOICHIOM ETRIC QUANTITIES OF VARIOUS O X ID AN TS

uompt/wum .. rrvuMutd
Oxidant Density, g/ec* Kcal, Total Col/g Comp Calico Comp• Assumed

A1(C10«)S 2.70 est 1,603 est 2,960 est 7,990 est A l 2 Oa-AlClg
M g(C 10«). 2.64 3,230 2,930 7,750 Al 2 Og-MgCl2
LiC10« 2.53 1,590 2,970 7,520 AlgOg-LiCl
Be(C10 4 ) 2 2.38 est 3,200 est 3,030 est 7,220 est Al 2 0 8 -BeCl2
KCIO* 2.58 1,598 2,530 6,540 AI2 O3 -KCI
B e (N 0 8 ) 2 2.51 est 1 , 8 8 6 est 2,810 est 7,070 est A l 2 Og-BeO-N2
Pb(N O a ) 2 3.90 691 1,585 6,190 Al 2 0 3 -Pb-N 2
NaNOg 2.39 1,624 2,080 4,980 A l 2 Og-Na2 0-N 2
F 2 0 (liq ) 1.95 1,038 3,850 7,510 AljjOg-AlF 8
0 2 (liq) 1.64 798 3,910 6,430 A l2 0 8
F 2 (liq) 1.37 622 3,700 5,070 A IF s
CuO 5.11 288 984 5,030 A l 2 Oa-Cu
MeOs 3.81 2 ib 1,105 4,210 A12 0 3 Me
Fe 2 0 8 4.18 203 948 3,960 AI 2 O3 -F 6
W 08 5.46 198 693 3,780 A^Oa-W
v 2o » 3.19 876 1,075 3,340 A12 0 3-V
H 2 0 (liq ) 1.46 194 1,800 2,620 a i 2 o 3 -h 2

* Baaed on calculated true density.

the visible, to the volume emission resulting from chloride, or Dechlorane are generally used as color
scattering by the solid particles of MgO -which are intensifies because they are a ready source of
essentially transparent in that environment. chlorine. As shown in Figure 6-30, 4he addition
White light can be produced b y : (1 ) developing of increasing amounts o f polyvinylchloride reduces
an extensive continuum, ( 2 ) exciting an extensive the candlepower o f a magnesium-strontium nitrate
discrete band system, and (3) exciting two nearly flare; however, its color value (see Paragraph
complementary band systems. The light produced 6-2.5.5) as a red flare increases as shown in Figure
by incandescent carbon particles, or the extensive 6-31. Red color values o f greater than 0.40 are
sodium continuum produced by the magnesium-
impossible to obtain unless the color intensifier or
sodium nitrate illuminating flare, are good ex­
binder is a chlorine containing compound. As al­
amples o f method (1 ). The extensive band system
ready indicated, in the absence of a chlorine com­
o f barium Oxide (BaO) (400 to 800 millimicrons)
pound, the red color may be due to strontium oxide
is an example o f method (2 ). Suitable blending of
while, in the presence o f chlorine, strontium chlo­
the emission from strontium chloride (SrCl) (red),
ride appears to be the emitting species. 85
calcium chloride (CaCl2) (yellow), andl barium
chloride (BaCl2) (green) is an example o f method The production of a saturated green light by
(3 ).' ■ ■: . I . pyrotechnic means is more difficult than produc­
tion of a red light of relatively high saturation.
6-3 5.4 Color iBtensifien In most pyrotechnic items, the production o f green
Highly chlorinated organic compound^ such as light appears to depend on the green emitter,
hexachloroethane, hexachlorobenzene, polyvinyl­ barium chloride, formed from the decomposition

6-37
 AMCP 706-185

TABLE 6-7
H EATS OF REACTION OF MAGNESIUM W ITH
STOICHIOMETRIC QUANTITIES OF VARIOUS OXIDANTS

Heat of Reaction
Composition t •UUiVVtp
Oxidant Density, g fee* Real, Total Cal/g is-tnp Cal/cc Comp* Assumed

A1(C10 4 ) 3 2.14 est 1,732 est 2,810 est 6 ,0 1 0 est MgO-AlCl8

M g(C104)2 2 .1 1 1,163 2,785 5,880 MgO-MgCU
LiCIO* 2.04 573 2,810 5,740 MgO-LiCl
NaCIO* 2 . 1 0 est 581 2,650 5,560 est MgO-NaCl
KCIO* 2.13 576 2,440 5,200 MgO-KCl
B e (N 0 8 ) 2 2.04 est 681 est 2,675 est 5,420 est MgO-BeO-N 2
AgNOs 3.00 804 1,656 4,970 MgO-Ag-N 2
LiNOs 2.03 631 2,430 4,940 MgO-Li2 0-N2
P b (N 0 8 ) 2 3.03 756 1,584 4,800 MgO-Pb-N 2
C a (N 0 8 ) 2 2.04 647 2,265 4,620 MgO-CaO-N2
S r (N 0 8 ) 2 2.38 627 1,880 4,480 MgO-SrO-N 2
N aN0 8 2 .0 0 594 2,035 4,070 Mg0 -Na2 0 *N2
B a (N 0 8 ) 2 2.54 616 1,610 4,080 MgO-BaO-N 2
KNOs 1.95 570 1,760 3,430 M g0-K 2 0-N 2
F 2 (liq) 1.29 264 4,230 5,460 MgF 2
0 2 (liq) 1.44 288 3,570 5,140 MgO
Pb02 5.37 222 770 4,140 MgO-Pb
BaC>2 3.53 137 630 2 ,2 2 0 MgO-Ba

* Based on calculated true density.

products of barium nitrate and an organic chlorine proved the green color, but to a lesser degree.
containing compound. Ethylcellulose, the one nonchlorinated organic ad­
Magnesium also combines readily with chlorine ditive tested, improved the color of the flAre slight­
and, therefore, will compete with the barium for ly as a larger percentage of it was used. This
the available chlorine. There is also competition slight improvement in color is believed to be due
between chlorine and oxygen for the barium. To to the decrease in luminous intensity. The im­
select the best chlorine donor (CI2 is ideal but too provement in color o f the compositions containing
difficult to handle), several compositions were chlorinated organic additives resulted from an
tested which contained Organic chlorides having increase in the amount o f barium chloride formed
different percentages of chlorine. These compounds as well as from decreased luminous output.
lowered the candlepower, with generally improved It has also been suggested that the addition o f
color, and increased th« amount of barium chloride a chlorine containing compound to a flare mix­
formed. The best results were obtained with a ture may, by shift of equilibrium, result in the
composition containing 40 percent magnesium, 45 formation of barium hydroxide which emits strong­
percent barium chlorate, 1 0 percent polyvinylidine- ly in the green. 2 2
chloride, and 5 percent Laminae. The chlorine-to-
barium ratio was 3.48 to 1.0; the magnesium-to- 6-3.5.5 Binders
barium ratio was 1 1 . 8 to 1 .0 , and the chlorine- Binding agents— including certain resins,
(available to barium)-to-barium ratio was 0.272 to waxes, plastics, and oils— serve multiple purposes
1.0. All other chlorine containing additives im­ in pyrotechnic compositions. They are added to

6 -3 8
 AM CP 706-185

catalyzed, they undergo a transition from liquid

gel to solid as they cure .42
The results of a series of tests involving poly­
ester resins, presented in Table 6-9, led to the
conclusion that the majority of these resins would
be satisfactory and that mixtures containing these
materials would be as stable and have the same
burning characteristics as mixtures containing
Laminae as a binding agent.
The luminous intensity for all mixtures tested,
including a binary mixture not containing a binder
of any kind, varied greatly during the first month
of storage. This strongly indicates that the binder
is not the cause of this variation. There is, how­
ever, little, if any, change in burning rate asso­
ciated with this change in luminous intensity.

6-3.5.6 Particle Size

The rate of reaction of . a pyrotechnic composi­
tion is related to the specific surface of the in­
gredients. Factors such as size, shape, distribu­
tion, and surface of the particles affect the proper­
ties of the particulate material and must be ac­
Figure 6 -2 2 . Zones in Flame P ropa g a tio n curately controlled. These factors affect the pack­
ing properties of the ingredients which, in turn,
prevent segregation and to obtain more uniformly affect the weight-volume relationship of the par-
blended compositions. In addition, they nerve to tides.
make the finely divided particles of metal and As has been indicated in the discussion of prop­
oxidizer adhere to each other and help to obtain agative burning (Paragraph 3-3.6;, the burning
maximum density and, therefore, efficiency in rate and candlepower of a pyrotechnic composi­
burning. Hinders also frequently desensitize mix­ tion depend on the particle size of the metal pow­
tures which would otherwise be very sensitive to der fuel. This effect is shown in Figures 6-32(A)
impact, friction, and static electricity and, as and 6-32(B), and Table 6-10 for an illuminant
binder content is increased, burning rats is de­ mixture containing magnesium, sodium nitrate,
creased and candlepower reduced. polyvinylchloride, and Laminae. A decrease in
Materials such as linseed oil, used, earlier in particle size for the spherical particles results in
most standard pyrotechnic compositions as binders, an increase in the specific surface— the surface area
oxidized and hardened during storage causing a associated with one gram of powder— an increase
change in the burning characteristics. The re­ in the candlepower, and an increase in the burn­
placement of linseed oil by Laminae, a polyester ing rate. This is in agreement with the theory pre­
esin,41 greatly reduced this problem . 8 It was sented in Paragraph 3-3.6.
found that self-hardening polyester resins tended The above results were obtained for composi­
to minimize the need for high consolidation pres­ tions in which the magnesium was essentially a
sures. Most of the polyester resins usecl are es­ sphere; any other particle shape will result in a
sentially esters manufactured from glycolf and un- larger specific surface than that of a comparable
taturated acids, and monomeric cross-linking addi­ sphere. In Table 6-1 i, the burning characteristics
tives such as styrene and diallyl phthalate which of similar compositions prepared with ground and
are utilized to cure the resin. When the resins are with atomized magnesium having the same sieve
 AMCP 706-185

3 .4 0

Figure 6 -2 3 . Temperature D istribution in a Pyrotechnic Flame

6-40

X
 AMCP 706-185

Figure 6 -2 4 . Luminous Intensify as a Function o f Iagnesium C ontent o f Binary M ixtu re s C ontaining Various O x id iz in g
Agents

sizes are compared .48 The ground magnesium 6-3.5.7 Consolidation44

(which for some sieve sizes will have the neater The degree of consolidation (loading pressure)
specific surface) gives a higher luminous intensity has a varying effect on the burning rate and lum­
and a faster burning rate. An increase in burning inous intensity o f a pyrotechnic mixture, depend­
rate and luminous intensity generally follows the ing 1 on the physical characteristics of the com­
increase of specific surface of the ingredients. It ponents. Increased consolidation pressure results
is to be noted, however, that an increase in burning in an increased pellet density which approaches a
rate and luminous intensity may be accompanied maximum, which is usually five to ten percent less
by a reduction in the overall efficiency. than the theoretical value. In Figure 6-33 and
The burning characteristics of pyrotechnic Table 6-12 are shown the effects of loading pres­
compositions are also affected by the specific sur­ sure on burning rate, luminous intensity, and
face of the oxidizers and other ingredients. While other characteristics, between 2000 psi and 25,000
relatively little data are available on the specific psi for magnesium-sodium nitrate flares. The lin­
effect produced in a particular system, in is im­ ear burning rate shows a slight decrease with load­
portant that they be considered. ing pressure while the mass burning rate and lum-

6-41
 AMCP 706-185
B U R N I N G R A T E , IN C H E S PER M INUTE

Figure 6 -2 5 . Burning Bale a t a Function o f Magnesium Content o f Binary M ixtures C ontaining Various O x id iz in g Agents

6-42
7T

AMCP 706-185

TABLE 6-8 (A)

PHYSICAL DATA AND BURNINGl CHARACTERISTICS FOR STOICHIOMETRIC
MIXTURES OF VARIOUS OXIDANTS WITH ATOMIZED MAGNESIUM

Stoichio­ ‘ Ci Iculated Luminous

metric Heat 1/ Reaction Intensity Burning Rate Efficiency,
Oxidant Ratio Real Cal/g Candle/sq in. in./min candle-sec/g

LiNOs 53.2/46.8 631.0 2430 109,000 13.9 17,500

NaNOs 58.3/41.7 595.4 2060 10 2 ,0 0 0 13.1 15,500
kno8 62.5/37.5 569.8 1760 27,500 6.9 8 ,0 0 0

C a (N 0 8 ) 2 57.5/42.5 647.1 2260 64,000 6 .8 18,000

S r (N 0 8 ) 2 63.5/36.5 626.8 1881 50,500 7.7 12,500
B a (N 0 8 ) 2 68.8/31.8 615.5 1606 45,000 5.1 14,000
KCIO 4 58.8/41.2 515.8 2441 37,000 5.2 15,000

inous intensity show an increasing trend. These other cases the results have varied considerably.
data have been found consistent with the trends With certain compositions, investigators have ob­
observed in most pyrotechnic compositions con­ served an apparent maximum in linear burning
taining magnesium although they are not is con­ rate associated with a particular flare diameter.45
sistent for compositions containing aluminum. Investigations of typical yellow, green, and red
Insufficient consolidation of tracer comp osition flare compositions with diameters varying between
in the tracer cavity may result in the tracer mal­ 0.6 inch to 1.1 inches indicated that the luminous
function known as “ blow out,” where the pyro­ intensity could be expressed mathematically by an
technic composition is ejected from its cavity. This equation of the form :48
usually happens shortly after the projectile leaves y = axn (6-15)
the gun. In ammunition depending on tracer func­ (for diameters less than approximately 4 in.)
tioning for self-destruction, this usually results where y is the luminous intensity (candela), a
in a premature projectile functioning. is a constant, x is the flare diameter in inches, and
The required loading pressure or extent of n is a constant, The value of n, which was ob­
consolidation depends on the setback forces and tained when the results were plotted on log-log
amount o f rough handling to which the item is paper, indicated that » is slightly greater than 2.0
to be subjected. Generally, the greater the setback which may be due to some change in the flame
forces, the greater the required loading pressure. geometry, or to an increase in the flame tempera­
ture. The flame area tended to exhibit a direct
6-3.5.8 Flare Diameter proportionality with the square of the flare diam­
The influence of flare diameter on the linear eter. Yellow and green flares showed an increase
and mass burning rate, luminous intensity, tem­ in luminous efficiency with increased luminous in­
perature distribution, color value, luminous effi­ tensity; however, their flames appeared to become
ciency, and flame geometry may vary considerably less saturated with increasing flare diameter. Red
depending on general configuration of the system flares exhibited maximum luminous efficiencies for
and the pyrotechnic composition. A basic end­ intermediate values of luminous intensity and the
burning flare, free from the influences of case color characteristics did not appear to change with
geometry and composition and associated mate­ an increase in flare diameter.
rials, should possess a linear burning rate essen­
tially independent of the flare diameter. This has 6-3.5.9 Case Materials and Coating
been the case in many investigations conducted Both the physical and chemical characteristics
over rather limited diameter ranges; however, in of pyrotechnic case material and associated coat-

6-43
AMCP 706-185

Figure 6 -2 6 . C h n m a tic ity D a ta for Red, Yellow, a n d Green F la n s

6-44
 AM CP 706-185

Flgun 6 - 27 . Typical Spectra o f Signal Flans

ing may affect the burning characteristics and the steel case may more than compensate for the
luminous output of flares. Steel cases with high increase observed with red and yellow flare com­
thermal conductivities, as compared to thosie con­ positions. Some compositions also have been ob­
structed o f paper or other materials, may preheat served to bufn more rapidly and produce a greater
the composition and thus tend to decrease the time luminous intensity in laminated plastic cases than
to ignition and increase the burning rate. In addi­ when loaded into paper cases. In this case, the
tion, the increased wall temperature may affect character o f the adherence of the composition to
the coating material and promote side burning. the wall may be important; however, a completely
Both o f these conditions tend to increase the lumi­ satisfactory explanation is difficult.
nous intensity; however, they can cause unpredict­
able performance. 6-3.5.10 Temperature and Pressure
In studies of colored flare illuminating compo­ Ambient pressure and temperature have been
sitions,47 it was found that red and yellow flares found to have varying effects on the operating
had higher burning rates and luminous intensities characteristics of illuminating flares, depending
when using steel cases as opposed to paper cases. on the composition. In a study48 made on yellow,
When paper-lined steel cases were used, luminous red* and green compositions it was found that at
intensity values were midway between those for a reduced temperature., —65°F, the candlepower
steel and those for paper, although. burning rates and burning time o f the flares, except for green,
were comparable to those obtained for paper cases. decreased. The color value Was found to be affected
In contrast, the relatively cooler-burning green differently, depending on the composition at this
composition gave lower luminous intensity! values temperature. (See Tables 6-13, 6-14, and 6-15.)
in the steel case than in the paper case (for which A t high simulated altitudes, the burning time in­
intermediate values were obtained) even though, creased while the candlepower decreased for most
the burning rates remained essentially the same. flares tested in this study. Color values were in­
In this case, the heat loss to the surroundings from creased at the higher simulated altitudes with the

6-45
\MCP 706-185

TABLE 6-8(B)
CHARACTERISTICS OF BINARY MIXTURES CONTAINING OXIDIZING AGENTS
AND ATOMIZED MAGNESIUM, GRADE A

Commmtion*
Parts by Weight Horisontal •Pendulum Pridian j*rc V
Luminous Impact Test Reaction with Vacuum Efficiency,

III
Atom. Or. A Intensity, Burning Ignition /pnitibifify Test Stability CaruSe*
Sodium Candles per Koto, Temperature A s Black B.W . App.A Sieei Fiber Test, cc, Density Seconds
Nitrate mepnrttum Square Inch in ./m n *N Powder, q cm Shoe Shoe gasH O Art. gae/tc per gram
_ _

1
80 20 4,600 2.4 636 >5 86 None 0.30 1.91 3,600
70 30 38,600 7.7 — 630 >5 96 None — 0.36 1.87 9.700
42 13.1 0.026 630 0 .5 100+ None — 0.82 1.82 16,600
58 102,000
64 46 155,000 16.6 0.024 636 0 .5 100+ None — 0.31 1.79 20.000
50 60 180,000 16.6 0.026 035 1.26 100 None — 0.36 1.74 20,000
40 60 388,000 28.7 0.029 620 1.26 100 None — 0.32 1.71 31,000
30 70 686.000 89 0.036 620 1.76 100 None — 0.32 1.66 36.000
25 75 786,000 43 0.033 — >5 100+ None. — — 1.62 41,000
20 80 670,000 43 0.038 670 2.76 100+ None — 0.33 1.69 30.000
16 85 446,000 32 0.041 870 >6 100+ None — 0.23 1.61 33,000
Barium Atom.Or.A
Nitrate M agnetium
so 20 6,600 2.9 pale green 680 >6 100+ None — 0.26 2.48 3,300
68 82 46.000 5.1 pale green 670 >6 100+ None — 0.25 2.24 14,000
64 36 63,000 6.7 pale green 640 >5 100+ None — 0.16 2.21 13,000
60 40 69,600 10.7 pale green 635 >5 100+ None — 0.18 2.08 9,800
60 60 186.000 18. g pale green 616 1.26 100+ None — 0.21 1.66 13,000
40 60 348.000 38.1 pale green 626 1.26 100+ None — 0.16 1.86 17,600
30 70 860.000 40.3 pale green 616 >6 100+ None — 0.20 1.64 17,600
20 80 Erratic Burning — 625 >8 100+ None — 0.22 1.83 *—
Strontium Atom.Gr.il Red Color
Afoonuium Value
80 20 10,600 2.7 0.20 616 >5 100+ None — 0.13 2.32 6,600
70 30 34.000 8.0 0.19 600 >5 100+ None — 0.16 2.05 10.000
63.6 36.5 60,500 7.7 0.18 600 >5 100+ None — 0.16 1.96 12,600
60 40 68,600 8.9 0.16 600 >6 100+ None — 0.14 1.92 12,000
60 60 152.000 21.1 0.22 610 >5 60 None •— 0.14 1.79 14,500
40 60 260,600 24.8 0.24 610 >5 100 None — 0.19 1.72 22,000
30 70 307.000 28.0 0.26 616 >8 100+ None — 0.27 1.63 24,QOQ
26 76 286,000 24.0 0.31 620 >5 100+ None — 0.18 1.67 27,600
20 80 260,000 20.4 0.27 610 >6 100+ None — — 1.52 33,000
Lithium Atom.Gr.A Red Color
N itrate Magnesium Value
80 20 Erratic Burning 1.98
70 30 21,000 0.17 1.77 7,200
60 40 76,600 13.3 0.16 1.68 12,600
68 47 109,000 13.9 0.18 1.62 17,600
40 60 236,000 27.9 0.20 1.64 20,000
80 70 860,000 41.6 0.21 1.49 20,000
20 80 370,000 46.1 0.20 1.43 22,000
Calcium Atom.QrA Red Color
N itrate Magnesium Value
80 20 3,600 1.8 0.22 1.99 3,600
70 30 25,000 4.0 0.16 1.96 11,600
67 48 64,000 6 .8 0.16 1.86 18,600
62 46 86,000 8.4 0.18 1.81 20,000
40 60 188,000 12.5 0.26 1.73 82.000
30 70 382.000 22.0 0.28 1.66 40.000
26 76 400,000 23.3 0.29 1.51 41.000
20 so 362,000 21.6 0.80 1.60 41,000
P d a u iam Aiom.Qr.A
Nitrate Magnesium —
80 20 900 2.3 660 >5 80 None 0.16 1.81 600
70 30 1,100 4.7 White 660 2.76 80 None — 0.18 8.75 600
88 27,600 6.9 White 660 1.6 90 None — 0.15 1.73 3,400
62
68 42 36,000 8.6 White 666 2 76 None — 0.11 1.72 9.000
60 60 66,000 13.3 White 660 1.76 90 None — 0.15 1.68 9,000
40 60 86,000 21.8 White 646 1.75 90 None — 0.13 1.63 0,000
30 70 119,090 29,3 White. 636 1.6 100 None — 0.13 1.56 9.600
25 76 116,000 31.1 White — 4 100+ None — 0.19 1.53 0,000
20 80 70,000 26.4 White 630 >6 100+ None — 0.18 1.63 8,300
PcfeMtum Atom.Or.A
Perchlorate Magnesium
80 20 2,600 2.2 White 700 >6 100+ None 0.30 1.01 2.100
70 30 17,600 3.8 White 710 >5 100+ None — 0.24 1.78 9,600
69 41 37,000 8.2 White 706 >6 100+ None — 0.28 1.72 15.000
60 60 46,000 7 .0 White 718 >5 100+ None — 0.26 1.66 14.000
40 60 64,000 10.3. White 700 >6 100+ None — 0.26 1.60 12,000
30 70 171,000 26.6 White 700 100+ None — 0.36 1.54 14,600
20 80 240,000 46 White 100+ None — 0.22 1.61 12,600
it 86 167,000 47 White 100+ None 1.60 8,800
"

'Loading Preaeuro 10,000 pair in 1.4 Square Inch Candle Caaea.

tBonau hi Mince Apparatus.
 AMCP 706*185

■"■K'p
TABLE 6*9
CHARACTERISTICS OF PYROTECHNIC COMPOSITIONS
CONTAINING V A R lO US POLYESTER RESIN BINDERS

Total Integral CIS Coordinates

Candlepo Burning Rate, Light, 10*
Polyester Resins 1000 Candies inch/minute Candle-seconds X V
Hetron-92 84.0 4.4 3.7 0.52 0.36
Paraplex-43 70.3 3.6 4.0 0.64 0.36
Paraplex-444 66.0 4.2 3.2 0.60 0.36
Laminae 4116 64.6 3.8 3.3 0.51 0.36
Paraplex-13 62.5 3.3 3.7 0.63 0.36
Paraplex-47 62.0 3.4 3.5 0.52 0.36
Glidpol-1001-A 61.2 3.5 3.4 0.52 0.36
Interchemical-401 60.6 3.9 3.5 0.57 0.32
Pleogen-1150 60.3 4.0 3.2 0.64 0.34
Aropol-7120 60.0 3.3 3.6 0.56 0.33
Polylite-8001 89.3 4.1 3.3 0.66 0.33
Interchemical-937 68.0 4.0 3.3 0.67 0.33
PoIylite-8007 66.8 3.8 3.2 0.66 0.34
4116-85%:4134-16% 56.6 4.1 3.2 0.65 0.33
Aropol-7300 66.4 4.3 3.0 0.56 0.33
Pleogen-1006 ' 66.4 4.1 3.0 0.66 0.34
ED-199 66.2 4.1 3.2 0.67 0.32
PLL-4262 66.0 4.1 3.1 0.68 0.32
Vibrin-1088-B 64.5 3.4 3.4 0.66 0.33
Paraplex-49 64.4 3.4 3.1 0.52 0.36
Laminac-4134 63.7 3.9 3.0 0.66 0.34
Vibrin-117 62.9 3.9 3.0 0.66 0.33
Interchemical-312 51.7 4.1 2.9 0.66 0.32
Celanese-MX-314 61.4 4.0 2.8 0.66 0.34
Interchemical-1191 51.4 4.0 2.9 0.56 0.33
Interchemical-730 51.4 3.7 3.1 0.67 0.32
Interchemical-1154 60.2 4,0 2.9 0.66 0.33
Stypol-4051 49.6 3.8 2.8 0.66 0.33
Stypol-405 49.1 4.0 2.7 0.66 0.34
Aropol-7110 49.0 4.2 2.7 0.66 0.33
Selectron-5027 48.4 3.7 2.9 0.66 0.34
Celanese MR 28-C 46.0 4,0 2.6 0.66 0.34

Rpoxu Resin
Bakeute ERL-2796 ' 81.2 5.1 3.8 0.69 0.30
■ 1

exception of green which remained essentially con­ resistance offered by the air molecules. Inter­
stant. mediate reactions occur further away from the
The range o f altitudes at which pyrotechnic flare surface and, in many cases, a “ dark zone”
items may be used is from zero to approximately can be observed just above the flare surface and
250,000 feet. The effects produced under reduced initial reaction zones. I f the pressure becomes low
pressures can be attributed to both the reduction enough, a point will be reached where the reaction
in oxygen and ambient pressure. The effects of will not be self-sustaining.
oxygen reduction may be greater when fuel-rich The inverse relationship between candlepower
mixtures are burned. For stoichiometric or near­ and color value is attributed to the increasing im­
stoichiometric compositions, the effect is mainly portance of the color line and band emission from
that of pressure. It has been shown that by main­ excited atoms and molecules at the higher altitudes.
taining a pressure over the flare surface through
partial confinement by use o f a nozzle, the burning
rate at high simulated altitude could be ifaised to 6-3.5.11 Rotational Spin
the same level as that at sea level.49 The effect of rotational spin on the burning
Larger flame plumes are produced as the am­ characteristics o f compositions has been investi­
bient pressure is reduced due to the decrease in gated. It has been found that the rotational spin

6-47
AMCP 706*185

Figure 6 -2 6 . Spaefral Energy D irlrib v fio n o f Groan Flora

of a 105 mm illuminating projectile canister con­ ated by the fact that flares which are rotated at
siderably shortened the burning time of the il- the slowest speeds (which have the longest burning
luminant. The effect of rotational spin on flares times) show much less slag residue than those ro­
loaded in 1.5-inch O.D. steel flare cases was also tated at higher speeds. Flares tested at speeds
studied. Examination of burned out flare cases o f 3,000 to 5,000 rpm, however, all contain ap­
indicated that the resulting centrifugal forces pre­ proximately the same amount of slag.
vents the expulsion o f much of the slag. The slag In another study, the trace duration of a tracer
builds up and effectively decreases the internal was found to be shortened, as shown in Figure
diameter o f the case. This decrease in internal case 6-34,60 by rotational spin. Burning rates for tracer
diameter prevents the efficient expulsion of gases compositions increased with an increase in diam­
formed and thus causes an increase in the internal eter, or length of tracer column and this increase
pressure. As a result of the pressure increase, the was more pronounced as angular speed was in­
illuminants burn more rapidly. This is substanti­ creased. In general, for each composition the per-

6-48
 AMCP 706-185
■T

TABLE 6-10
EFFECT OF PARTIBLE SIZE ON BURNING RATE
AND CANDLEPOWER FOR MAGNESIUM-SODIUM NITRATE-
POLYVINYLCHLORIDE-LAMINAC MIXTURE

Average Particle
Ingredients Size, microns Percentages

Magnesium, At., 20/50 437 48

Magnesium, At., 30/50 322 48
Magnesium, At., 50/100 168 48
Magnesium, At., 100/200 110 48
Sodium Nitrate, DR, ULP 34 42 42 42 42
Polyvinylchloride 27 2 2 2 2
Laminae Resin 4116 8 8 8 8

, Time-Intensity Data
Candlepower, 10s candles 130 154 293 285
Burning Rate, in./min 2.62 3.01 5.66 5.84

2 40
3
3» .3.8. -
Z
<9
< 30
2
t 28
O
at 20 -

18.
70 72 74 78 78 80 82
PERCENT PURITY
Figure 6 -2 9. Magnesium Content Versus Excitation Purity
for a Yellow Flare

centage loss of slag decreased for each diameter

with an increase in rotational speed. Total! light
ontpnt expressed in candlepower seconds decreased
with an increase in rotational speed.00

6-3.5.12 Moisture and Stability

One of the important factors in determining Figure 6 -30. Effect o f Polyvinylchloride on the Candle-
the stability and shelf life of a pyrotechnic item power o f Mixtures Containing Strontium Nitrate and
Ground Magnesium, Grade A
is the sensitivity of the pyrotechnic composition
to atmospheric moisture. In the presence of
moisture, the oxidant will react with the metal hydroxide, or both. This nonreaotive layer changes
particles to form a layer of metal oxide, metal the ignition and propagative characteristics of the
 AMCP 706-185

TABLE 6-11
EFFECTS OF CHANGE IN SPECIFIC
SURFACE OF MAGNESIUM PARTICLES

Ground Atomized
Magnesium Magnesium

COMPOSITION, %
Ground magnesium 66.6 ’ — V

Atomized magnesium • . — '■ 66.6

Sodium nitrate 28.6 28.6
Resin 4.8 4.8
(100.0) (100.0)
CH ARACTERISTICS
Candles per sq in. 200,000 178,000
Burning rate, in. /min 9.4 57
Density 1.56 1.65
Candle-seconds/gram 50,000 69,200

pyrotechnic mixture so that reduced luminous

intensity or nonignition may result. 20 SO 40 SO 60 70
The critical relative humidity is a measure of MAGNESIUM, KARTS
the sensitivity o f oxidants to moisture. It is deter­
Figure 6-31. Effect o f P olyvinylchloride on the C o lo r Value
mined by exposing samples of the oxidizers to at­ o f M ixtures C ontaining Strontium N itra te and Ground
mospheres o f known relative humidities and «• Magnesium, G rade A
mining the change in weight of the oxidizer. s
critical relative humidity is that at which, with in­ In some cases, it has been found, expedient to
spect to moisture content, the oxidizer is in equi­ compromise due-to an oxidizer's excellent oxidizing
librium with its surroundings. Roughly, the higher ability. This has been the case with sodium nitrate
the critical relative humidity, the less soluble the that formerly had a critical humidity of 50 percent
oxidant. Small traces of impurities may lower the for the specification grade. The use of U.S.P.
critical relative humidity of a compound. double-refined sodium nitrate with A critical

■ . . , ■. - ■ .. TABLE 6-12 ■; \ = ■ ■
EFFECTS OF LOADING PRESSURE ON BURNING CHARACTERISTICS
OF MAGNESIUM-SODIUM NITRATE FLARES ......

L u.ninc e t ‘, m p o siiio n
L u m in ou s
B u rn in g h u n tin g C h rom a ticity E fficien cy, D en sity ,
l o a d in g I n te n s ity , T o ta l L ig h t,
P ressu r e, 1000, I X to * Candle- B a te, 1; elite B ute- O C olor ' : C ofd iiia tes, 1000 C -Scc ■ Grains
P er con d JSatio V P e r Grai.i P er r G
P ei C andles S econ d s P e r M in u te »

2,000 278 7.2 6.20 i;/,t 0.036 0.48 0.46 42.6 1.54
4,000 292 7.0 6.33 7.20 0.036 0.48 0.46 40.7 1.64
7,000 262 7.1 5.62 (-.75 0.037 0.48 0.46 38.7 1.74
10,000 270 7.8 5.47 7.1:2 0.085 0.48 0.46 37.9 1.90
15.000 286 7.4 5.63 7.69 0.035 0 48 0.45 37.2 2.03
20,000 291 7.6 5.67 7.55 0.035 U.48 0.46 38.6 1.95
25,000 290 7.5 5.92 7.69 0.037 0.49 0.45 37.8 1.88

6 -5 0
 AMCP 706-185

TABLE 6-13 ...........

E F F E C T OF SIM U L A ! ED ALTITU DE AND TEM PERATURE
ON ILLUMINATION CHAJRACTERISTICS OF YELLOW SIGNALS

COT Y -l LOT Y-2

Average Average
Simulated ' Luminous Burning Yellow** Luminous Burning YeUow**
Altitude,* Temperature, Intensity, Time, Color Intensity, Time, Color
Feet °F Candles Seconds Value Candles Seconds Value

0 70 53,300 19 .038 124,000 9.3 .052

10.000 70 39,200 21 .047 113,000 11 .062
20.000 70 19.200 24 .058 91,000 9.5 .062
40.000 70 6,650 49 , 064 55,000 12 .072
0 — 65 44,500 16.5 .055 78,000 9.5 .074,

* Pressure reduced to simulate condition at alti tudes 9hown. ,

** The color value was determined using the pro< edure given in PA Tech Beport' No. 1385.

TABLE 6-14
E F F E C T OF SIMULAT ED ALTITUDE AND TEMPERATURE
ON ILLUM INATION Cl IARACTERISTICS OF RED SIGNALS

LOT R -l LOT R-2

•

Average Average
Simulated Luminous Burning Red** Luminous Burning Red**
A ltitu d e* Temperature, Intensity, Time, Color Intensity, Time, Color
F eet °F Candles Seconds Value Candles Seconds Value

0 70 26,400 18.3 .44 48,000 14 .56

10.000 70 17,200 22.5 .47 30,000 19 .59
20.000 70 14,500 27 .53 25,700 22 .60
. 40,000 70 9,300 41 .62 15,500 35 .69
0 — 65 25,400 16.5 .40 38,000 14.5 .60
* Pressure reduced to simulate condition at alt. tudes shown.
** The color value was determined using the pro: edure given in PA Tech Beport No. 1385.

humidity of 75 percent partly alleviatec i this mospheres of nitrogen and oxygen exerted only a
problem.48 slight influence on the corrosion rate whereas hy-
The effect o f moisture on a finely po srdered drogen and carbon dioxide were observed to have
metal can be determined by placing a sam pie in retarding and accelerating effects, respectively.
distilled water and maintaining the system at a Further, the rate of corrosion increased with an
specified constant temperature. By collectirig the increase in specific surface,
gas evolved at constant pressure, the rate of cor- One way that the deleterious effect o f moisture
rosion of the metal can be established, For on magnesium or other metal can be avoided is
atomized magnesium,51 it was found that t i e rate to coat the metal with a thin chromate film. Pro-
of corrosion increased with time but only si ightly tection of the atomized magnesium in consolidated
between the temperatures of 30°C and 65°0 . At- illuminating and signal compositions may also be

6-51

■
AMCP 706-185

TABLE 6-15
EFFECT OF SIMULATED ALTITUDE AND TEMPERATURE
ON ILLUMINATION CHARACTERISTICS OF GREEN SIGNALS

LOT 0-1 LOT G-2

Average Average
Simulated Luiiwnous Burning Green** Luminous Burning Green**
Altitude,* Temperature, Intensity, Time, Color Intensity, Time, Color
op Candles Seconds Value Candles Value
Feet Seconds

0 70 14,300 16.5 .36 38,700 16 .35

10,000 70 14,300 21.5 .39 20,500 15 .36
20,000 70 11,500 26.5 .37 20,500 17 .36
40,000 70 11,000 30 .41 19,500 26 .35
0 — 65 27,800 20 .36 35,700 15 .35

* Pressure reduced to simulate condition at altitudes shown.

*• The color value was determined using 'the procedure given in PA Tech Report No. 1385.

Figure 6-3 2 .1 . Burning Rate vs Particle Size o f M agnesium Figure 6 - 32.2 . Candlepower vs Particle Size o f Magnesium

accomplished by the use of binders and water minants because they do not contain binders and
proofing agents, usually an oil, wax, or plastic lire loose-loaded which changes the manner in
resin. Containers and nonhygroscopic first-fire which they react to produce light. Consolidated
compositions are used to keep moisture from the compositions burn comparatively slowly while non
main illuminating compositions. consolidated mixtures, under confinement, react
rapidly producing a bright flash of light.
6-4 NONCONSOLIDATED ILLUMINANT The major uses for nonconsolidated illuminant
CHARGES charges are in photoflash bombs and cartridges for
. As pyrotechnic reactions, in general, are based night aerial photography, and in spotting charges
on the chemical reaction of a fuel with an oxidizer, for tracking and acquisition purposes. Nonconsoli­
the manner in which these two basic ingredients dated fillers include: (1) intimate mixture of a
are incorporated into a pyrotechnic device will powdered metal and powder oxidant, (2) a pow­
greatly influence its performance. Nonconsoli­ dered metal, such as aluminum, magnesium, or
dated illuminants differ from consolidated illu- their alloys, and (3) a powdered metal and a

6-52
 AM CP 706-185
INCHES PER MINUTE
RATE,
ftURNfNR

Figure 6 -3 3 . E ffect o f Loading Pressure on Burning Riiite o f

■ Pyrotechnic Compositions

powdered oxidant segregated from each ( ther

in concentric cylinders. *■■
Figure 6 -3 4 . E ffect o f Spin U pon Trace D u ra tio n o f V arious
S tandard Tracer Compositions When Loaded In to Caliber
6-4.1 A E R IA L PHOTOGRAPHIC .5 0 M l Jacket •
ILLUMINANTS
The mission of aerial photography is to obtain tion of the light reflected from the area to be
information regarding the static content of an area photographed which reaches the photographic film,
(buildings, roads, etc.), and the movement o f per­ and :
sonnel and equipment. A t night, this requires a c. Exposure time which, for night aerial pho-;
light source that will produce sufficient illumina­ tography, may be the duration of illumination and
tion to obtain usable negatives. High intensity not the shutter speed.
light sources for night aerial photography may , The intensity of the light source and its rela­
be broadly divided into two classes, pyrotechnic tive location determine the illumination received
light sources, and the electronic flash tube.®2 As by the area to be photographed as well as the uni-
flash tubes are unable to produce as much light as fora ity of the illumination produced. As shown
pyrotechnic light sources, their use is limited to in Figure 6-35, the location of a pyrotechnic light
low altitudes. A t higher altitudes, photoflash car­ source can be specified by giving the trail angle
tridges and photoflash bombs are the only prac tical and the burst altitude. The trail angle must be
sources o f intense illumination for night aerial sufficiently greater than the camera half-angle to
photography using conventional aerial cameras assure that only the reflected light from the area
and photographic film. being photographed will reach the camera lens. !
The film speed, basically, determines the amount For a normal trail angle value, the optimum
of light which must fall on the film in order to burst altitude has been determined to be about 0.6
obtain a satisfactory negative. The amount of light o f the flight altitude, when the required intensity
which reaches the photographic film depends on: of the light .source is a minimum.58 A t the opti­
a. Amount of light reflected from the area to be mum burst height the amount of light required for
photographed, which depends on the illumination a satisfactory negative is approximately:®2
and the terrain reflectance o f the area,
6'AUt{kf)*
b. Relative aperture o f the camera lens which is (6-16)
T
normally expressed by / values on a lens barrel are
the diameter o f the lens aperture divided by the where l is the candlepower of the light source, T
focal length o f the lenses. The transmission char­ is the exposure time, / is the effective / value for
acteristics of the atmosphere determine the por- the lens, X is the slant distance from the camera
AM CP 706-185

pelling charge which ejects the inner charge. At

the same time, the delay fuze is initiated and, at
the end of the delay time, a relay explosive charge
is initiated and, in turn, initiates the photoflash
mixture. As the delay time determines the location
of the burst behind (and below) the aircraft, the
proper delay time will depend on the speed of the
aircraft during the photographic mission. For this
reason, photoflash cartridges are furnished with the
different delays indicated in Table 6-16 which sum­
marizes the characteristics of some photoflash car­
tridges. Characteristics of a typical photoflash
composition are shown in Table 6-17.

8 » TR A IL ANG LE H - FLIGHT ALTITUDE 6-4.1.2 Photoflash Bombs

a m CAMERA HALF-ANGLE h - BO M B B U R ST A L T IT U D E Illumination for high altitude night photog­
raphy is provided by photoflash bombs which are
Figure 6 -3 5 . D ia g ra m o f Bomb Burst and T ra il A n g le
released from the aircraft during the photographic
run. A typical photoflash bomb is shown in Figure
lens to area being photographed^ and P4 is a fac­ 6-38. Descriptive data and characteristics of photo­
tor best determined experimentally. However, as flash bombs containing photoflash powder are sum­
shown in Figure 6-36 (which is a typical charac­ marized in Table 6-18.
teristic carve for black and white negative ma­ Photoflash bombs containing a relatively large
terial), it is impossible to estimate the exposure P4 amount of flash powder can be very dangerous
required to produce a negative of satisfactory since they can be exploded by impact. Because of
photographic density. Military specification for this danger, dust-type photoflash bombs were de­
film is based on the reciprocal of twice the ex­ veloped. The characteristics of dust-type photo­
posure of a point on the curve at Which the slope flash bombs are summarized in Table 6-19.
of the longest is one-half gamma; for this film In 1950, the development of a segregated oxi­
the military speed is 300 ASA. A satisfactory ex­ dant bomb in which the burster oxidant and metal
posure would correspond to about one-half way dust were loaded separately in coaxial cylinders
up the linear part of the characteristic curve, i.e., was started. Such a configuration appeared to
for this material an exposure of approximately offer the possibility of safety from impact initia­
0.05 log E units. ' tion, and also of producing the high peak candle-
power of the flashpowder bomb, along with the
broad peak associated with the metal dust-type
6-4.1.1 Photoflash Cartridges
photoflash bomb. No photoflash bombs of this type
Illumination for relatively low altitude night were standardized. Results obtained with some
aerial photography is furnished by photoflash car­ experimental segregated oxidant bombs are sum­
tridges. As shown in Figure 6-37, these cartridges marized in Table 6-20.
contain a photoflash charge and a delay fuze assem­
bled into a charge case. This subassembly is put
into an electrically primed outer cartridge case 6-4.1 A Other Photographic Illaminant Systems
along with a small expelling charge. The cartridges Attempts have been made to increase the output
are loaded into specially designed ejectors. Ejec­ of the standard flash bulb by a factor of 100 so that
tion and functioning of the cartridge are initiated it could be used as a night aerial photographic il­
by an electric pulse which causes the electric laminant Unfortunately, it was found that this
primer to t unction which, in turn, ignites the ex­ increase could not be obtained without incurring

6-54
 AMCP 706-185

TABLE 6-16
DESIGNATION AND DESCRIPTION OF PHOTOFLASH CATRIDGES

• ' Ponder
T im

Sice, in.
Total F,nmute Peak
Jntentity,
■ to
Peak, ■ CPS But
Duration
o f N oth,
- Cartridge Detignation L X Dim WT M Type C latt 10° Candle* m ec Total CPS* 6 nuec Casing Pu*e
T10 ■ 7.71X 1.86 ■; 5.25 11 B 24 5 0.77 — ■' Standard M il Tima dolay
Signal cast 1 toSaco

T12 7 .7 2 X 1 .ST 0.72 8.75 11 B 60 8 I — 30 Modifiod M il Time delay 1.2. or 4

see
M tl2 7.73X 1.87 1 7 III A 119 3 1.4 ■— ■ 30 Modified M il Time delay
1,2, or 4 eco .■

M123 (T89) 8 .3 7 X 2 .9 '■7 ” 27.2 111 A 240 4 8 4.8 40 Al Obturated delay fuie,
2,4, or 6 sec

T90 About same About fifteh itar: (b) 8.6 2.5 690 Outer case Obturated delay fuse,
as M112 sane as NiNO i/atom- axrilar to 1 or 2 sec
M112 ued Wg biod- Ml 12; con­
ar, 80/ 70/2 tains 5 stars

TI02- 9X 1.78 1.25 12 rn A • 161) 4 2.4 31(a) Al. 0.051 in. Obturated delay fuse
wall similar to M12& ■
T103 11X2.378 5 .5 27.2 in A 325 4 7.2 A.6 47(a) Al. 0.051 in. Similar to M)23
wall

(•) to 0.1 max.

(b) Contains a high intensity illuminating composition, not photoAssh powder.

disadvantages which essentially nullified anj' gain as well as the use of small arm projectiles as spot­
in output. . ting rounds for major caliber weapons, led to a
Other pyrotechnic light, sources have been ti*ied requirement for more effective spotting charges.
which were designed to produce illumination cn a
continuous basis rather than in short hursts for 6-4.2.1 Small Arm Spotting Rounds
use with strip-type cameras which do not contain Small caliber spotting rounds (ran be used to
a shutter. The film is moved continuously across a aim a major caliber weapon. In operation, the
slit at a speed which matches that o f the in age small caliber spotting rifle, which is rigidly at­
motion. One of ithe early attempts was the us : o f tached lo the main, weapon, is fixed and the point
the T90 photoflare cartridge. This consisted o f the of impact is indicated by a flash of light and a puff
same easing as the M112 with a charge of five stars of smoke formed by the functioning of the small,
which were made of a high intensity consolidated caliber spotting projectile._ As. the trajectory of
illuminating composition. The light output was the small arm spotting projectile and that of the
not adequate as no visible image was obtainec on main round arc nearly identical at the critical
the negatives exposed in flight test at 1000 fe:t.M range, the burst provides information for adjust­
Another attempt was a burner for magnesium dust ment of aim. A hit with the spotting round means
which was developed for use on aircraft.®8,56 that the main projectile will also strike close to the
target.47,58
6-4.2 SPOTTING CHARGES A typical 20 mm spotting round is shown in
Spotting charges are used for locating point of Figure 6-39. This round contains about 6.5 cubic
impact, for target acquisition, for tracking, and for centimeters of a flash mixture and can produce a
indication of item or component functioning. For flash o f 1.5 million candlepowder with a duration of
many years, spotting charges of black powder were 700 milliseconds.
used m practice bombs and projectiles to locate
po’ut of impact. Because the observation distances 6-4.2.2 Tracking .
were relatively short and because a relatively H ig h ly accurate trajectory information is re­
large volume was available for the spotting charge, quired in the development of a missile system.
an adequate flash could be produced with black One method of obtaining this information for a
powder. The development of long range missiles, missile at high altitudes is to photograph the flash

6-55
AMCP 706-185

3 E2 Ei 2 I

LOG EXPOSURE METER CANDLE - SECONDS

Figure 6-36. Typical Characteritiict of Black and White Negative Material

produced by a'photoflash-cartridge ejected a dis­ can be accurately determined.60,61 A typical flash

tance sufficient to prevent damage to the missile charge for this purpose is shown in Figure 6-41.
in flight. Flash cartridges of the type shown in
Figure 6-40 (which are of the same general type 6-4.3 TY PICAL COMPOSITIONS
discussed in Paragraph 6-4.1.1) were developed Typical nonconsolidated illuminating composi­
for this purpose. Modifications to reduce weight tions used as photoflash and spotting charges are
and simplify mounting problems resulted in a flash summarized in Table 6-21.
device which produces a series o f flashes with a
known time interval between them.58 6-4.4 Light Production
As has been indicated, nonconsolidfttcdi illu-
6-4.2.3 Indication of Functioning minants differ from consolidated illuminants in
Flash charges are used also to provide a visible the manner in which they react to produce light.
indication of the functioning of an item or com­ Consolidated compositions propagatively burn in
ponent such as a warhead fuze. The flash signal a relatively slow manner while nonconsolidated
provides a brilliant light flash and can be photo­ compositions react rapidly producing a bright
graphically recorded by remote cameras, providing flash o f light. Because of the rapidity o f the reac­
data so that the time and location of functioning tion, functioning of devices containing noncon-

6-56
 AMCP 706*185

TABLE 6-17
CH ARACTERISTICS OF T YPE III PHOTOFLASH COMPOSITION

Ingredients: Specification Microns Percent

Aluminum, atomized JAN-A-289 15 40

Potassium Perchlorate PA-PD-254 24 30
Barium Nitrate PA-PD-253 147 30
Physico-Chemical Data:
Heat of Reaction, cal/g— 277 4 (calc)
Reaction Temperature, °C— approx. 3500
Gas Volume, c c /g —24 (calc)
Tapped— 1.67
Vac. Stab, 120°C, cc gas/40 hrs— 0.16

Sensitivity Data:
Impact: PA, inches—40-f-
Friction P en d : Sti>el— Crackles; Fiber— No Action
Ignition Temp, ° C : 5 uec value— 610; D TA— No Ignition
H ygroscopicity: 57% RH, room temp; Hrs 24; % W t Gain < 0.1
Electrostatic
Sensitivity: Joule, Min 2.14; 50% Pt— 3.5; 100% P t—4.5
Temp— 6 5 °F ; % RH— 40; Unconfined— Yes

solidated illuminants can cause disruptive effects ration o f the flash (milliseconds). The total amount
in their surroundings similar to the effects pro­ of light produced determines the maximum ex­
duced by high explosives. posure which can be obtained at any altitude,
using open shutter techniques where the duration
6-4.4.1 Light Output Characteristics of the flash determines the exposure time. Unless
The light produced by the functioning of a image movement compensation techniques are used,
device containing a nonconsolidated illumin mt is the speed o f the aircraft must be low enough that
characterized by its relative high peak int ensity image relative movement will not result in unac­
and the relatively short flash duration. ceptable photographic definition. Until the develop­
ment of image motion compensation techniques,
6-4.4.1.1 Time Intensity63'*8 many night aerial photographs were made with
A typical time-intensity curve for the light an exposure time o f He second (40 milliseconds).
produced by the functioning o f a photoflash device In this case, the exposure obtained depended on the
containing a flash powder (intimate mixture o f amount o f light produced in 40 milliseconds, and
powdered metal and oxidant) charge is shown the maximum photographic exposure was obtained
in Figure 6-42. The curve for most spotting with the shutter open for the best 40 milliseconds.
charges would be similar. As indicated in this (See Figure 6-43.) Peak candlepower is important
figure, the important characteristics o f the light as. it greatly influences the amount o f light pro­
output of a photoflash device a re: (1) total amount duced in the best 40 milliseconds. The time-to-peak,
of light produced (candleseconds), (2) amount of and the variation in the time-to-peak are important
light produced in the best 40 milliseconds, CPS 40 for synchronization o f the shutter open time and
(candleseconds), (3 ) peak intensity (candles )> (4) the best 40 milliseconds of the light flash.
time to peak intensity (milliseconds), and (5) du­ Dust-type photoflash devices produce flashes

6-57
AMCP 706-185

CARTRIgpi

EXPELLING
CHARGE

Figure 6 -3 7 . Typical Photoflash C a rtrid g e

which have lower peak intensities and longer dura­ 6-4.4.2 Nature of the Photoflash Burst67'68
tions than those produced by devices containing The light-producing characteristics of a flash
flash powders, as shown in Figure 6-44. Image item depend principally (as discussed in greater
compensation techniques are normally required detail in Paragraph 6-4.5) on the composition, the
when dust-type photoflash bombs are used in order amount and shape of the explosive which is used
to efficiently utilize the light produced. to initiate the composition, and the case. Flash
radiographic studies show that when a relatively
6-4.4.1.2 Spectral Distribution small amount of high explosive— centrally located
As shown in Figure 6-45, the spectral distri­ in a case containing photoflash powder or metal
bution curve of the light produced by a photoflash dust— functions, a bubble o f explosion products
device consists of an intense continuous back­ is formed in the first few microseconds o f the
ground on which a discrete spectra is superim­ initiation of the explosive. The shape o f this
posed.64 The spectral distribution of the radiation bubble and the rate at which it expands are de­
produced by a dust-type photoflash bomb is similar. pendent on the properties of the material sur­
While the more efficient pliotoflash compositions rounding it, as well as that of the explosive initi­
at low altitudes produce light which is mainly ator. For example, the shape of the bubble pro­
continuous, the more efficient compositions at high duced by a small quantity. of explosive in flake
altitudes (100,000 feet) are those which produce aluminum which has a low density tends to be in­
an extensive discrete spectra in the visible.66'66 ( See fluenced more by the nature of the explosive and
also Paragraph 6-4.5.) its confinement than the bubble produced in an-

6-58
 AM CP 706-185

TABLE 6-18
DESIGNATIONS AND DESCRIPTIONS OF F LA SH POW DER PH OTOFLASH BOMBS

Powder Integral Light

10* Candleseconds Duration
ToU Peak rime to
IP S *

o f Flash.
i l l

S iu , in. m, Wl. Intensity, Peak, CPS msec to

L X D ia . lb lb Type C lou 10* Candles msec Total C PSio O .t max, Caring
M12 (Tl) 32X 7.25 32 25 1 325 10 2500 Paper tube divided into 2 compartments;
powder filled 4/5 of volume; plywood
partition; 2 grenade fuses ana parachute
m 1/5
M23 (T2) 25X 4.25 10 7 I — 100 to 300 — 13.5 — — Fiber cylinder; later fitted with steel outer
oasa for improved ballistics
M « (T 3 ) 48X 8 50 25 11 A.B 770 18 50 26 140 Inner fiber charge container; outer steel
ease 0.03 in. wall
T4 Enlarged M46 — 50 II B 970 20 65 36.4(c) Light weight sheet metal case, powder in
fiber container
TS Enlarged M46 — 100 II A 1670 20 132 71.5(c) - light weight sheet metal case, powder in
fiber container
T6 (M60) 31.72X 4.92 25 10 II B 300 11 15.4 8(c) — 0.02394n. wall. Thin metal case
T8E1 — — — — — 0.026-in. wall
T0E2 500 — . “ - — 0.048-in. wall;
NDRC 80 Best Best
Types 58X 10.75 200 to Various 1700») 15<b> 1189» 60.5<*>.«> 250-lb TI casing
1-6 88

T9 145 70 u B 850 2 99 30 270

T9E1 36X8 115 35 ii B — — — — — 125-lb demolition bomb, case, 0 .19 in.
T9E4-6 — — Various — — . —
- wall '
T9E8 35X 8 166 70 hi A . 2100 5 140 65 153 M70; 0 . 19-in. wall
MI2G 52.25X 8 150 70 hi A 3490 6 165 75.6 153 Modified M70 chemical bomb body, box
type fin, 0.188-in. wall
M120 III B 52.25X 8 165 85 HI A 449b 6 223 95.6 188 Same as M120
T92 39X11 280 138 III B 5840 5 290 140.5 226 Optimum design to fit in RB-4 aircraft;
shallow, wide no
T93 59.18X 14.18 496 224 III A 4000 5 373 108 255 5004b G.P. bomb casing, AK-M46;
M109 fin assembly
T94 69.5 X 1 8 .8 926 450 III A 5600 65 666 163 299 1090-lb G.P. bomb casing AN-M65
T99 4.25 or 13 95 70 — — ' — — - 42 — Thin copper casing, or steel, 0.0625 to
to 180 0.5-in. wail

T104 64 I ll B (End on)

or 104 2900 4 189 82 163 Modified M30A11004b G.P. bomb body;
(thin 3570 or thin ease model modified M47A3
cue) (thin case) 6 284 88 228(a) chemical bomb body

(a) Total duration (b) With Type II, Clam B powder (e) During (MO msec

odized aluminum. The subsequent shape of the inder of metal dust. In all cases initiation and
bubble in the metal dust depends on the resistauce burning of the dust takes place in the air after case
encountered in different directions. I f the ©on- breakup.
fining case deforms slowly without rupture, the I f the. surrounding material can react rapidly,
shape of the explosion products will tend tow:ard gases resulting from the vaporization o f the reac­
the shape of the deformed ease. I f the case ru P- tive material at the outer surface o f the expanding
turcs quickly at one point, the dust may be fori<:ed bubble o f explosive products will increase the
through this opening while some o f the dust will rate at which the bubble expands. The amount of
remain in the case. For small quantities of 5 X - this contribution depends on the reactivity o f the
plosive, the shape o f the explosive is o f little im- mixture. The piston action o f the expanding bub­
portance. For larger quantities o f explosive, ;he ble forms a spherical shell o f compressed flash
shape and its method o f initiation must be co n- composition. Rapid chemical reaction starts at
sidered. An extreme example is an end-initia ted the shock front when it reaches the case and the
line charge axially located in a surrounding cyl increase in pressure results in case rupture. After

6-59
6-60

AMCP 706-185
T A B L E 6-19
C H A R A C TE R ISTIC S OF D U ST PH O TO FLASH BOMBS

Powder - Integral Light

10* C andLaea Bunt Duration
Total Peak Tim e to Attitude o f Flash,
Bomb S u e. in . n n Integrity, P eak, CP8 Best Attitude and meet to
D m aoaBon LX D u 16 Form ula 10» C an S a m eet Total C PS*o Flown,,ft P etition , ft 0 .1 max Casing - Burster
T7 48.73X 8 85(7) 30 Mg, Grade B — — — — - Modified M46 ease with ■
dost charge ‘
T8 200 70 Flake Mg, Grade B 41 44 9 1.9!»> — . Modified 2504b AN-M57 Tetryl; conical;
T8E1 40X 10.76 G. P. Bomb ease, 0.3-in. tinplate container
160 35 Flake A l, Grade A 1100 10 49.4 35.1 wall
T9B2 36X8 103 17 f U t A1 42 — 39 - - 1254b demolition bomb Tritonai 5 lb
case, 0 . 19-in. wall
T9E3 36X 8 136 40 Pigment Al/S. 75/35 38 - . 45 - - Same as T9E2
T9E7 36X 8 2 in. diameter each:
Type 1 62 Atomised Mg 660 14 20 Sheet steel, 0.00 in. Tritonai, 5.84b
3

Mini
62 Atomised Mg 600 13 20 wall; casin&'burster Sod&td 6.1-lb
3
4
5
6
60
60
31
21
Atomised Mg-Ai alloy
Atomised Mg-Al alloy
Flake Al
Flake Al
1300
1300
760
660
13
16
13
14
30
25
25
20
] di&m. ratio: 4:1 Tritonai 5.84b
Sodatol 6.1-lb
Tritonai 5.84b
Sodatol 8.1-lb
T85 (BaDiatw 88X 8 100(7) 66 ’ — ' — 0.2-in. case thickness —
Design)
T88E1-4 36X 8 Various metal d o te Varied: Varied: Varied: Varied: 25.000­ 5,000­ HO- M47 chemical bomb Various
36X10 86 70 1400­ 34­ 164.5­ 50-94 36,000 16,000 812 case; 0 .0 6 in. wall
30X11 3450 121 660
34X13
M122 (T88E2) 64X 8 110 75 Atomised 65/35 Mg-Ai 820 60 31.9 5,000­ 8.000; M26,1-in. diam.
alloy (20± 5 mfcrons) 20,000 30° bail cylindrical; 24b cast
angle beet 70/30 tritonai;
M147E1 fuse
T88E5 13 - Atomised Al - - - — - - " - Thin Al cr steel - TNT and booster
0-89 3 7 .5 X 4 18 0 .5 Al dost and K Q 0 « -. 672 38 — 20.2 82 Concentric bursts, oxi­ Hand packed TNT;
segregated ' dant, metal dust tubes Tetryl booster; M146
face .
0-70 4 8 .8 X 8 96 70 ' Same as 0-69 Beat, 42 Best, To Atleaat M46 case adapted to Hand packed TNT;
3490 130 30,000 13.000; concentric loading Tetryl booster;
30° trail M146 fuse
T il! 64X 8 . no 84 Same >a 0 8 0 Beat. 28 Best, To At least. Modified M47A3 Larger than 0-70
1470 48.9 30,000 13,000 diem, bomb case burster
30° trail
angle best
XE2 30X10 176 114.2 Same as 0 6 9 Beat. — — 160 — Concentric caring, Hand tamped crys­
4890 specially designed talline 2-in. TNT,
4-lb; Tail fuse

X53 33X 8 60 34.3 Al with 3% S O , gd. Concentric raring, 1 .74b hand tamped
KCIO. specially designed TNT, Tetryl
" boaster; Tail fuse

^TOuring 0-60 maee

*
 AMCP 706-185

TABLE 6-20
SEGREGATED OXIDANT PHOTOFLASH BOMBS

Integral Light
Total Powder Peak lOKIandleseet,
Bomb Site in. Weight, Central Intensity, Best 40ms.
Designation LxDia. lb Outer Shell Inner Shell Burster 10* Candles Period
0-69 4X 27.5 18 8.41b 3.11b TNT burster 672 20.2
A1 dust Kao,
0-70 M46 easing 96 A1 dust 70 lb Kao, TNT 3490 130
total chg.

T115 M47A3 110 A1 dust Kao, TNT 1470 48.9

Chemical 841b
bomb ease total ehg.

X62 10X30 175 Atomized 361b TNT 4890 130

A1 78 lb Kao,
X53 8X22 50 Atomized 121b TNT 2200 74
A1 26 lb-3% Kao, (expected)- (expected)
silica gel

A R M IN G
W IRE

WITH M I25 FIN WEIGHT 160LB APPROX

Figure 6 -3 8 . Typical Photoflash Bomb

case rupture the cloud expands against the at- Some o f the more important o f these factors are:
mospheric pressure, resulting in cooling of the (1) charge weight, (2) composition, (3) particle
cloud. The cloud must contain fairly large sized size, (4) burst diameter and shape, (5) igniters
particle aggregates (approximately 250 microU ) u and bursters, (6) confinement, and (7) ambient
so as to reach the size observed experimeniually. pressure.
The light output reaches a peak value and then
slowly decreases. 6-4.5.1 Charge Weight
Generally, flash powder in items which produce
6-4.5 FACTORS AFFECTING PERFORMANCE a b u n t approaching a spherical shape (see also
The light output o f bright flash-producing de­ Paragraph 6-4.5.4) develop a total light output
vices is dependent upon many interrelated fa<store. which is proportional to the charge weight (as is

6-61
 AMCP 706-185

TABLE 6-21
T Y PIC A L COMPOSITIONS FO R PHOTOFLASH AND SPOTTING CHARGES

Type Class Nominal Composition Remarks .

P H 0 T 0 F L A 8 H POW DERS
I — 34% Magnesium Used at start of World W ar II
26% Aluminum in M46 Photoflash Bomb
40% Potassium Perchlorate

II A 60% 50/50 Magnesium- Developed because of shortages

Aluminum Alloy at start of W orld W ar II of
40% Potassium Perchlorate Aluminum and Magnesium Powder

B 45.5% 50/50 Magnesium- Later development led to

Aluminum Alloy substitution of Barium Nitrate
54.5% Barium Nitrate for Potassium Perchlorate

III A 40% Aluminum, Class C

30% Potassium Perchlorate
30% Barium Nitrate

B Same as III-A except that the

Potassium Perchlorate is coarser ■

IV 80% Calcium Experimental Efficiency at

20% Sodium Perchlorate 100,000 feet is 45.7 X 10s
candlesec/g

SPOTTING CHARGES
30% Atomized Aluminum Developed to give short time to
10% Flake Aluminum peak but with less brisance than
60% Barium Nitrate photoflash powders

the light produced iu the best 40 milliseconds, gives better results in nonconsolidated illuminat­
CPS*o). The duration o f the flash increases as the ing compositions.
cube root o f the charge weight, while the peak in­ Thermodynamic data for stoichiometric mix­
tensity increases as the two-thirds power o f the tures of aluminum and various oxidizing agents
charge weight.69,70 71 The efficiency and light out­ are given in Table 6-23.7a The trend is similar to
put for a given weight of charge, therefore, decrease that for consolidated illuminants. (See Paragraph
with charge weight. 6-3.5.1.) As the molecular weight of the oxidant
increases, the aluminum content of the stoichio­
6-4.5.2 Com position metric mixture decreases so that the heat o f reac­
As indicated in Table 6-22,06 aluminum and tion also decreases. Of the oxidizers listed in this
magnesium are the best fuels for use in photoflaah table, potassium perchlorate produces the highest
mixtures at low altitudes.18,72 While atomized mag­ heat o f reaction with atomized aluminum. Lumi­
nesium gives higher luminous intensities than nosity values for various nitrates with atomized
other fuels in consolidated illuminating composi­ aluminum and atomized magnesium are given in
tions, it has been found that atomized aluminum Table 6-24. As indicated by this table, which is

6-62
 * S tU T t APt M fS M
A X C P 706-185

O M K r -A 9 J V -|

ctmwce

XM101 S p o t t in g Px o j e o t i l e
Figure 6-39. Ty’jpical 20 mm Spotting Round

Figure 6 -4 0 . Pho loflash "Daisy” Cartridge

for fuel-rich compositions, the light output »f nesium, and atomized magnesium-aluminum al­
stoichiometric mixtures are relatively low; an<d loys. Atomized aluminum is difficult to ignite and
alkaline earth metal nitrates are much more sati; i 8 - has not been used efficiently in metal dust photo­
factory than alkali metal nitrates in nonconso>li- flash bombs. Flake aluminum, which requires a
dated illuminating compositions. weight of burster approximately equal to that of
For dust-type bombs, there are marked differ- the dust, produces a flash of relatively short dura­
ences in behavior of flake aluminum, atomized mag tion and a rapid time to peak. Atomized mag-

6-63
 AMCP 706-185

TABLE 6-22
LUMINOSITY CH ARACTERISTICS AT SEA LEVEL OF PHOTOFLASH COMPOSITIONS
CONSISTING OF HIGH-ENERGY FUELS IN STOICHIOMETRIC AND FUEL-RICH
COMBINATIONS W ITH POTASSIUM PERCHLORATE

Time to Integral Light, Duration, Efficiency, Increase

Type of Peak, Peak, 10® candlesec, msec 10s candlesec/g1 in
Fuel Composition!*) 10® candles msec (Mo max) Mo max. Total Fuel Efficiency, %

s 41 1.2 147 9 14 10.3

35
Aluminum
X 41 1.7 226 11 16 13.8

Magnesium
s 18 1.2 142 16 24 10.0
15
X 20 2.3 189 17 25 11.5

Zirconium
s 38 0.7 92 7 14 2.8
147
X 55 0.9 278 11 23 6.9

Titanium
s 18 0.4 65 9 15 4.9
4
X 16 1.3 80 12 21 5.1

Calcium
s 12 1.2 75 13 16 5.7
30
X 13 1.7 115 15 19 7.4

Boron
s 0.5 23.0 18 68 89 3.5
85
X 2 14.8 51 55 92 8.5

Silicon
s Did not ignite
X Did not ignite

8 = Stoichiometric, X = 14% excess fuel.

nesium, which requires a much smaller burster, eral, indicate that these additives do not increase
gives a flash of much longer duration and has a the output of those photoflash items which are near
longer time to peak. The magnesium alloys are optimum. Conflicting results have been obtained.
intermediate in their behavior. The difference in Some earlier investigators obtained results which
the metal dust-to-burster ratio may be due to the indicated improvement with some additives.18
relative ignitibility of the metal fuels. Powdered
magnesium is easier to ignite than powdered alu­ 6-4.S.3 Particle Size
minum ; as a consequence, atomized aluminum has Much of the research and development concern­
not been used efficiently in a metal dust bomb. ing photoflash compositions has centered around
The longer time to peak and flash duration of the determination of the optimum particle size
magnesium can be explained by the reaction be­ and shape. While it has long been known that
tween magnesium and nitrogen which precedes the the average particle size and particle size range
reaction with oxygen. are important parameters in determining the lumi­
Small amounts of additives, principally metals nosity characteristics of pyrotechnic flash mix­
and silica gels, have been tried to increase the light tures,18 detailed relationships were difficult to es­
output from photoflash devices. Results, in gen­ tablish until methods became available to classify

6-64

\
V
 AMCP 706-185

systems in which the aluminum was in the 22 ± 8

micron particle size range would produce enough
light for pyrotechnic applications.74 Regardless
of the oxidizer size, system containing coarser alu­
minum — 8.4-40 microns and 24-62 microns—did
not produce a usable amount of light. When the
aluminum particle size was held constant, de­
creasing the oxidant particle size resulted in an
increased efficiency (candle seconds per gram)
at both sea level and at 80,000 feet simulated alti­
tude. (See Figure 6-46.) At high altitude, the
peak and integral light intensity vary similarly.
At sea level, however, the composition with the
coarse oxidizer produced the highest peak and in­
tegral light intensity, due to the greater tapped
density with the coarse oxidizer fraction, so that a
greater sample weight could be loaded into the
test cartridge. 1
The marked differences in the behavior of the
dusts used in dust-type photoflash bombs (Para­
graph 6-4.5.2) result in the existence o f an opti­
mum particle size for each metal or alloy and each
method of dispersion.73 Excessively large particles
will not ignite after dispersal. Efficiency j tends
to decrease, in the case of magnesium and; mag­
nesium-aluminum alloys, if there is too large a
percentage of fines in the dust. As a consequence,
the use of “ run of the m ill,” less than 100!mesh,
atomized magnesium is preferable to the use of
TABLE 6-23 mixtures containing a large amount o f 325 mesh
THERM ODYNAM IC D A TA FO R STOtCHIO- fine particles.18
M ETRIC M IXTU RES OF O XID IZIN G AGENTS In order for the diameter of the burst produced
AND ATOM IZED ALUMINUM by dust-type photoflash bombs to be as large as
observed experimentally, calculations indicate that
..Calculated the tnetal dust particles must “ clump” together
Stoichiometric Heat of (possibly due to the pressure produced by the ex­
Ratio Reaction, Cal/g plosive burster) in fairly large particles, at least
250 microns in diameter. These ‘ ‘ clumps, ’ ’ due to
Sodium nitrate 65.4/34.6 1955 air-drag breakup as they move through the air,
Potassium nitrate 69.2/30.8 1766 leave small particles (particles having the initial
Strontium nitrate 70.2/29.8 1899 size distribution of the metal dust) which burn in
Barium nitrate 74.4/25.6 1598 the air.18
Potassium perchlorate 65.8/34.2 2529
6-4.5.4 Cloud Shape j
the fuel and oxidant powders into narrow particle Since most photoflash bursts are essentially
size ranges. spherical in shape and essentially opaque to visible
For potassium perchlorate-aluminum (60/40 by radiation, the amount of light radiated is propor­
weight) flash compositions, it was found that only tional to the square of the burst radius, provided,

6-65
 AMCP 706-185

TABLE 6-24
LUMINOSITY VALUES OF VARIOUS OXIDAN TS W ITH ATOMIZED
ALUMINUM AND ATOMIZED MAGNESIUM TESTED
IN M112 PHOTOFLASH CARTRIDGE

Time Total
Peak Integral
Intensity, Peak, Light,
Oxidant JO® Candles msec l(fi Candle-Seconds

Aluminum Compositions
Sodium nitrate Burned without detonation
Potassium nitrate Burned without detonation
Strontium nitrate 124 3 1.61
Barium nitrate 139 3 1.64

Magnesium Compositions
Sodium nitrate 4 — —

Potassium nitrate Failed to ignite

Strontium nitrate 21 5 0.33
Barium nitrate 42 5 0.65

siderably by enlarging the effective surface area of

the burst. Theoretically, an optimum system, as
long as the temperature remains high, consists of
an infinite number of infinitesimally small point
sources.™
Line photoflash charges, as well as a large
number of small photoflash charges have been at­
tempted with some success. Both methods, which
effectively increase the amount of radiating area
for a given charge weight, are difficult to use
practically.18 As a result o f recent improvements
in aerial photographic techniques and equipment,
which permit the utilization o f light over longer
periods o f time (up to 250 milliseconds), pellets of
pressed illuminating composition have been used in
place of short duration photoflash charges. Results
indicate that efficiencies are much greater than
the temperature of the surface of the burst re­ those obtained with photoflash compositions.™
mains constant. Since the volume of the sphere is
proportional to the charge weight, and the maxi­ 6-4.5.5 Bursters and Igniters
mum temperature is limited to about 3000°C, the A great many explosives have been tried (Table
peak intensity should, as has been verified experi­ 6-25) as bursters in dust-type photoflash bombs.
mentally (Paragraph 6-4.5.1), vary as the charge In general, the most powerful or brisance buster
weight to the two-thirds power. The efficiency of seems to perform best. R D X is better than tetryl
the larger charges is, therefore, less than that of which, in turn, is better than TNT, other conditions
the smaller charges but could be increased con­ b6ing equal. Aluminized explosives at optimum

6-66
 ■ 'Iv *# ' -iaj ■

AM CP 706-185

at
i
a

T IM E
Figure 6 -4 4 . Tim e-intensity Curves fo r M120A1 Flash
Figure 6 - 4 5 . S ynchronization o f Shutter Powder a n d M 1 2 2 Dust Photoflash Bombs

concentrations have greater power than the pure appreciably influence the output of the dust bomb.
explosive and, therefore, perform better as Centrally located bursters, all factors considered,
bursters.18 gave results comparable to those for any other lo­
As has been indicated, there are markei dif­ cation. The shape of a relatively small amount of
ferences in the behavior of flake aluminum, explosive in an essentially nonreacting metal dust
atomized magnesium, and atomized magm^sium- should have little influence except to change the
aluminum alloys when dispersed and ignitea as a center o f the gas bubble formed. (See Paragraph
dust cloud. Flake aluminum requires a weight of 6-4.4.2.)68
burster approximately equal to the weight if the For a reactive photoflash mixture where the
metal dust. Atomized magnesium requires much reaction contributes to the growth of the gas bub­
less weight, approximately 1/100 o f the weight of ble, the effect o f location, shape, and amount of
the metal dust.73 The maximum radius o f s mag­ initiator are important. The use o f an initiator
nesium dust flash depends, approximately, on the too powerful for a particular case and composition
cube root, o f the dust-to-burster ratio for the lower might cause too rapid expansion o f the gas bubble,
ratios and on a somewhat lower power at the higher resulting in case rupture before a desirable initia­
dust-to-burster ratios. A t a constant dust-to-t urster tion of the photoflash mixture. For a long column
ratio, the radii o f magnesium dust flashes increase, of flash composition with an initiator in one end,
roughly, as the cube root of the quantity of dust. a stage can be reached where reaction in the
In general, for magnesium and magnesium-alu­ photoflash mix will propagate through the mixture
minum alloys, an increase in the dust-to-t urster resulting in some measure o f independence from the
ratio results in an increase in time to peak, an in­ mode o f ignition.18'68 During this process, the case
crease in flash duration, along with an increase in must continue to maintain confinement in order to
integrated light values, and, to a lesser extent, an have, adequate ignition of the balance o f the photo­
increase in light intensity. Because of the large flash mixture.
amounts o f burster required for flake aluminum,
variations in the dust-to-burster ratio within the 6-4.5.6 Confinement
useful ranges seem to have little effect. The characteristics of the case surrounding a
Other factors— including shape o f the burster, reactive photoflash mixture affect the amount of
loading techniques, and confinement— have been time available for ignition o f the mixture as well as
studied. Most dust-type bombs that have been the way the mixture is released and disseminated.
studied use a cylindrical burster or a truncated A case o f excessive strength, requiring an ap­
cone. The method used to load a burster did not preciable amount o f energy to rupture, may divert

6-67
 AMCP 706-185

WAVELENGTH, MILLIMICRONS

Figure 6-45. Spectral Energy Distribution Curve of Ml20 Figure 6-47. Size and Light Output of Flash Cloudys Time
Photoflash Bomb

sufficient energy to reduce the light output. Too TABLE 6-25

thin a case may allow the mixture to be released HIGH EXPLOSIVES TRIED AS BURSTERS
before adequate ignition has taken place, thus IN FLASH BOMBS
reducing the effectiveness o f the flash. This effect,
which would be emphasized at low ambient pres­ Nonmetallized Metallized
sures, was illustrated in tests conducted with metal Comp. A-3 Al/KClCU/cellulose nitrate,
and plastic cases. With the metal case, the ex­ Comp. C 49/49/2
pected light output was obtained at ambient con­ Gunpowder Comp. A-3/A1,80/20
ditions and 80,000 feet and with the plastic case Photoflash Powder Comp. B /A l,80/20 ,
at ambient conditions; however, a sharp drop oc­ Type III, Class C HBX-3
curred for plastic cases at 80,000 feet. Variations Primacord HBX-6
in thickness within narrow limits for metal cases Pyrotechnic Compn. Minol 2 '
were found to cause negligible changes in light RDX R D X /A l/w a x
output.®8 R D X /T N T R D X /TN T/A 1,
R D X /T N T , 60/40 42/40/18 (Torpex 2)
.3 ■ Sodatol 20/50/30
Tetryl RD X / TNT / A l/ Carbon,
Tetryl/TNT, 30/70 20/55/25/2.5
TNT R D X /A 1/P IB ,
78.5/20/1.5
T etryl/A l
TNT/A1 • . '
Tritonal: TNT/A1
. 70/30
75/25 . . . •
80/20

For dust-type photoflash bombs, the casing ma­

AVERAGE PARTICLE SIZE POTASSIUM PERCHLORATE, MICRONS
terial has a relatively unimportant influence on
the light output. The thickness o f the case has a
Figure 6-46. Effect of Particle Size of Potassium Perchlo­
rate on Luminous Efficiency of 60/40 Potassium Perchlo­ limited but not critical effect on the output, espe­
rate-Aluminum Compositions cially with large bursters.78,77

6-68
 AMCP 706*185
{■■■■y

TABLE 6-26
LUMINOSITY CH A R A C TE R ISTICS OP PHOTO FLA SH COMPOSITIONS CONSISTING OF
H IGH-ENERGY FU E LS IN STOICHIOMETRIC COMBINATION W IT H
POTASSIUM PERCHLORATE*

Composition Time to Integral Light, Duration, Efficiency,

Pels msec 10s candlesee/g
Fuel g 10® candles misec (Ho max) Ho max Total Composition Fuel

Sea Level
34% Aluminum 42 41 i 2 147 9 14 3.5 10.3
41% Magnesium 35 18 i 2 142 16 24 4.1 10.0
57% Zirconium 58 38 0.7 92 7 14 1.6 2.8
41% Titanium 33 18 0.4 65 9 15 2.0 4.9
58% Calcium 23 12 1.2 75 13 16 3.3 5.7
17% Boron 31 0.5 23.0 18 68 . 89 0.6 3.5
29% Silicon 35 Did not ignite

100,000 Feet
34% Aluminum 42 49 1.3 103 7 14 2.5 7.3
41% Magnesium 35 16 0.5 10 1.2 33 0.3 0.7
57% Zirconium 58 65 0.7 92 3 11 1.6 2.8
41% Titanium 33 29 0.6 49 4 13 1.5 3.7
58% Calcium 23 26 0.5 176 21 29 7.7 13.3
17% Boron 31 No deflection
29% Silicon 35 Did not ignite

*Test vehicle, M112 charge case reduced to 1 72-inch length..

6-4.51.7 Ambient Pressure of light results because the flash diameter at alti-
As indicated'by the data in Table 6-26 the tude (Figure 64 7 ) is greater than at sea level.68
light output of most possible photoflash mixtures The effectiveness o f photoflash mixtures con­
is less at an altitude of 80,000 feet than at sea taining calcium depends on the formation and
level. O f the high energy fuels evaluated, alu­ energy content of discrete bands.78 The phenome­
minum and magnesium were most efficient at sea non of increasing light output observed with com­
level and calcium was most efficient up to |l00,000 positions containing calcium metal, calcium alloys,
feet.46 As the boiling point and extent of dissocia­ calcium perchlorate, and calcium nitrate also re­
tion of the reaction products depend on the am­ suits when adding an inert calcium salt such as
bient pressure, the final flash temperature will calcium oxide or calcium fluoride to a composition
decrease with increasing altitude. The radiation producing a high temperature such as aluminum-
produced by most photoflash items is continuous potassium perchlorate. The magnitude o f the in­
(see Paragraph 64.4.1.2) approaching that of a crease in light output, however, is considerably
gray body with a high emissivity and lowjer light less than for other calcium-containing composi­
values obtained. Some compensation for this loss tions.06

6-69
 AMCP 706-185

REFERENCES
1. Alan St. H. Brock, A History of Fireworks, port 1758, Picatinny Arsenal, Dover, N. J.,
George G. Harrap and Co., Ltd., London. January 1950.
2. Jean Appier (alias Hanzelet), La Pyrotechnic, 14. S. A. Richer, The Photoflash Bomb, Picatinny
Pont a Mousson, 1630 (quoted in Brock, A Arsenal, Dover, N. J., April 1955.
History o f Fireworks). ■ ' 15. H. J. Eppig, D. Hart, Bomb, Photoflash, T9
3. Claude Buggieri, “ Siemens de Pyrotedm ie,” Series: A Study o f Light Emission Character­
Fortune, Paris, 1801 and 1821 (quoted in istics o f Safe, Dust Type Photoflash Bombs,
Brock, A History o f Fireworks). Picatinny Arsenal Technical Report, 1757,
4. Claude Ruggieri and Thomas Morel, “ Die Picatinny Arsenal, Dover, N. J., February
1950.
Pyrotechnie,” Nach der Vorschriften, Leipzig,
16. S. A. Richer, The Photoflash Cartridge, Pica­
1807 (quoted in Brock, A History o f Fire­
tinny Arsenal, Dover, N. J., April 1955.
works) .
17. M. G. M. Clarke, Development o f the Photo­
5. Claude Ruggieri, “ Pyrotechnie Militaire,”
flash Bomb, ORDW ES Report 1949-5, Wes­
Fortune, Paris, 1812 (quoted in Brock, A
leyan University, Middletown, Connecticut,
History o f Fireworks).
April 1949.
6. James Cutbush, “ Chinese F ire,” American
18. The Compilation o f Flame and Shockwave In­
Journal of Science, V II, 1823 (quoted in
formation Applicable to Photoflashes, Final
Brock, A History of Fireworks).
Summary Report, Contract DAI-28-017-501-
7. Summary Technical Report, Vol. 2, Chapter
ORD(P)-1096, Arthur D. ^ittle, Inc., Cam­
4, NDRC Division 11, National Defense Re­
bridge, Mass., September 1955.
search Committee, Office of Scientific Research 19. R. M. Blount, G. Francis, R. W. Evans, Study
and Development, Washington, D. C. of Light Sources for Night Aerial Reconnais­
8. D. Hart, Research and Development Progress sance Photography, Contract DA-36-039-SC-
in Military Pyrotechnics, Research and De­ 78333, Denver Research Institute, Denver,
velopment Lecture No. 24, Picatinny Arsenal, Colorado, August 1960.
Dover, N. J., 1955 (DDC-AD 82 678). 20. George Shortley and Dudley Williams, Ele­
9 . ' T. Stevenson, E. R. Rechel, Delay Action ments of Physics, 3rd Ed., Prentice-Hall, Inc.,
Tracer Ammunition, Frankford Arsenal Be- Englewood Cliffs, N. J., 1961.
port R-44, Frankford Arsenal, Philadelphia, 21. S. Gladstone and B. Lewis, Elements of Phys­
Pa., 1940. ‘ ical Chemistry, Van Nostrand Co., Inc., Prince­
10. T. Stevenson, Delay Action and Dim Igniters ton, N. J., April 1960.
fo r Small Arms Tracer Bullets, Frankford 22. B. Douda, The Theory o f Colored Flame Pro­
Arsenal Report 708, Frankford Arsenal, Phila­ duction, RDTN-71, Naval Ammunition Depot,
delphia, Pa., 1946. Crane, Indiana; Bureau of Naval Weapons,
11. Develop, Manufacture and Test Flashlight Washington, D. C.
Bombs, Picatinny Arsenal Technical Report 23. E. J. Bowen, The Chemical Aspects o f Light,
803, Picatinny Arsenal, Dover, N. J., March 2nd Ed., Clarendon Press, Oxford, 1946.
1937. 24. International Encyclopedia of Chemical Sci­
12. J. H. Robinson, Investigation o f Failures o f ence, Van Nostrand Co., Inc., Princeton, N. J.
M23 Photoflash Bombs, Picatinny Arsenal 25. A. C. Gaydon, The Spectroscopy of Flame,
Technical Report 1068, Picatinny Arsenal, Chapman and Hall, Ltd., London, 1957.
Dover, N. J., January 1941. 26. A. C. Gaydon and H. C. Wolfhard, Flames,
13. H. J. Eppig, D. Hart, Bomb, Photoflash, T9 Their Structure, Radiation and Temperature,
Series: Development of Improved Photoflash 2nd Ed., Chapman and Hall, Ltd., London,
Composition, Picatinny Arsenal Technical Re­ 1960.

6-70
 AM CP 706-185
5 •
'K.X&'&j'}

REFERENCES (cont’ d)
27. Wallace R. Brode, Chemical Spectroscopy, tion Characteristics o f Transparent and Trans­
John Wiley & Sons, N. Y., 1943. lucent Material Under Nonisotkermal Condi­
28. A. Fran,son, S. Katz, and £ . Raisen, ‘ Radia­ tions, ASDTDR 62-719, A ir Force Systems
tion Characteristics o£ Black Body Soirees,” Command, Wright-Patterson A ir Force Base,
Symposium on Temperature, Its Measurement Ohio, June 1964.
and Control, Reinhold Publishing Co., N. Y., 41. B. Jackson, S. M. Kaye, G. Weingarten, Resins
1962. Other Than Laminae 4116 as Binders in P yro­
29. R. Kinglake, Ed., Applied Optics and Optical technic Compositions, Picatinny Arsenal Tech­
Engineering, Vol. I, Academic Press, 1965,
nical Note 40, Picatinny Arsenal, Dover, N. J.,
p. 8.
January I960.
30. J. Thewlis, Ed., Encyclopedia Dictionary
42. H. J. Eppig, J. D. Stracham, Self-Hardening
Physics, Pergamon Press, Ltd., London, 1961.
Pyrotechnic Compositions, Picatinny Arsenal
31. M. G. Mellon, Ed., Analytical Absorption Spec­
Technical Report 1801, Picatinny Arsenal,
troscopy, John W iley & Sons, Inc., N. Y.,
Dover, N. J., December 1950. 1
1950.
43. D. Hart, Research and Development in Mili­
32. R. L. Weber, M. W. White, K. V. Manning,
tary Pyrotechnics, Picatinny Arsenal, Dover,
Physics for Science and Engineering, IV'cGraw-
N. J., February 1955 (DDC-TIP U10769).
Hill Book Co., Inc., N. Y., 1957.
44. B. Jackson, An Investigation of the Effects
33. R. C. Casperson, H. P. Lenzyck, R. C. Chan­
of Loading Pressure, Flare Case Coating, and
nel, Visibility Data as It Applies to Pyrotech­
Magnesium Particle Size on the Burning Time,
nics, Contract DAI-28-017-501-ORD($)-1294,
■Luminous Intensity, and Color Characteris­
Dunlap and Associates, Stamford, Conneeii-
tics of Pyrotechnic Flare Compositions, Pica-
cut, April 25, 1955. I
tinny Arsenal Technical Note 14, Picatinny
34. E. Freeman, G. Weingarten, A Thermal
Arsenal, Dover, N. J.
Theory for Rates of Propagative Burning,
45. R. M. Blount, R. W. Evans, Experimental In ­
Picatinny Arsenal Technical Report 2o96,
vestigation o f Infrared Radiating Sources,
Picatinny Arsenal, Dover, N. J., June 1959.
Denver Research Institute, Denver, Colorado,
35. D. Hart, H. J. Eppig, Long Range Research
July 1961 (DDC-AD 324 807), March 1962
on Pyrotechnics: Burning Character istics of
(DDC-AD 328 630), November 1962 DDC-
Binary Mixtures, Picatinny Arsenal T<echnical
AD 332 848). :
Report 1669, Picatinny Arsenal, Dove r, N. J.,
46. B. Jackson, The Effect o f CroSsjjSjctional Area
October 1947 (D D C -A T l 66 289).
and Case Material on Burning Characteristics
36. Herbert Ellern, Modern Pyrotechnics Chem-
ical Publishing Co., N. Y., 1961. of Pyrotechnic Compositions, Picatinny A r­
37. B. E. Douda, Relationships Observed in Col­ senal Technical Note 7, Picatinny Arsenal,
- ored Flares, RDTR-45, Naval Ammunition Dover, N. J., September*1957.
Depot, Crane, Indiana; Bureau ojf Naval 47. A. F. Tasehler, S. M. Kaye, Effects of Mag-
Weapons, Washington, D. C., September 1964. ntsium Content Case Material and Case Coat­
38. R. F. Barrow and E. E. Caldin, ‘ ‘ Some Spec­ ing on Burning Characteristics o f a Flare
troscopic Observations of Pyrotechnic 1Hames, ’ ’ System, Picatinny Arsenal Technical Note 42,
Proceedings of Physical Society of London, Picatinny Arsenal, Dover, N. J., April 1960.
62 (1949). . 48. S. Resnick, Simulated High Altitude Tests of
39. B. E. Douda, Emission Studies of Selected P y ­ Illumination Compositions, Picatinny Arsenal
rotechnic Flames, RDTN-77, Naval Ammuni­ Report 2166, Picatinny Arsenal, Dover, N. J .,
tion Depot, Crane, Indiana; Bureau of Naval April 1955. ^
Weapons, Washington, D. C., August 1964. 49. W. A. Schmeling, Applied Research JgfJThreat
40. R. C. Folweiler, W . J. Mallio, Thermal Radia­ Signattire Generation Techniques, Final Re-

6-71
 t

*
AMCP 706*185

REFERENCES (cont’ d)
port, Denver Research Institute, Denver, Col­ 60. R. G. Weldon, Development of the Signal,
orado, August 1963 (DDC-AD 340 411). Flash, Guided Missile M K 37 Mod O fo r the
50. R. Shulman, Effects of Variation'of Cavity Sparrow II I Missile, NAVORD 5860, Bureau
Geometry Upon Small Arms Tracer Burn­ of Naval Weapons, Washington, D. C., May
ing, Frankford Arsenal Report 1421, Frank­ 1958.
ford Arsenal, Philadelphia, Pa. 61. J. W. Haldeman, Development of the Signal,
51. E. S. Freeman, “ The Kinetics of the Under­ Flash, M K 49 Mod O for the Terrier BT-3 Mis­
water Corrosion of Powdered Magnesium,” sile and the Signal, Flash, M K 56 Mod O for
Journal of Physical Chemistry 59, 1009 the Corvus Missile, NAVORD 7055, Bureau
(1955). of Naval Weapons, Washington, D. C., Sep­
52. R. M. Blount, G. Francis, Study of Light tember 1960.
Sources for Night Aerial Reconnaissance Pho­ 62. Air Force Manual 55-6, Department of Air
tography, Contract DA-36-039-SC-78333, Den­ Force, Washington, D. C.
ver Research Institute, Denver, Colorado, Au­ 63. Air Force Manual 95-3, Department of Air
gust 1960.
Force, Washington, D. C.
53. J. R. Quick, R. T. Johnson, Simplified Method
64. S. Haffner, A Survey of Available Literature
of Determining Optimum Burst Altitudes for
on the Rapid Combustion of Metals in Air,
Aerial Photoflash Bombs Under Various Con­
Picatinny Report 2061, Picatinny Arsenal,
ditions of Light Output and Flight Altitude
Dover, N. J., September 1954 (DDC-AD 44
for Fixed Camera Trail-Angle Combination,
543). '
WCLR-55-5, Wright A ir Development Center,
65. A. A. Shidlovsky, Fundamentals of Pyrotech­
Air Technical Service Command, Wright-Pat-
nic, Government Publication of the Defense
terson Air Force Base, Ohio, November 1956
Industry, 1st Ed., Moscow, 1943 (Library of
(DDC-AD 110 518).
Congress Call No. UF 860.85), 2nd Ed., Mos­
54. Night Aerial Photography, A Technical His­
cow, 1954 (Library of the University of Cali­
tory, Wesleyan University, Middletown, Con­
fornia, Berkeley, Calif.).
necticut, July 1954 (DDC-AD 46 595).
66. S. Lopatin, Sea Level and High Altitude Per­
55. The Magnesium Burner: Uses Other Than
formance of Experimental Photoflash Composi­
Photographic, Wesleyan University, Middle­
tions, Picatinny Arsenal Technical Report 29,
town, Connecticut, May 1951 (DDC-ATI 168
Picatinny Arsenal, Dover, N. J., October 1961.
202) .
56. The Magnesium Burner, 11. Fuels, Wesleyan 67. J. Hershkowitz, The Action o f an Explosive
University, Middletown, Connecticut, October on Surrounding Nonreacting Metal Dust, Pica­
1952 (DDC-ATI 171 350). tinny Arsenal, Dover, N. J., December 1957
57. R. T. Eckenrode and F. L. Marian, The Spot­ (DDC-AD-150 486).
ting Technique: The Question of Spot vs 68. J. Hershkowitz, The Mechanism of Ignition and
Smoke and Spot Duration, Memo for Record, Propagation of Oxidant-Metal Flashes, Pica­
Project TS 4-4020, Frankford Arsenal, Phila­ tinny Arsenal, Dover, N. J., April 1958 (DDC-
delphia, Pa., November 1964. ? AD 156 424).
58. R. T. Eckenrode, The Spotting Technique: E f­ 69. R. M. Badger, A. L. Wahrhaftig, Further
fect of Ambient Illumination, S p ot’Intensity Studies of the Effect of Composition on the
and Color, Memory Screen Information, Memo Properties of Flash Powders, Contract W-535-
for Record, Project 754, Frankford Arsenal, AC-24521, California Institute of Technology,
Philadelphia, Pa., October 1955. Pasadena, California, July 1942.
59. D. D. Collins, Pyrotechnic Flashes and Flares 70. R. G. Clarke, W. C. Nelson, R. W. Stallbaum,
in Guided Missile Tracking, Redstone Arsenal, Photoflash Bomb. IV . The Effects of Cast and
Huntsville, Alabama, December 1959. Hand Packed Bursters, ORD 1951-2, Wes-

6-72
 ■i rtf'li':; 6-41

REFERENCES (cont’ d)
leyan University, Middletown, Connecticut, search Laboratory Technical Report 44, Pica-
June 1951 (DDC-AD 51 317). tinny Arsenal, Dover, N. J., November 1961
71. Further Investigation of Photoftaih Pov>ders, (DDC-AD 266 486).
Memo Report ENG-M-59-676-15-26, A A F Ma­ 75. S. Lopatin, C. A Knapp, Pelletization of II-
teriel Center, Photographic Laboratory Sec­ luminants to Improve Photoflash Efficiency,
tion, A ir Technical Service Command, Wpight- Picatinny Arsenal Technical Note 24, Pica­
Patterson Air Force Base, Ohio', February tinny Arsenal, Dover, N. J., August 1959
1943. j (DDC-AD 207 077). ■ *
72. P. Tavernier, Contribution to the Study of 76. R. G. Clarke, The Photoflash Bomb. III. The
Flash Powders, Translation by. -U. S. Joint Casing and the Dust Charge, ORDW ES Re­
Publication Research Service of report from port ORD 1950-4, Wesleyan University, Mid­
Liberateire de la Commission des Substances dletown, Connecticut, June 1950.
Explosive, 17 May 1944, Picatinny Arsenal 77. R. G. Clarke, C. B. Ford, The Photoflash
Technical Memorandum 1072, Picatinny A r­ Bomb. II. Technical Developments in 1947-9,
senal, Dover, N. J., October 1963., ORDW ES Report 1949-11, Wesleyan Univer­
73. G. Weingarten, Chemistry of Pyrotechnics, sity, Middletown, Connecticut, May 1949.
Presentation at Picatinny . Arsenal, !Dover, 78. S. Lopatin, High Altitude Flash Characteris­
N. J. ’ ' tics of Calcium/Potassium Perchlorate and
74. S. M. Kaye, J. Harris, Effect of Fuel and Oxi­ Standard Photoflash Compositions, Picatinny
dant Particle Size on the Performance Char­ Arsenal Technical Report 2646, Picatinny A r­
acteristics of 60/04 Potassium Perchlorate/ senal, Dover, N. J., October 1959 (DDC-AD
Aluminum Flash Composition, Feltman Re- 313 204). '
+

f- ; *
r. 4,

V
V

* -V * ’h
A

6-73
 I

AMCP 706-185

mixture of pitch, tallow, black powder, and salt­ rial or a suitable method for producing large-area
peter. The obscuring power of the smoke was due screens.
to incomplete combustion of the solid particles in The smoke munitions available in 1940 included
the pitch. Screening smoke was used on a large projectiles, bombs, smoke pots, grenades, and air­
scale by the Canadians in their attack on Messiner. plane spray tanks, which were sufficient to enable,
Ridge in September 1915. During the following ground tactical units to conceal their movements
year, the use of smoke continued to increase as its by laying curtains of smoke across the battlefront.
value became apparent to all of the major bellig- , The tactical employment of small, smoke-produc­
erents.1 - ing munitions was established as a result o f actual
Both red and white phosphorus were soon intro­ experience in field maneuvers and demonstrations.
duced as smoke-producing materials. White phos­ The principal screening materials available in­
phorus proved to be the more efficient of the two and cluded sulfur trioxide-chlorosulfonic acid (F S ),
was by far the most efficient smoke-producing ma­ a liquid solution for use in projectiles and airplane
terial introduced during W orld W ar I. Sulfur spray tanks; hexachloroethane-metallic zinc mix­
trioxide was the next most efficient smoke-produc- ture (H C ), a solid mixture used in burning-type
i ing material used, in spite o f the fact that humid munitions such as grenades and smoke pots; and
air was required to form the sulfuric acid fumes. white phosphorus (W P ), used in grenades, pro­
- Other materials which produce sulfuric acid fumes jectiles and bombs. These materials were superior
on contact with humid air, such, as oleum, chloro- to similar materials developed and used during
sulfonic acid, and su lfu ryl. chloride, were also W orld W ar L * ,
widely used. The two latter materials also pro­ The effectiveness of German air operations
duced hydrochloric acid fumes: Metallic chlorides, . against British cities, during 1940-41 was consider­
including tin tetrachloride (British K.J., French ably reduced through the use o f large-area smoke
screens which prevented accurate aiming. The
Opacite), titanium tetrachloride (German F -Stoff;
British protected important industrial centers with
United States F M ), and silicon tetrachloride, were
smoke pots of an oil-burning type similar to the
also used. ' ' 1
smudge pots used in United States orange groves.
Another group of materials, producing the so-
Lines of smoke pots were laid out in such a manner
called zinc smokes, were basically mixtures of zinc
that the vital area was screened under-any wind
dust and an organic chlorine-containing compound.
direction. The operation of this type of stationary
The;’ Berger mixture, used by the French during
smoke pot line required an extensive supply system
W orld W ar I, was composed o f zinc dust, carbon
since all important areas needed protection. As a
tetrachloride, zinc oxide, and kieselguhr. An im­
result, the British developed truck-mounted mo­
proved mixture was developed in 1917 by the U. S.
bile generators, the most suitable o f which was
Bureau o f Mines and was known as the BM Mix­
known as the “ Haslar” which produced a gray-
ture. This mixture consisted o f zinc dust, carbon
brown smoke by burning and vaporizing crude
tetrachloride, sodium .chloride, ammonium chloride,
o il4,5 .
''a n d magnesium carbonate, f\
In the United States, the Defense Department
The introduction o f military aircraft;, especially
and the National Defense Research Committee,
bombers which could attack important "rear-area along with several universities and industrial con­
targets, created a definite need for large-area cerns, cooperatively embarked on a research pro­
smoke screens for protection. Consequently, much gram to produce large-area smoke screens. Early
„of the effort between the two W orld Wars was di­ in 1942, the optimum particle size for a hydro­
. rected toward developing techniques for producing carbon smoke was determined and mechanical
these iarge-area smoke screens, including the use smoke generators were developed to produce this
. of aircraft for this purpose.4'5 A t the beginning type o f screen.5 Work on smoke pots based on the
o f W orld W ar II, however, neither the United venturi .principle was started at this time using
States nor Great Britain had a satisfactory mate­ fuel blocks to vaporize volatile materials; however,

7-2
 AMCP 706-185
<".v 4'<-%?■< f^r,
•* * • • . ,
these devices were not fully ready for production by the Services. Little information on the manu­
during W orld W ar II. facture and application of colored smoke Signals
\ The smoke-producing materials such as W P, was available in the United States at the beginning
FS, a n d'H C had disadvantages which at rimes, of W orld W ar I due, mainly, to the curtailment in
limited their usefulness in W orld W ar II. jill of fireworks manufacture. Investigations were started
the ^smokes produced from these materials were by various civilian and military agencies. Various
irritating. FS smoke was corrosive in the presence types of smoke signals— including both parachute
of moisture. W P Smoke tended to rise rapidly, or and nonparachute rockets, rifle grenades, Very
to pillar, due to the heat given off by the burning pistol cartridges, hand grenade signals for avi­
phosphorus. HC, and similar smoke composi tions, ators, submarine recognition signals, and smoke
produced zinc chloride which was toxic. In spite pots for ground use— were developed in a variety
o f the disadvantages, these items were used, along of colors. Inasmuch as the American Expedition­
with the newly developed, mechanical smoke-pro­ ary Forces were to operate in a sector held by the
ducing devices, in advancing the strategic and French Army, it was found expedient to adopt the
tactical use of smoke during World War II. For entire French Army system of pyrotechnics.
the first time, large areas, including whole cities, The French used colored smoke signals which
could be screened from aerial observation fo:: rela­ consisted of red and yellow smokes in signal para­
tively long periods o f time.4 ® chute rockets, rifle grenades, 25 mm and 35 mm
Screening smoke again proved to / be of value Very pistol cartridges, and a messenger signal.
in the Korean action in which the United Nations’ The only French smoke manufactured in the
Forces Operated without the benefit of air superi­ United States was yellow smoke, since this item
ority for much of the time. Hence, large-area could be produced from available ingredients; the
screens were employed to protect vital port areas other colored smokes, such as red, could not be
as well as forward combat areas.7 In addition, manufactured because necessary dyestuffs were in
much of the Korean action was a struggle fo r dom­ short supply at that time. The United States did
inating terrain, and smoke was constantly used in not develop mortar or artillery projectiles produc­
relatively small-scale operations. Colored smoke ing colored smoke during W orld W ar I.
was also used for screening personnel withdrawal The British Army also recognize.d the need for
operations because it persisted longer than the colored smoke signals and developed a number of
white phosphorus smoke normally used for this such munitions early in W orld W ar I. Red, yel­
purpose.1-6'8 t
low, blue, and violet smokes were developed for
use in rifle grenades (with or without parachutes),
7-1.2 SIGNAL SMOKES in Very pistol cartridges, and in 3-inch mortar
The need for methods o f signaling when neither projectiles. A red and blue smoke filling for the
hand signal nor flag is visible, nor the sound of 4.5-inch projectile was developed for artillery spot­
voice or horn is audible, has long been recognized. ting and aviation signaling. Dummy drop bombs
Smoke signals have been used for this purpose since or subcaliber bombs containing colored smoke fill­
ancient times. However, the thick haze ok black ings were developed for training purposes. B y the
powder smoke which enveloped battlefields vir­ close of W orld W ar I, the Allies succeeded in de­
tually eliminated smoke as a signaling agent for a veloping experimental colored smoke rifle grenades
time. The introduction of smokeless powdel again as well as rockets and Very cartridges in a variety
made smoke signals a valuable method of com­ of colors. They also made some use of colored
munication in military operations. In spit^ of the smoke for artillery spotting. Virtually no informa­
many improvements in communications methods, tion is available concerning the use of colored
signal smoke continues to have an important place smoke by the Germans and Italians during W orld
in modem warfare. W ar I.
Prior to W orld W ar I, a limited number of Although the research and development effort
pyrotechnic items, mainly colored flares, were used in the United States proceeded at a reduced rate

7-8
 /

AMCP 706-185 /
i
»

in the period between World Wars I and II, a suited in a decrease in the flame color and intensity.
considerable number of munitions for producing Since the flame tracer was considered most im­
colored smoke were developed. Included among portant, the work was not pursued. After W orld
these items were colored smoke hand and rifle gre­ War II, a requirement for smoke tracers was re­
nades, canisters containing colored smoke fillings established, and improved smoke tracers were de­
for various calibers of projectiles, colored streamer veloped based on the use of organic dyes,10 the
smoke bombs, colored smoke markers for aerial best o f which were of the anthraquinone series
delivery containers, and colored bursts for the 4.2- producing orange-red smoke. These smoke tracers
inch chemical mortar projectile. All of these were were developed primarily for training pilots to
produced in a variety of colors. The British Army improve their gunnery score with wing-mounted
also developed colored smoke rifle and hand gre­ guns. Due to the pilot’s extreme forward position
nades, and colored smoke fillings for most of their in the aircraft, flame tracers coming from the wing
artillery projectiles. The German Army limited guns in the rear were difficult to pick up and. fol­
their colored smoke signals to various small hand low visually as they passed. Smoke tracers, on the
signals. other hand, left a lingering trail which was easier
Extensive use of signal smoke in W orld W ar II to sight and point at the target. However, since
and the Korean Conflict proved that the use of they could not be seen readily at night they were
colored smoke for signaling purposes has an im­ not considered all-purpose tracers and, consequent­
portant place in the communications system of ly, did riot become standardized.
modern warfare. Four colors— red, green, yellow, In 1950, development of spotting bullets as an
and violet— were found to be the most suitable. additional aid for fire control and target acquisi­
Smokes were also of value in marking a specific tion was undertaken.11 A smaller caliber spotting
operations area or target. They also played an bullet was designed to match the trajectory of the
important part in antisubmarine warfare and in major round at the critical range. Upon impact
air-sea rescue operations. In many instances, espe­ with the target or nearby, the spotting bullet ex­
cially in the Korean Conflict, the use of pyrotech­ ploded to give flash and smoke. Since the flash was
nic signals, including smoke, was much faster and of extremely short duration (30 to 50 millisec­
more effective than more modern communications onds), the smoke puff became of greater impor­
methods when the tactical situation was degen­ tance because it rose and lingered over the point
erating.9 of impact for a longer period so that the gunner
could readily correct his aim. This development
resulted in the standardization of the caliber .50
7-1.3 TRACKING AND ACQUISITION
M48 combination spotter-tracer round and the de­
SMOKES
velopment of a new family of spotting rounds.
Smoke has been found to definitely complement
Another use for the smoke-producing, devices
the observance o f tracer projectiles and, more
resulted from the increasing speed of air or space
recently, has been used as a space vehicle tracking
vehicles which were developed after W orld W ar
aid. Tracer bullets, while developed as a light-
II. In order to assist test personnel in the optical
producing device for improved aim and fire con­
tracking of these vehicles, it was necessary to de­
trol for automatic weapons, emit distinct amounts
velop smoke-producing tracking aids, some of which
of white smoke which is composed essentially of
were required to function at extremely high alti­
metal oxide particles. Under certain atmospheric tudes.
conditions, such as firing into bright sunlight, the
smoke trail is easier for a gunner to follow than a
red flame tracer, although the flame tracer is the 7-2 PROPERTIES OF SMOKE
best under most other conditions. In 1923, studies The value of a military smoke, whatever its use,
were undertaken to develop a smoke tracer. It is related to the scattering, reflection, and absorp­
was soon apparent that attempts to increase the tion of incident radiation by Small suspended par­
volume of the smoke trail along the trajectory re- ticles. These properties are associated with the

7-4

J
 AMCP 706-185

■r-l ?&■'s

mu.
m

rmcto. sMfcitt
SMB
eas o m im h

os. a w

.a m .

*
1a9 f
c«
•'M
a» c
SttMOkOS MUMS*
1 <r» sr*
l L _ J C.
_________£ _ L± - f * ------------Ir< -1 -| f f I
rf
i
J
i

S g 5 i
<«• g t U W ffLOQTT
o'
if” r
Iff* Iff*
f 1 f
1 _1 1 1 10 w
1* 0
K io" ; « * sr* O'* «r* * sr* *
____L ___________________ __L_ ______________ ____ ---------------- - i
OO OOt 00009 000 0109 0 i <r 0
o 09 » s> i» 10 0
marcl l OHMc m . memo » BO MlBO

Figure 7-1. A p p ro xim a te Size Range o f A irb o rn e P article*

number, size, and nature of the suspended par­ Dusts are particulate clouds made up o f solid
ticles. The number of particles, their size, and particles formed by the mechanical disintegration
initial behavior depend upon the smoke agent, the of matter. The diameter o f the particles in a
particular munition, and the method of release. dust range from about 0.1 micron to greater than
The density, persistency, and subsequent behavior 100 microns.
of the smoke cloud also depend on meteorological Mists are gaseous suspensions o f liquid droplets
conditions, such as humidity, wind speed, wind di­ produced by the condensation of a vapor or atom­
rection. and air stability. ization of a liquid. Mists, especially those occur­
ring naturally, consist o f relatively large particles
7-2.1 PRO PERTIES OF PARTICU LATE ranging in size from around 5 microns to larger
CLOUDS812 than 10 microns. I f the concentration of droplets
The classification of types of suspensions in is great enough to interfere with vision, it is called
terms o f their nature, origin, and particle size has a fog.
not been completely successful due to their indefi­ A smoke is a suspension in a gaseous medium,
nite characteristics and because of the differences, such as the atmosphere, of small particles which
not always clear-cut, between descriptive ferns in have a relatively low vapor pressure and which
scientific and common usage. A gaseous suspension settle slowly under the influence o f gravity. A l­
of liquid or solid particles the diameter of which though smokes are often characterized by their
is less than 100 microns is commonly called a par­ mode of formation, the main criterion is one o f
ticulate cloud. There are three broad classes of particle size. While, at one time, only clouds
particulate clouds: (1) dusts, (2) mists, and (8) formed by combustion and destructive distillation
smokes. I f the particles in any particulate cloud were classified as smokes, at present any gaseous
are less than approximately 10 microns in di­ suspension o f particles ranging in size from ap­
ameter, they are called aerosols. The term aerosol proximately 0.01 to perhaps 5.0 microns in diam­
was introduced to cover only fine, aerial suspen­ eter, and which cannot be classified as a dust or
sions. It has, however, been applied in recent years mist, is considered to be a smoke. In many oases
to almost any aerial suspension o f particles. In the smoke particles are aggregates of many ex­
some cases, especially in the United States, the tremely small, primary particles. Carbon smokes,
term aerosol is used instead of particulate cloud. for example, are composed o f extremely small,

7-5
AMCP 706-185

I 97 0 .7 8 5 0524 0 .3 9 3 0 .3 1 4 0 262 0 .2 2 4 0 .1 9 6 0 .1 7 4 0 .1 5 7 0 .1 4 3

X IN M ICRONS <r*0.3 M IC R O N S )

Figure 7-2. Scattering by Spherical Particles With Indicated Refractive Indexes

7-6
 AMCP 706-185

primary particles of approximately 0 . 0 2 micr on m scattering of vehicle light will occur when the
diameter which coagulate into irregular filaments droplets are about 0.3 micron in diameter.
that may reach a length of several microns. In The angular distribution of the scattered light
Figure 7-1 is shown the approximate particle is also a function of r/X. For Rayleigh scattering
size ranges for typical airborne particles. by small particles, the forward and backward scat­
tering is the same. With an increase in the particle
7-2.1.1 Optical Properties of Particulate Clouds radius, the forward scattering becomes much
greater. For a particle whose radius is equal to or
Particles suspended in a gaseous medium scat­
greater than the wavelength of light, this factor
ter, reflect, and absorb radiation in a manner which
may be 1 0 0 0 or more in favor of the forward scat­
depends on the nature, size, and shape of the
tering.
particle, and the wavelength of the incident radia­
Smoke clouds, which have a distribution of
tion. These factors, in turn, determine the effec­
particle sizes, exhibit the scattering which would
tiveness of a smoke for screening and its visibility
be observed for a mixture o f a large number of
when used for signaling or similar purposes
different uniformly sized smokes mixed in varying
The scattering o f light by a particle can be
proportions. No completely satisfactory analysis
treated as the interaction between the electro­
of the amount of scattering that may be expected
magnetic waves and the particle. When light
from such a polydispersed smoke cloud has been
strikes a particle which is comparable in size to, or
made.
smaller than, its wavelength; reflection and re­
fraction, in their normal sense, no longer occur. The theoretical treatment o f the scattering of
Interaction between the radiation and particle light by particles which also absorb is a difficult
results in energy being removed from the wave problem, especially when absorption is selective.
When the incident light is white, the scattering
front. Some of this energy is degraded to heat but
much is re-radiated as scattered radiation. Each by each of the particles will remove some o f the
particle becomes, in effect, a self-luminous source. light selectively absorbed so that the light finally
The theory of scattering by spherical particles scattered by the cloud will be colored.
was developed from Maxwell’s equations by Gus­
7-2.1.2 Properties of Particulate Clouds Affecting
tave Mie. 18 For spherical particles which arc small
Their Stability
compared to the wavelength o f light, this theory
gives results which are in complete agreement with Smoke clouds and other particulate clouds are
the results obtained from the less-general Rayleigh essentially unstable and will eventually disappear
theory which states that the amount of ra<Ration with time due to: (a) motion of the particles, (b)
scattered is inversely proportional to the fourth evaporation and/or condensation, and (c) coagu­
power of the wavelength. As the particle radius lation and agglomeration.
increases in size to approximately the wavelength
of the light, the scattering becomes a comple s func­ 7-2.1.2.1 Motion of Smoke Particles
tion of the particle radius, the refractive index of Movement of smoke particles under the in­
the particle, and the wavelength of the incident fluence of gravity and as a result of random bom­
light. The scattering coefficient, i.e., the scattering bardment by gas molecules (Brownian motion)
index, is an extremely complex function o f the may cause particles to disappear by sedimentation
parameter r/X, where r is the radius of the particle or diffusion. Sedimentation effects are important
and X is the wavelength of the incident light, and for particles one micron and larger, while diffusion
exhibits one or more peaks before approaching the effects are important only for much smaller par­
limiting value of 2.0 as is shown in Figure 7-2. As ticles.
the refractive index of the particle increases, the
peak in these curves moves toward smaller radii 7-2.1.2.1.1. Sedimentation
particles. For screening smoke made from fog oil An individual particle settling under the in­
which has a refractive index of 1.50, the maximum fluence of gravity will reach a terminal velocity

7-7
 AM CP 706-185

when the aerodynamic drag on the particle is equal collisions between particles and resulting in coagu­
to the effective weight of the particle. I f the par­ lation or agglomeration o f the particles.
ticle is a rigid sphere which is large with respect
to the mean free path of the gas, but not so large 7-2.1.2.1.2 Diffusion
that, inertia effects are important, Stokes’ Law is
Diffusion of particles due to Brownian motion
applicable, and the terminal velocity v is given
results because the particles are impacted by the
by:
gas molecules o f the suspension medium. The mo­
gd«(p — p’ ) tion imparted to the smaller particles is greater
(7-1).
18t| than that imparted to the larger particles so that
where d is the diameter of the particle, p is the the amount, of diffusion is inversely proportional
density of the dispersed phase, p' is the density of to the diameter of the particles. 8 Diffusion effects
the gas, y] is the viscosity of the gas, and g is the ac­ are relatively unimportant for most particulate
celeration due to gravity. Particles which are small clouds of military interest. ■
with respect to the mean free path of the gas fall
somewhat more rapidly than this equation indi­ 7-2.1.2.2. Evaporation and Condensation
cates, while large particles settle somewhat more The evaporation rate for a given material de­
slowly. . , pends on the difference between the vapor pres­
The rate of sedimentation for some particles is sure of the dispersed material and the actual
given in Table 7-1. It is to be noted that the sedi- partial pressure of its vapor present in the air.
A t a given temperature, the vapor pressure o f a
TABLE 7-1 liquid increases with the degree o f curvature of
TERM INAL VELOCITIES AND DIFFUSION its surface; this increase becomes marked as the
COEFFICIENTS OF R IG ID SPH ERES OF droplet size decreases. Hence, a critical droplet
UNIT DEN SITY IN A IR AT 760 mm Hg exists for any temperature and vapor concentra­
PRESSURE AND 20°C tion. Droplets smaller than the critical size will
evaporate because their vapor pressure is higher
Diameter, Velocity, Diffusion Coefficient, than the partial pressure in the vapor phase, while
microns cm/sec cm2/sec those larger than the critical size will grow as a
result of condensation. The same considerations
0 .1 8.71 X 10-® 6.84 X 1 0 -#
apply to the sublimation pressure of a small, solid
0 .2 2.27 X 10- 4 X
2 .0 2 10~#
particle. ,
0.4 6.85 X 10- 4 8.42 X 10- 7
1 .0 3.49 X 1 0 -8 2.76 X 10- 7
2 1.19 X 10 - 2 1.28 X 10 - 7 7-2.1.2.3 Coagulation and Agglomeration
4 5.00 X 10 - 2 6.16 X 1 0 -8 The process of continuous and spontaneous for­
10 3.06 X 10 - 1 2.41 X 10 - 8 mation of larger particles is one of the striking
20 1 .2 , ' . '— ‘ . ■; -' ; characteristics o f any particulate cloud and can
40 5 , - - - - - be a major factor in the diminution of a smoke
10 0 25 ■ ---- cloud; liquid particles coalesce while solid par­
ticles agglomerate when they collide. As this
process continues, the smoke becomes coarser and
mentation rate of a screening smoke which has a finally settles out. It has been found experi­
particle radius of 0.3 micron is about one mile per mentally that the rate o f decrease of the number of
year.
particles, , is proportional to the square of
Nonspherical particles generally attain a lower
terminal velocity; however, this effect is not com- . the concentration n, o r :
pletely predictable. I f the smoke is heterogeneous,
(7-2)
the particles will settle at different rates causing

' 7-8
 AMCP 706-185

where C is the coagulation constant. In integrated motions of from one to many feet in diameter are
form : observed. The amount of atmospheric diffusion
is indicated by the angle of rise and angle of spread
(7-3) of the cloud as it travels downwind from the source.
The initial angles of rise and spread usually will
where n0 is the number of particles at t = 0 . be different than those measured farther away
While it is difficult to calculate the exact de­ from the point of generation.
gree o f pblydisperity, it can be shown that the
probability of collision between particles of un­ 7-2.2.1 Meteorological Factors
equal size is greater than that between particles of While the initial behavior of a particulate cloud
equal size. Hence, polydisperse smokes coagulate normally is due to the transient effect of the heat
faster than those which are monodisperse. Morer'- and turbulence resulting from the process by
i/fer, differential settling also increases thj prob­ which the particulate cloud is generated, the be­
ability of collisions between particles o f different havior of the cloud at a distance from the gen­
sizes. The coagulation rate of smoke is increased by erator depends on the meteorological conditions
stirring, since eddies and swirls result in particles prevailing. The principal meteorological factors
having , a higher relative velocity which increase affecting travel o f this type of cloud are wind speed,
chances of collisions resulting in an increa sed co­ direction, turbulence in the lower atmosphere, and
agulation rate. . thermal gradients.
7-2.2 TR A V E L AND PERSISTEN CE OF
P A R TIC U LA TE CLOUDS 8 - 1 2 7-2.2.1.1 W ind Speed and Direction
The behavior of a particulate cloud is strongly To obtain a cloud concentration in an area
influenced by the diffusive properties of the at­ from a limitpd number p f stationary sources, a
mosphere. For example, the persistence of screen­ wind velocity of fixed speed and direction is de­
ing smokes, which are composed of par tides too sirable. Too high a wirai spaed requires an ex­
small to fall out appreciably by Stokes’ Law and orbitant rate o f productujju in order to maintain
which have too low a vapor pressure to evaporate, proper coverage, while too low a wind speed re­
is almost completely dependent on meteorological quires excessive time to develop the cloud. I f there
factors which tend to dilute the cloud. The form is no wind, good results can only be obtained by
of a particulate cloud in the atmosphere depends producing the cloud from a moving vehicle such as
upon the location, type, and configuration of its a plane or boat, or by the projection of smoke
source. When a cloud is emitted from a jet at a generating munitions into the area. The latter
considerable velocity, mechanical turbulence and method is feasible only in offensive operations.
rapid mixing with the air results. This initial con­ Conditions of very low wind speed are likely to
dition of turbulence disappears by the time the be -accompanied by sudden variations in the wind,
cloud has traveled a short distance from the gen­ carrying the particulate cloud into areas where it
erator. Also, the formation o f particulate clouds is not desired.
of military interest is accompanied by sufficient When a particulate cloud is emitted by a sta­
heat so that the cloud as a whole will rise. As tionary generator in a steady wind, the plume
the cloud becomes more and more diluted with travels downwind with the speed o f the wind and
cooler air this effect will be less observable unless the axis of the plume is parallel to the wind di­
there is a very great initial rise in temperature, as rection. The density of the cloud at any point
is the case when smoke is produced by the burning downwind will be, in general, approximately in­
of white phosphorus. (See Paragraph 7-3.3.2.1.) versely proportional to the wind speed.
The process by which smoke is diluted and mixed
with air is called “ atmospheric diffusion,” This 7-2.2.1.2 Turbulence
process is also termed “ eddy diffusion” to distin­ W ind speed and direction are subject to rapid
guish it from molecular diffusion since eddy-like and violent fluctuation. This unsteadiness in wind

7-9
AMCP 706*185

velocity and direction can be considered to be due per 1 0 0 meters, there will be no tendency for the
to pulsations taking place in three directions; air to rise because the air inass carried upward
namely, in the general direction of the wind, and will become colder and heavier thah the surround­
in horizontal and vertical directions at right angles ing air. This decrease o f temperature with alti­
thereto. The total of these pulsations in the dif­ tude of 1°C per 100 meters is termed by the meteor­
ferent directions is a measure of the gustiness or ologist the adiabatic lapse rate for dry air, and the
turbulence of the atmosphere. degree of stability or instability of the atmosphere
- One obvious cause of turbulence is mechanical. will depend upon the extent to which the tempera­
The higher the wind velocity, the greater the tur­ ture gradient departs in one direction or the other:
bulence, "particularly over rough terrain. Over a from this critical value. An extreme condition,
smooth surface of water there will be no turbu­ when the temperature increases with altitude, is
lence produced by mechanical causes at low wind known as inversion, which causes extreme. sta­
speeds. Wind speeds greater than 10 to 11 knots, bility in the lower atmosphere. The meteorological
however, will produce waves which, in turn, pro­ factors described contribute to the degree o f sta­
duce mechanical turbulence in the lower air layers. bility o f the atmosphere which exerts a consider­
Another important factor in producing turbu­ able influence on the performance of a smoke cloud.
lence is thermal instability in the lower atmosphere. Extreme conditions of stability or instability will
During the day in bright sunshine, the ground influence the effectiveness o f the smoke cloud in a
surface receives a great deal of heat from the sun particular tactical situation. ...
and, since the earth is a poor conductor, the tem­
perature of the surface will rise many degrees. 7-2.2.2 Stability of Aerosol Clouds Under Various
The layer of air in contact with the ground is Meteorological Conditions ' ; .
heated and, since it becomes lighter by expansion,
the layer rises. Since the warm lower layer of air
7-2.2.2.1 Stable Conditions ; . . •
cannot rise everywhere uniformly, it must break
Under inversion conditions over smooth ter­
through the upper cooler layers somewhat as bub­
rain such as calm water, the only tendency shewn
bles burst upward through a liquid. The actual,
by a smoke cloud to rise and spread is due to the
driving force is the weight of the cooler air, which
initial transient effect caused by the heat and'
settles toward the ground displacing the warmer,
turbulence produced by the smoke generator. The
lighter air. These upward, convective currents
turbulence; is quickly damped out but the heat
cause the bumpiness of the air which is noticeable
produced may be sufficient to cause a very pro­
in an airplane. The passage of a warm or cold
nounced rise, as is the case with White phosphorus
front may completely alter the temperature rela­
smoke munitions. In the case of oil sinoke, where
tion between the ground surface and air and pro­
the amount of heat produced is small, the tempera­
duce stability or instability regardless o f time of
ture of the smoke at any dilution is only slightly
day or sky conditions. ..
greater than the temperature required to produce
a buoyancy sufficient to offset the increase in
7-2.2.1.3 Thermal Gradient density caused by the presence o f the smoke ma­
Stability conditions in the atmosphere are de­ terial. As the smoke rises, the temperature falls
termined by the temperature gradient therein. If because o f two effects; namely, further dilution
the temperature decrease with height is more than with cool air, and adiabatic expansion due to a de­
1 °G per 100 meters, the air will be unstable; i.e., crease in barometric pressure. Since, in an in­
the lower layer o f air will tend to rise and con­ version, the temperature o f the surrounding air
tinue to rise as long as this condition prevails. This increases with increasing altitude, an elevation is
is caused by the rising mass of air, expanding and soon reached at which the smoke is stable, possess­
cooling as it rises, becoming warmer and lighter ing a density identical with that o f the surround­
than the surrounding air. I f the decrease in tem­ ing air. . ■' ■ : ■, ■ . ■ ' .■ v " .
perature with altitude is between zero and 1°C Oil vapor smoke is often observed to level off

7-10
 AMCP 706-185

at an elevation of approximately 1 0 0 feet under wind velocity. An instantaneous view o f the cloud
stable air conditions. Certain types of smoke ex­ would show that it is furrowed and broken by
hibit an erratic behavior because o f abnormal den­ variations in the wind direction and sudden up­
sity. Examples o f these are: (a ) the smoke pro­ ward convective, currents.
duced by burning oil in an orchard heater in which The lower air is thermally unstable when the
carbon particles and carbon dioxide gas are pres­ negative temperature decrease with altitude is
ent, and (b ) HC smoke in which large particles of more than 1°C per 100 meters of elevation near
zinc chloride and other heavy materials are fam ed. ground level. This negative gradient may con­
While a substantial amount of heat is produced tinue indefinitely upward. Thus, in thunderstorms,
in the formation o f these smokes, much of it is cumulus clouds often rise to a height of several
quickly lost by radiation, particularly at night. miles; a smoke cloud would be carried to the same
Since the heat produced in the generation c f the height.
smoke will usually cause the smoke cloud to rise Under other circumstances, a current, of warm-
even under the most stable conditions, it may be
or air may be blowing at an elevation of a few
anticipated that the cloud will lift entirely off the
hundred feet so that the temperature gradient
ground Sifter a short distance of travel. If, how­
may become zero, or even positive, giving an in­
ever, a wind o f considerable velocity is blowing,
version at this elevation. There is no. tendency
this lifting from the ground will not occur.
for the lower air to rise through this warmer light­
Although the heat produced in the smok( gen­
er layer, and a definite ceiling w ill be established
erator promotes a rise, it has little effect upon the
for the convective turbulence. Within this layer
spread of the smoke cloud. The spread that oc­
the atmosphere turns over and over, and the smoke
curs is due to initial turbulence and this soon
damps out. Consequently, if it is desired to pro­ may become diffused throughout the layer before
duce continuous clouds of smoke from a series of it has traveled very far. However, eddy diffusion
individual generators, it is necessary to place always occurs at the boundaries of the .upward
the generators very close together; otherwise, the convective currents, causing some smoke to diffuse
individual plumes may riot merge for a long way throughout the settling layer of cooler air even
downwind. This situation holds for Smoot i ter­ with a high convective ceiling.4
rain. However, if the terrain is covered with The rate of rise of the convective current in­
shrubbery, for example, the lateral spread of the creases with thermal instability. The angle of rise
cloud is greatly increased as a result o f the me­ of the smoke cloud (as a statistical average) is in­
chanical turbulence produced by tbe wind flowing versely proportional to the wind velocity. With
through the Shrubbery. zero wind, the convective currents rise directly
upward. As the wind increases, the direction of
7-2.2.2.2 Unstable Conditions the convective current is inclined increasingly
away from the vertical.
When the air current is turbulent because of
therm al: instability, atmospheric diffusion takes
place to such an extent that the initial, transient 7-2.2.2.3 Estimation o f Atmospheric Diffusion3 .
behavior o f the cloud, due to the heat and ;urbu- Two expressions were derived which enable the
lence from the generator, is of little significance. concentration x (grams per cubic centimeter) at
The aerosol cloud continues to rise and spread as a given point in a smoke cloud to be predicted from
it travels downwind until the cloud becomes so knowledge of the rate of emission ot' particulate
thin that its boundaries are no longer distinguish­ matter and of certain meteorological properties of
able to the eye. I f a time exposure were to be the atmosphere. These equations: for predicting the
taken o f the cloud, it would appear as a con: with concentration from continuous point and line
its apex at the generator and its axis rising at an sources at ground level are:
angle from the horizontal, the: angle of rise de­ Continuous point source emitting Q grams per
pending upon the degree of instability ai d the second:
AMCP 706*185

a* (x,y,z) = c. Be persistent when disseminated, i.e., it will

2Q not evaporate, fall out or coagulate rapidly.
*CvCeUx2- ” d. Be effective at a low concentration of ma­
terial.
Continuous crosswind infinite line source emit­ e. Be substantially nontoxic; noncorrosive to
equipment, and, except for control agents,
ting Q grams per second per centimeter:
nonirritating to the eyes, throat and skin.
2Q —z f. Be suitable for large-scale manufacture,
x L(x,z) =
‘z'ACzUx1~2n
exp
[ C *x 2—n ] (7-5)
storage, and transportation, without hazard
or deterioration.
where the space coordinates x, y and z (origin at
the source) refer to the downwind, crosswind, and
vertical directions, respectively; V is the mean 7-2.3. 1 Screening Smokes
wind velocity; Cv and Cz are generalized eddy Screening smokes are usually white and can
diffusion coefficients; and n is a parameter refer­ be used to:
ring to the stability of the atmosphere, the nu­ a. Conceal movements, intentions, equipment,
merical value of which varies between zero and and installations of friendly forces from
unity These equations indicate that the concentra­
ground observation.
tion varies directly with the source strength Q and
b. Blanket friendly positions and installations
approximately inversely with the mean wind ve­
in order to conceal them from air observa­
locity U. The distribution of concentration in the tion and attack.
crosswind direction and in the vertical direction is c. Prevent aimed fire on approaching friendly
approximately Gaussian; however, due to ground aircraft, i.e., to screen the landing of air­
reflection, the vertical distribution corresponds to borne troops by parachute and glider.
only one-half of the Gaussian curve. I f the terrain d. Provide an extensive, thin haze for conceal­
is level and there is only a small temperature ment 1 of friendly areas without seriously
gradient, n is approximately 0.25. Under these impeding close-range vision.
conditions, the peak concentration downwind from e. Establish dummy screens to deceive observ­
a point source will decrease as x ~ 175, and for a ers.
line source as a- - 0 - 88 f. Communicate.
g. Form a thermal radiation attenuation screen.
7-2.3 SPECIFIC PROPERTIES OF M ILITARY
There are three types of smoke screens. A
SMOKES
smoke screen laid over friendly areas to hinder
Smokes are used for four basic military pur­
enemy aerial observation and visual precision bomb­
poses: (1 ) for screening, (2) for signaling, (3) for
ing is called a blanket screen. This type screen is
tracking and acquisition, and (4) for disseminat­
formed by the gradual merging, downwind from
ing (see Paragraph 7-3) of agents in riot control
the source of generation, of individual smoke
and other applications. While smoke may be pro­ streams. A smoke haze is normally established in
duced from a large number of chemicals in a a battle area to conceal friendly activities from
variety of ways, only a few of these meet the spe­ observation and ground fire. It is formed in much
cific requirements for a military smoke. The ideal the same manner as a blanket screen. Usually,
military smoke material will: however, a smoke haze is less uniformly dense than
a Be available in sufficient quantities for large- a smoke blanket. A smoke curtain is a dense,
scale production of the mixture at a rela­ vertical development to conceal objects at ground
tively low cost. level from observers at ground level.
b. Be easily and efficiently disseminated with­ Under many circumstances these distinctions
out the use o f elaborate equipment. disappear. For example, a smoke curtain may in-

7-12
 AM CP 706-185

terfere with aerial observation or a blanket screen dissemination, measurement, etc., o f colored smokes
may settle to the ground and become a snoke is contained in Paragraph 7-3.4.
curtain. These distinctions are important foi de­
fensive screening only, inasmuch as offensive nse 7-2.3,3 Tracking and Acquistion Smokes
of smoke has the primary objective of blin
Smoke-producing devices such as generators or
unfriendly forces by enveloping them in a dense
tracers are used as an aid in the optical tracking
blanket of smoke at ground level. Due to the re­
of projectiles, high speed aircraft, and missiles
quired subsistence o f smoke screens, large qu mti-
both at sea level and high altitudes. These devices
ties of near optimum materials must, be used.
optimize the ability to locate and track vehicles
Of the large number of available smoke-producing
along the flight path and minimize the possibility
chemicals, only a few have been found suitable for o f losing significant data. Requirements for optical
use in the production of military smoke screens. tracking aids vary considerably because of the
wide range of conditions encountered in the track­
7-2.3.2 Signal Smokes ing o f test vehicles operating over a wide range
It is h prerequisite that smokes used for sig­ of altitudes and speeds. No single smoke agent or
naling and communications be clearly disting lish- generating system will satisfy all requirements
and numerous smoke-producing methods are neces­
able from other smokes (and other clouds) pro­
sary. Each is designed for a particular applica­
duced for different purposes. Thus, the use of
tion, emphasizing certain ideal characteristics. :
white,-gray, .and blanket smokes for signaling is
While the value of a screening smoke is due
very limited and colored smokes are normally used
to its absorbing and light-scattering power, the
lot this purpose. In addition, the use of several
visibility of a smoke tracking aid is due, chiefly,
different colors allows more information to be
to its light scattering power. The ideal tracking
'transmitted and also results in a clearer distinc­
.’'and- -acquisition '.smoke. should have the following,
tion between the sinoke signals and a varying back­
characteristics:
ground. Effective methods for the production o f
a. Be efficient, on a weight and volume basis.
colored smoke, including explosive dissemination,
b. Have the ability , to function and perform
involve the vaporization and condensation of a
at altitudes where pressure is low, and water
dye; therefore, the dye must be heat-stable so
vapor and oxygen concentrations are small.
that it can be rapidly vaporized at a relatively
c. Have the ability to function through the
high temperature without appreciable thermal
range o f temperatures encountered from
degradation. In addition to its color, important
ground temperature to the minimum high
characteristics of a colored smoke include:
altitude temperature.
a. Visibility (the conditions under which the d. Require little power for generation and dis­
cloud can be seen and its color recognised). persion.
b. Duration (the time period during v rhich e. Be as nontoxic, nonexplosive, and noncor­
smoke is evolved from a munition). rosive as possible with regard to both smoke
c. Persistence (the total period o f time during chemicals and products.
which a cloud is visible).
d. Volume (the quantity o f smoke emitted; for
7-2.,3.4 Smoke for Dissemination of Agents
colored smokes, volume has also been de­
fined as the cross-sectional area o f a cloud Agent smokes for riot con trola n d other pur­
presented to an observer). poses are produced in much the same way as col­
ored signal smokes. In many cases, a vaporization
Although not as important as in the ca s of process is followed by a condensation process in
screening smoke, the smoke cloud should ' j as which the agent condenses to form the disperse
nontoxic, .nonirritating, and noncorrosive as pos- phase o f the smoke. Agent smokes may be dis­
sible; Information on the composition, metho d of seminated by explosive means as well as by some

7 -1 3
AMCP 706-185

of the other methods discussed in Paragraph 7-3. librium is reached. The production of a super­
The physiological effectiveness of materials dis­ saturated vapor and formation of a dispersed phase
seminated in this way depends strongly on the by condensation are complex processes and pro­
particle size. 'While visibility of the smoke may or ceed essentially simultaneously. Consequently,
may not be important, the volume of smoke and its little direct information has been obtained on the
duration is important. It is also necessary that the early stages of particle formation.
vaporization and condensation process be efficient Condensation of a vapor is facilitated by the
and produce a minimum of undesired changes in presence of foreign particles. Insoluble foreign
the agent being dispersed. particles can absorb a thin film of vapor on their
surfaces and behave as liquid droplets of equal size.
7-3 DISSEMINATION TECHNIQUES If the foreign particle is soluble in the condensed
Dissemination refers to the process by which a liquid, the vapor pressure o f the liquid is decreased
chemical agent is converted into a cloud consisting and, consequently, the supersaturation required for
either of vapor or fine particles, suspended in the rapid condensation is reduced. Charged droplets,
air. For agents such as smoke, which are dis­ which are formed due to the presence of ions, tend
seminated as a particulate cloud, the process to have a larger surface and, hence, a lower vapor
usually involves the formation of small particles pressure which result in condensation at a lower
of the dispersed phase and the distribution of these supersaturation. If condensation, in the absence
particles in the air. of foreign particles, were to start from a single
molecule, the theory indicates that a much higher
7-3.1 FORMATION OF THE DISPERSED supersaturation would be required than that ob­
PH ASE served experimentally. Therefore, it is postulated
The dispersed phase can be formed in two that small aggregates of molecules, of approxi­
ways: (a) by condensation processes in which mately the critical size, are continually produced
molecules of a vapor unite to form the particles by random fluctuation in the vapor. Molecular ag­
of the dispersed phase, and (b) by dispersion gregates smaller than the critical size will disap­
processes in which the particles are formed by pear, while those larger than the critical size will
the breaking up of a solid or liquid material. In continue to grow.
the first case, the specific surface (the total surface In many cases of military interest, the super­
per unit-volume of the material) decreases; while saturated vapor is produced by the evaporation of
in the second case, the specific surface increases. a substance, followed by the mixing with cooler
air of the relatively warm vapors produced. Con­
7-3.1.1 Vapor Condensation Processes densation then follows, resulting in the formation
of the dispersed phase. The particles in a smoke
The dispersed phase of most particulate clouds
produced as the result of combustion are also due
is produced by condensation from the vapor phase
to vapor condensation. In this case, due to the
and involves the uniting of vapor molecules to form
higher temperatures involved, it is impossible to
larger particles. The formation of a dispersed
analyze the process in detail. Chemical reactions,
phase by this method involves two steps: (a) pro­
including several for producing smokes of mili­
ducing the vapor in a supersaturated state, and
tary interest, often involve a component of the at­
(b ) condensing the supersaturated vapor. The
mosphere (such as water vapor) as one of the
supersaturated vapor is usually obtained b y : (a)
reactants.
the cooling of a warm vapor, or (b) a chemical
reaction which results in the formation o f a super­
saturated vapor. In either case, the excess vapor 7-3.1.2 Dispersion Processes
will condense to form the particles of the dispersed The formation of a dispersed phase by disper­
phase. The condensation of a supersaturated vapor sion methods involves the subdivision of a solid or
is accompanied by the liberation o f heat so that this liquid into fine particles. The actual mechanisms
process will continue, once initiated, until equi­ by which the fine particles are produced and dis-

7-14
 AMCP 706-185

persed in the suspending medium are intiniately the venturi nozzle type, where the smoke-produc­
related and not always completely understood. ing material is atomized prior to evaporation.
In the case of a liquid, energy applied to it causes There are two other important types o f atom­
the liquid to assume an unstable configuration izers which are of somewhat lesser military im­
which then breaks up into small droplets. A solid portance. The first of these types is tbs'centrifugal
substance may be disrupted and dispersed into fine atomizer in which the liquid is fed onto the center
particles by application of energy, or the solid of a rotating disc, cone, or top and centrifuged
can be preground to the desired size and then dis­ off the edge, producing droplets of relatively uni­
persed into the suspending medium. • form size. In the second type, the hydraulic
In the atomization of liquids, the energy is ex­ atomizer, liquid is forced through a nozzle and is
panded mainly i n : (a) forming new surfaces, broken up into droplets. In this latter case, the
(b) overcoming viscous forces in changing the atomization depends more on the physical proper­
shape of the liquid, and (c ) meeting losses due to ties of the liquid and the conditions of ejection
inefficient application of the energy to the liquid. from the nozzle than on the interactions between
Devices commonly used to disperse liquids Ire of the liquid and the surrounding gas.
three main types. Dusts can be formed by the disruption of solid
One type employs a high velocity gas or air material or by the dispersion of a material, finely
jet to break up a liquid emerging from a nozzle. preground to a desired size.
Atomizers of this type produce a very wide range The forces required to disrupt the solid ma­
o f droplet sizes which can be somewhat reduced terial may be applied rather slowly by milling,
by trapping the larger droplets within the atomizer. crushing, or grinding, or rapidly through ex­
The degree of atomization obtained by this rriethod plosion or impact. In either case, the applied forces
is influenced by the following factors: I cause disintegration by splitting or cracking along
a. The relative velocity of the air pant the planes of weakness in the material. The result is
droplets. the formation o f small fragments and fine particles
b. The physical properties of the liquid, in­ released from the freshly formed surfaces by
cluding surface tension, viscosity, and den­ cracking on a microscale as the material is torn
sity. apart.
c. The relative quantity of air expressed as the
ratio of volume of air to volume of liquid. 7-3.1.3 Combined Processes
Within a limited range, the Nukiyama Tanasawa Since mist dispersion methods will not pro­
equation applies, even though it is dimensionally duce particles of the correct size, in many cases the
incorrect. 8 dispersed phase for smokes o f military interest is
obtained by condensation from a vapor phase which
° « ( 10000,, v
d0 = ^ + 597 ( - L ) (7-6) is formed by evaporation o f the smoke-producing
vy/p ' V»P > \ Qa )
agent. However, in order to facilitate the trans­
where d0 is the diameter in microns o f a single drop fer of heat to and the removal of the vapor from
with the same ratio of surface-to-volume as a repre­ the surface o f the agent, it is often atomized be­
sentative sample o f the atomized droplets; v is fore it is evaporated. Particulate clouds can be
the velocity of the air in centimeters per second developed by the atomization of a solution con­
relative to that of the liqu id; Ql /Qa is the volume- taining a nonvolatile or slightly volatile solute in
flow-rate of liquid to the volume-flow-rate of air; a volatile solvent. The solvent evaporates and leaves
p is the density of the liquid in grams per cubic the solute which condenses to form the dispersed
centimeter; p. is the velocity of the liquid in poises; phase of a particulate cloud. The explosive dis­
and v is the surface tension in dynes per centi­ persion of volatile materials, such as the dyes used
meter. This equation is used in estimating t he per­ for colored smoke, is also a combined process. The
formance of particulate cloud generators such as explosion mechanically disperses, vaporizes, and

7-15
 AH CP 706-185

mixes the material with cooler air, resulting in the materials the proper references should be con­
formation of a particulate cloud. sulted1 4 ' 1 0 1 6 1 7 and if little or no information is
available, extreme caution should be exerted.
The remaining sections of this chapter em­
7-3.2 M ILITARY PRODUCTION OF SMOKE
phasize production of smoke by pyrotechnic means;
Pyrotechnic munitions for producing smoke,
however, the same principles are applicable to
whether for screening, signaling, or other purposes,
other methods for producing smoke, some of which
are usually one o f the following general types:
are briefly discussed.
a. Venturi Thermal Generator Type. The
smoke-producing material and the pyro­
7-3.3 W H ITE SMOKES
technic fuel block required to volatilize the
White smokes are widely used for screening, ac­
smoke material are in separate compart­
quisition and tracking, fire control, and signaling
ments. Tlie smoke-producing material is
purposes. They can be produced from many chem­
atomized and vaporized in the venturi noz­
icals in a variety of ways and, in general, are more
zle by the hot gases formed by the burning
efficient on a weight basis than colored smokes.
of the fuel block.
Relatively few of the methods for producing
b. Burning Type. Burning-type smoke com­
white smoke are of value for production of the
positions are intimate mixtures of chemicals.
large amount of smoke required for screening
Smoke is produced from these mixtures by
purposes which is one of the important uses for
either o f two methods. In the first method,
white smoke. Because of the large amount of
a product of combustion forms the smoke or
smoke required, it is important that the maximum
the product reacts with constituents o f the
effect be obtained per unit-weight of smoke-pro­
atmosphere to form a smoke. In the second
ducing material. This will depend o n : (a) the
method, the heat of combustion of the pyro­
weight of the material available to form smoke
technic serves to volatilize a component of
particles, whether this was originally present in
the mixture which then condenses to form
the mixture or is contributed from the atmosphere,
the smoke.
and (b) the efficiency of conversion o f the smoke-
c. Explosive Dissemination Type. The smoke-
producing material into smoke particles having the
producing material is pulverized or atomized
optimum light-scattering and obscuring capability.
and then vaporized, or a preground solid is
Formation of smoke particles by condensation
• dispersed by the explosion of a bursting
from the vapor phase is the only practical way to
charge.
produce the large amount of white smoke required
It is to be noted that smoke is also produced for for military screening purposes. The hot vapor is
military purposes by other than pyrotechnic means. usually produced by volatilization or by chemical
For example, certain screening-smoke materials reactions in which one reactant is normally a com­
can be disseminated by mechanical smoke genera­ ponent of the atmosphere. Examples of the three
tors and others by the use of airplane spray tanks. most widely used screening smokes are :
Signals and tracking aids can be generated by a. Oil smoke, which is produced by the volatili­
using hot exhaust gases from aircraft or tank en­ zation and condensation of oil.
gines to vaporize the smoke-producing materials. b. White phosphorus smoke, which is produced
The ingredients used in smoke-producing chem­ by chemical reaction with the atmosphere.
icals and combustion products, and/or the con­ c. Zinc chloride smoke, which is produced
densed vapor particles produced in a smoke, should by a combination o f volatilization and chem­
be considered to be irritating and/or toxic. Care ical reaction.
should be exerted in working with smoke-producing
materials and the resulting smokes, especially re­ Oil smokes are normally produced by venturi-
garding the inhalation of high concentrations and type thermal generators, although intimate mix­
long exposures thereto. When investigating new ture burning types o f munitions have been de­

7 -1 6
 AMCP 706-185

veloped for dissemination of oil smoke. 2 inc A pressure tube connects the agent compartment
chloride smoke is produced by a burning-type and the fuel compartment and permits the pres­
munition. White phosphorus smoke for screening sure developed by the fuel block to aid in forcing
is normally produced by a bursting-type munition. oil through an orifice into the venturi throat.
Here the oil is mixed with the hot gas stream
7-3.3.1 Oil Smoke flowing through the venturi. The high velocity
A very satisfactory white screening smoke jean of the gases promotes atomization of the incoming
be produced by the vaporization and condensation oil stream and the droplets are quickly vaporized.
of an oil that has a high boiling point and a |low The rate of feeding is governed by the pressure
volatility. The first successful generator for pro­ differential between the agent compartment and
ducing oil smoke was the M l mechanical snjoke the throat, the size of the feed orifice, and, to a
generator. In this generator the smoke oil Was minor extent, the resistance to the flow through
flash evaporated at a relatively high temperature, the feed tube. Little decomposition of the agent is
with water added to prevent coking. The equip­ caused by the relatively high temperatures required
ment was heavy and complicated, including gaso­ for rapid evaporation due to the short period of ex­
line engines to operate the necessary pumps knd posure. The efficiency of this type of generator is
blowers, coils for the evaporation of oil md highest when the agent is heated to a rather high
water, and burners using fuel oil to heat the coils. temperature for the shortest possible time rather
In spite of their many disadvantages, these gen­ than a lower temperature for a longer period. The
erators, along with similar types, were widely r sed particle size of a smoke produced in a venturi
during W orld War II. thermal-generator type of munition can be defined
in terms o f : (a) the Nukiyama Tanasawa equation
7-3.3.1.1 Venturi Thermal Generators (Equation 7-6), modified to include the effect of
Toward the end of W orld W ar II another system heat upon the aerosol, and (b) the thermo­
smoke generator, the Hessien, was developed for dynamic properties of both the liquid and the
the U. S. Navy in which the fog oil was atomised, pyrotechnic combustion products at the point of
mixed with the hot gases produced by the com­ mixing, which controls the amount of liquid
bustion of a fuel, and vaporized in a venturi vaporized. Thus, the smoke formed can be con­
throat. The development of venturi-type thermal- sidered to be made up o f two parts: the larger
generator munitions using pyrotechnic fuel blocks particles produced predominantly by the atomiza­
was also accomplished during W orld W ar I I ; h ow­ tion process, and smaller particles produced by
ever, these items were not fully ready for produc­ vaporization and condensation.
tion until after the War. The portion of the liquid vaporized depends
on the heat transferred from the hot gases. The
7-3.3.1.1.1 Operation o f Venturi Thermal amount vaporized is significantly affected by mass
Generators flow rates, mean specific heat, and initial gas tem­
The operation of a venturi-type thermal gen­ perature. With proper design o f the venturi,
erator to produce a smoke involves the atomization there is sufficient time for the heat to be trans­
of the liquid, the vaporization of the droplets ferred from the gases to the liquid. The overall
produced, and the dispersion of the vapor in a process in the venturi can be considered to be
stream of hot gases. A typical unit, shown sihe- essentially adiabatic.
matically in Figure 7-3, consists o f: Generators of this type regulate particle size
a. a fuel block which, on burning, produces through rapid dilution of the vapor with cool air.
the hot gases, As mixing and cooling occurs, the saturated vapor
b. a chamber containing the liquid to be condenses. For oil smokes, a very rapid coagula­
vaporized and dispersed, and tion occurs for a very short period of time causing
c. a high velocity vaporizer tube in the form of the particles to grow. Dilution, however, occurs so
a venturi. rapidly that the coagulation is checked after a few

7-17
AMCP 706-185

d. Supply the carrier gas to remove the oil

VAPOR GAS EXIT vapor.

Ammonium nitrate-charcoal compositions have

proved to be a satisfactory fuel block for the
volatilization o f fog oil.
The reaction between ammonium nitrate and
carbon can be written:

N K U N O g-fC ----- ►CO + 2HaO + N 2

if it is assumed that all the carbon is oxidized to

carbon monoxide. I f all the carbon is assumed to
be oxidized to carbon dioxide the reaction i s :

2 NH 4 NO3 + C ----- ►C 0 2 + 4H20 4 - 2N2

The volume of gas, measured at 0°C and 760 mm

Hg, is about 0.97 liter per gram of mixture for the
first reaction and 0.92 liter per gram for the second
reaction.
Analysis of the gases produced by the burning
of a typical ammonium nitrate fuel block ( 1 1
parts charcoal, 3 parts linseed oil, and 83 parts
Figure 7 -3 . Typical V enturi Thermal G enerator
ammonium nitrate) gave the following:

h 2o 48.8% C02 13.5%

thousandths of a second, and a remarkably nar­
NHa 0 .6 % CO 5.2%
row range of particle sizes results. I f the generator
n2 26.1% h2 5.8%
is working well, it is possible to obtain a rough
check on the particle-size range by a simple color which corresponds, approximately, to the reaction:
test. I f the sun ’ 8 disc or any other bright light
6NH4N 0 8 -t- 4C ----- ►11H20 + CO + 3C02
source, when almost obscured, appears red, the
4" 6N2 -f- H2
particle size is somewhat smaller than desired; if
it appears magenta, the particle size is satisfac­ As illustrated in Chapter 3, this reaction should
tory; if it appears blue, the particle size is yield nearly one liter o f gas, measured at 0°C and
larger than desired for maximum screening effec­ 760 mm Hg, per gram of mixture burned. A p­
tiveness. I f the smoke produced is not of a uniform proximately 0.685 kcalories per gram of mixture is
particle size, the sun’s disc will appear white and evolved when the mixture is burned.
no conclusion can be drawn as to particle size be­ Fuel blocks can be pressed using a binder, or
ing produced by the generators. they can be cast. In either case, the burning rate,
which determines the heat and gas evolution rates,
is roughly proportional to the area o f the burning
7-3.3.1.1.2 Fuel Blocks418
surface. For a fixed burning area, the rate of
The heat and product gases produced by the
burning can be changed b y :
burning of a pyrotechnic fuel block m ust:
a. Varying the size o f the charcoal,
a. Raise the temperature of the oil to the b. Modifying the surface o f the charcoal, and/
vaporization temperature. or
b. Supply the latent heat of evaporation to the c. Changing the composition of the fuel block.
oil.
c. Supply the heat lost as sensible heat in the Carbon is normally the least-uniform ingred­
hot gases and hot container. ient and, therefore, causes most o f the variation

7-18
 AM CP 706-185

TABLE 7-2
CH A R A C TE R ISTIC S OF T Y P IC A L O IL SMOKE POTS

Characteristic T yp e D evice

F loa tin jf {F ig . 7 -3 ) Training {F ig . 7 -4 )

S ize, in. 13 high by 13 dia. 5.7 high (including

fuze) by 2.5 dia.
V en tu ri Orifice
D iam eter, in. 0.0890 0.076
W eig h t, lb 14.5 (0 il) 0.24 (o il)
12.0 ( f nel) 0.22 (fu e l)
O il A g e n t SGF N 0 . 1 or 2 SGF No. 1 or 2
F u el B lock C om position F a st-B u rn in g T op M ixtu re
86 % NH«NOs 82% NH<NO«
11% Charcoal 11% Charcoal
3% lin seed Oil 4% ENOa
| 3% Linseed Oil
S low -B u rn in g B ase M ixtu re
82% NH4N0*
8 % NH4CI
7% Charcoal
3% lin seed Oil
Ig n ition Bouchon faze (M 208) Bouchon fuse (M 201A1)
‘ *spits [ * through (sim ilar to
venturi igniting floating type)
quickm&tch St starter
B u rn in g T im e, min 12 ± 1.5 1.2 ± 0.25
A p p lica tion Screening, used singly Grenade type,
or in multiple on used fo r training
la n d o r water purposes
O bscurin g P ow er Single pot Alls
a 13,000 ou ft
room and totally
obscures objects
4-6 feet away.

in burning fo r supposedly identical fuel blocks. with charcoal. On the other hand) adding am­
Treatment o f the carbon with chemicals (each as monium chloride or substituting naphthalene (o r
potassium carbonate or similar alkali chemicals) starch in a cast fuel block) fo r charcoal w ill re­
increases the burning rate while treatmen t with duce the burning rate.
an acid w ill decrease the burning rate. The sub­ An increase in either the initial temperature
stitution o f potassium nitrate, sodium nitrate, or or the pressure in the fu el block chamber w ill also
ammonium chlorate fo r part o f the ammonium increase the burning rate. Surging (a rapid burn­
nitrate w ill cause an increase in burning rate, A ing with a high rate o f gas evolution follow ed by
reasonable explanation fo r the increase is that slower burning with a low rate o f gas evolution) is
these compounds form carbonates when burned sometimes observed. This objectionable cy clic be-
 AMCP 706-185

BOUCHON FUSE

PRESSURE
TUBE
VENTURI

metSP^ujg

-VyP°g^K
METAL

.Figure 7 -4 . Typical O il Smoke Pot (F loating )

havior is probably due to variations in the charcoal

used inasmuch as surging is favored when a blend
of slow- and fast-burning charcoal is used to
make the fuel block.
Because charcoal may cause undesirable varia­
tions in the burning characteristics of a fuel block,
attempts have been made to develop a fuel block
which does not contain charcoal. A mixture of
guanidine nitrate, ammonium nitrate, linseed oil,
and ammounium dichromate was found to be only
partially satisfactory. Reasonable success was ob­
tained using polysulfide ammonium perchlorate
as a’ binder and a substitute for all or part of the Figure 7 -5 . Typical O il Smoke Pot (Training )
carbon in a castable fuel block. This reduced or
eliminated the swelling and cracking observed in pots similar to those used in orange groves in the
standard ammonium nitrate-carbon fuel blocks. United States, and the Hasler generator developed
and used by the British in the Battle of Britain.
7-3.3,i.l.3 Typical Venturi Thermal Generators In all eases, the smoke produced was brownish-
Characteristics of typical venturi-type thermal gray to black in color because the oil was partially
generators are given in Table 7-2. Figures 7-4 and decomposed thus yielding free carbon. In general,
7 - 5 illustrate schematically two types of oil fed the smoke produced had poor screening properties
smoke pots. and limited persistence.
Two oil smoke generator mixes which were
7-3,3.1.2 Other Methods for Producing Oil Smoke reasonably satisfactory were developed during
Before the development of the M l smoke gen­ World War II. The first was a mixture of saw­
erator, common methods for producing oil-based dust and charcoal impregnated with a solution o f
smoke screens included the reduction of air supply potassium chlorate and a high-boiling point oil
to the boilers of naval ships, the use of smudge (D iolj which had been jelled by the addition of

7-20

\
 AM CP 706-185

a small percentage of soap. The other mixture smoke is formed. Phosphorus pentoxide and phos­
consisted of jellied oil and black powder. In each phoric acid are not toxic in small concentrations,
case, the ideal mixture was one in which all of the although they may be irritating to the eyes, res­
fuel but none of the oil was oxidized, and in which piratory tract, and skin. Phosphorus smokes have
the amount of heat produced was sufficient to relatively little effect on metals.
vaporize all of the oil. The smoke exit orifice was
important in controlling the flaming tendency of 7-3.3.2.1 White Phosphorus
the mixture, the particle size of the smoke pro­ White phosphorus is widely used in bursting-
duced, and the pressure within the smoke pot. type munitions to produce smoke screens for
Considerable effort was directed toward the ground-combat operations, and for signaling and
development of smoke generators, using the sen­ spotting purposes. Slow-burning fragments of
sible heat in exhaust gases from vehicle and air­ white phosphorus, produced and spread by an
craft engines for the evaporation of oil to form explosive burster, are incendiary while burning.
screening smoke. Results indicated that the Since burning white phosphorus produces flesh
amount of smoke produced was not adequate for burns which are slow to heal, it is an excellent
screening purposes but was adequate for signal harassing agent.
ing. Ir. an attempt to increase the amount of White phosphorus is the most efficient smoke
smoki' produced, the exhaust gases were burned in producer on a weight basis; however, the screen­
an afterburner, thereby increasing their tempera­ ing effectiveness of white phosphorus in bursting-
tures and heat content. With this modification, type munitions is slight. Most of the charge burns
satisfactory smoke screens were produced by air­ within seconds following the burst, resulting in n
craft using internal combustion engines. smoke concentration many times that required for
7-3.3.2 Phosphorus Smokes effective screening. In addition, the temperature
White smoke consisting of small droplets of rise in the cloud immediately surrounding the
phosphoric acid have been widely used for mili­ burst is sufficient to produce a strong thermal up­
tary purposes. These droplets result from the draft which rapidly lifts the cloud from the ground
reaction of phosphorus pentoxide, formed by the so that the smoke cloud pillars. This may be help­
burning of phosphorus or phosphorus-containing ful for signaling purposes but generally reduces
the effectiveness of white phosphorus as a screen­
compounds in the air, and the water vapor in the
ing smoke. ,
air, or:
Two general ways to improve smoke-producing
P4 -)- 5O2----- > 2PgO(j
efficiency are possible. The first involves reduction
P 2 0 5 + 3H20 ----- > 2 H 3 PO 4
of the heat of combustion, which can be accom­
H sP 0 4 - f nH20 ----- » E sP 0 4 (dilute)
plished only by using different phosphorus com­
The concentration of phosphoric acid in the drop­ pounds. The second method, which is more attrac­
lets is determined by the relative humidity. Meth­ tive, involves controlling the rate o f combustion
ods which have been used to form phosphorus pent- by reducing the fragmentation o f the phosphorus.
oxide for military smokes utilizing phosphorus in­ Several methods for controlling the fragmentation
clude : | of phosphorus have been tried, including the addi­
a. burning in air of white phosphorus (which tion of mechanical reinforcement such as steel
is spontaneously flammable), wool, 19 asbestos, plastic tubes; wire screens, and
b. burning in air of the phosphorus vapor (pro­ other devices, causing ejection of the phosphorus
duced by the evaporation of red phosphorus in pieces of predetermined size. Other methods
in & fuel-oxidant mixture), and attempted involve the alteration of the physical
c. burning in air o f phosphine (produced by properties of phosphorus so as to produce a plas­
the action of a metal phosphide with water). tic mass with low shattering characteristics.
Phosphorus vapor is extremely toxic and causes Plasticized white phosphorus, 20 PW P, was
bone decay; however, it iR not present after the found to be. the most promising development for

7 -2 1
 AMCP 706-185

30CaSO* + 19P* ----- > 6 C a (P 0 3)a + 12Ca2 P 2 0 7

+ 10P4 S3
The heat produced by this reaction vaporizes the
remaining red phosphorus contained in the smoke
mixture. The phosphorus vapor burns on contact
with air. Some sulphur dioxide is formed when
the P 4 S3 , produced in the above reaction, burns
along with the phosphorus vapor:

P4Sg -(- 8 0 2 — -> 3S0 2 -f- 2P2Og

In the presence of moisture, there is a tendency

for red phosphorus to slowly oxidize due to the
presence of small quantities of copper and iron.
This may result in ignition difficulty and an over­
all decreased performance of the smoke item.
Stable red phosphorus has been produced by de­
creasing or eliminating these impurities. 2 1 , 2 2 '28

7-3.3.2.3 Metal Phosphides

Metal phosphides, especially calcium phosphide,
which was first produced commercially in 1920,
Figure 7 -6 . Typical W P -F illed Device (M15 W P Smoke have been used in sea markers. In these markers
Hand Grenade) the metal phosphide reacts with water to form
phosphine, which then burns in air to produce
control of the fragmentation of phosphorus and phosphorus pentoxide and water. For calcium
pillaring of the smoke. This consists of an intimate phosphide:
mixture of granulated white phosphorus in a vis­
cous rubber solution. The material burns more Ca3 P2 + 6H20 ----- > 3Ca(OH ) 2 + 2PHS
slowly and the particles do not disintegrate by 2PH 3 + 4 0 2 ----- » P 2 0 5 + 3H20
melting. As a result, pillaring is reduced and the The rate of reaction is governed by the access of
effective screening time is greatly prolonged. Test the water and by the back pressure of the gas
results have indicated that plasticized white phos­ produced. Calcium .phosphide has been the most
phorus produces distinctly better smoke screens satisfactory for this purpose. Aluminum phos­
than similar phosphorus-filled rounds. The anti­ phide is difficult to react and is slow-burning,
personnel incendiary action of PW P is as good as whereas magnesium phosphide reacts too rapidly.
that of WP.

7-3.3.2.2 Burning-Type Mixtures Containing Red 7-3.3.2.4 Other Reactions for Producing Smokes
Phosphorus Containing Phosphorus
Red phosphorus, the comparatively inert allo- Other methods for producing phosphorus-con­
tropic form of phosphorus, is used in burning-type taining smokes include:
munitions mainly for signaling purposes. Compo­ a. The dispersion of phosphorus in a solvent
sitions consisting of red phosphorus and certain such as carbon tetrachloride or carbon di­
oxidants or fuels are relatively slow-burning and sulfide. The solvent evaporates and the fine­
are sometimes used in sea markers. The chemical ly divided phosphorus burns in the available
reactions may be quite involved. For example, the oxygen and produces a dense white smoke.
main reaction for a burning mixture of calcium b. The reaction of phosphorus trichloride with
sulfate and red phosphorus appears to b e : bases such as ammonia and amines. The

7-22
 AMCP 706-185

Figure 7 -7.. Typical Red Phosphorus-Filled Device

reactions are complex as illustrated in the 7-3.3.2.5 Typical Devices

following example: The characteristics of typical smoke-producing
devices containing phosphorus are summarized in
PC13 + NH 3 ----- > PCI2 NH 2 + HC1
Table 7-3. Illustrations of such devices are shown
PClo NH 2 + NH 3 ----- » PC1(NH 2 ) 2 + H(pl
in Figures 7-6 and 7-7.
PG1(NH 2 ) 2 + NH 3 ----- » P (N H 2 ) 8 + HCi
HC1 + NH 3 ----- » NH 4 CI
7-3.3.3 Metal Chloride Smokes
The smoke is composed of a mixture of
A large number of metal chlorides have been
aminophosphorus chlorides and NH 4 CI; the
used to produce white smoke. All of the metal
smoke produced is considered irritating but
chlorides react with water to varying degrees and
not toxic; phosphorus trichloride is not ex-
this characteristic determines, to a large extent,
cessively corrosive to any metal affected by
their efficiency as smoke agents. While the methods
nyd*ochloric acid; either wet or dry it is
by which they are disseminated depend on the
quite corrosive to flesh. ’
particular metal chloride, once disseminated the
c. The dispersion of phosphorus sulfides in
metal chloride reacts with the water vapor in air
carbon bisulfide. The solvent evaporates ind
resulting in the formation of hydrated oxides, or
the finely divided particles of phosphorus
hydroxides and hydrochloric acid.
sulfide burn readily in air; total combustion
of these sulfides yields phosphorus pentoxide
7-3.3.3.1 Liquid Metal Chlorides
and sulphur dioxide:
The liquid metal chlorides can be disseminated
P<S3 -(- 8 O2 — 2P 2 0 5 + 3S 0 2 by thermal vaporization followed by condensation,
2P 2 S 5 + 1502 -> 2P2 0 5 + IOSO2 or by atomization. FM, a commercial form of
Both products react with water to produce titanium tetrachloride, has probably been the most
sulfurous acid and phosphoric acid; the widely used liquid metal chloride smoke agent.
sulfides of phosphorus are harmless to both
metals and flesh. The smoke produced is also 7-3.3.3.1.1 FM Smokes
relatively harmless to metals and personnel FM smoke agent, TiCL, is extremely reactive
under normal conditions; however, pro­ resulting in the formation of hydrated oxides, or
longed exposure to high concentrations with atmospheric moisture and, when used for
should be avoided. screening, . is often disseminated from aircraft

7-23
 AMCP 706-185

TABLE 7-3
CH ARACTERISTICS OF TY PICAL DEVICES USING
PHOSPHORUS FILLING

Characteristic Device

W P Smoke Hand Projectile

Grenade (M15) ( T91 H E W ater Marker)
Size, in. .4% high .12% long
2% dia. 1% dia.
Charge 15 oz PW P 2.6 lb Comp B.
Weight 0.66 lb Stabilized
Red Phosphorus
Ignition M206A1 fuze M500A1 fuze
- IIE burster Comp. B
Screening Scatters W P Explodes on
Capability over a 20 yd impact— 50 ft
, radius high; 50 ft d ia;
cloud duration
3 min— 25 mph wind
Application Thrown, bursting Used in 90 mm
charge explodes, munition
4-5 sec delay. (white marker'1

spray tanks.24 Its reaction with water vapor is when dissolved in dichloroethane and similar ma
relatively complex. First, the titanium tetrachlo­ terials. The solvent evaporates and the titanium
ride is hydrated. This reaction is followed by letraihloride reacts with the water vapor in the
further hydrolysis yielding, finally, titanium hy­ air to produce smoke.
droxide and hydrochloric acid. The smoke consists
o f a mixture of fine particles of solid titanium hy­
7-3.3.3.1.2 Silicon Tetrachloride
droxide, T j (O H )«; the hydrated oxide, T i0 2*
II-O ; intermediate hydroxyehlorides of titanium; Silicon tetrachloride is another liquid metal
and dilute 1101 droplets. The sequence o f reaction chloride which has been used to produce smoke.
is: Silicon tetrachloride is, however, less reactive than
titanium tetrachloride and, unless considerable
TiCl4 + 5 H .0 — » TiCL • 5H20 moisture is present, little smoke is j.V 'd .i. cd. The
TiCl4 • 5H...0----- » TiCla(OH) • 4H20 + HC1 smoke particles produced from the reaction of sili­
TiCl,i ( O H ) • 4H20 —— * TiCl2(O H )2 • 3II20 con tetrachloride with water vapor are dilute hy­
+ HC1 drochloride acid droplets and hydrated silicon
TiCl2(O H )9 • 3H20 — * T i(O H )4 • H .O oxide. The reaction boiaeen silicon tetrachloride
+ 2HC1
and water vapor is similar to that tor titanium
Liquid FM is excessively corrosive to metal if tetrachloride.
moisture is present. With moisture, FM forms a Silicon tetrachloride is less corrosive to metals
solid, gummy deposit that clogs equipment. A 0.2 than titanium '.tetrachloride. If dry, it can be
percent phosphorus solution in CS2 and CC14, stored in aluminum or steel containers. With
added to the FM, alleviates this problem. moisture, silicon tetrachloride forms a gummy
Titanium tetrachloride can also be disseminated deposit which dogs equipment. Flesh burns from

7-24
 AMCP 706-185

silicon tetrachloride are similar to hydrochloric guhr. The last two ingredients served to absorb
acid burns. the carbon tetrachloride and to slow down the rate
of reaction. As the smoke produced contained
7-33.3.1.3 Stannic Chloride ' some carbon in addition to the zinc.chloride, it was
somewhat gray in color. An American improve­
Stannic chloride will produce a good smoke
ment, the addition of an oxidizing agent, resulted
from relatively small amounts of material. The
in a whiter smoke. Other changes were made lead­
reactions of stannic chloride with water vapor
are similar to those of titanium tetrachloride. The ing to the development of the smoke mixture,
smoke is composed of HC 1 droplets and a mixture available at the start of World W ar Unknown in
of four stannic hydroxy chlorides. In the presence the United States as HC. This mixture contained
of moisture they are nearly as corrosive as titan­ hexachloroethane as the chlorinating agent, zinc as
the fuel, a perchlorate as an oxidizing agent, and
ium tetrachloride. A gummy deposit. on metals
is formed by stannic chloride when moisture is ammonium chloride as a retarder. The British
present. The smoke is corrosive to anything af­ had a similar mixture containing hexachloroethane,
fected by hydrochloric acid. Stannic chloride pro­ zinc oxide, and calcium silicide as a reducing agent.
duces burns similar to strong acid burns. Since neither of these mixtures was completely
satisfactory early in World War II, the British
mixture was modified by replacing the reducing
7-3.3.3.2 Solid Metal Chlorides
agent, calcium silicide, with aluminum.
Solid metal chlorides are normally disseminated
by thermal vaporization followed by condens ition.
7-3.3.3.2.2 Chemistry of HC Smoke Mixtures2628
In most cases, ’the energy required to vaporize these
agents is provided by a pyrotechnic heat source. The basic reaction between a completely chlori­
The hydrolyses reactions for the metal chlorides nated carbon compound and metallic zinc can be
which have been used as smoke agents are: represented by the reaction:

CuCl2 + 2H20 - Cu (O H )2 - f 2HC1 CxClj. - f y / 2 Z n ----- > xC + y/2ZnCl 2

FeCl 2 + 2HoO - F e (O H )2 + 2HC1 This reaction is highly exothermic with the evolu­
FeCl 3 + 3H 2 0 - -» F e ( O H ) 3 + 3HCl tion o f 165.3 kilogram-calories or 581 gram-calories
AlCls + 3H20 - -> A 1 (0 H )3 + 3HC1 per gram of mixture if carbon tetrachloride is
ZnCl2 + 2H20 - -> Z n (O H )2 + 2HC1 used, and 244.6 kilogram-calories or 565 gram-
CdCl2 + 2H20 - -» C d (O H )2 + 2HC1 calories per gram of mixture if hexachloroethane
HgCl 2 + 2H20 • HgO • H 20 + 2HC1 is used as the chlorinating agent. I f zinc oxide is
SnCl2 + 2H20 - -» Sn (O H )2 + 2HC1 added, the mixture will burn more slowly. The
smoke produced is whiter due to the reaction be­
7-3.3.3.2.1 HC Smokes tween zinc oxide and carbon:
Zinc chloride is one of the most reactive of the
ZnO + C - — > CO -f- Zn
solid metal chlorides used as a smoke agen t. A l­
though toxic, zinc chloride produced as the result which removes the carbon from the smoke. The
o f a pyrotechnic reaction is widely used for screen­ zinc produced by this reaction then reacts with
ing and signaling purposes.1®y Inasmuch as hydro­ additional amounts o f the chlorinating agent. As
chloric acid is produced by the reaction between the reaction between zinc oxide and carbon is
zinc chloride and water vapor in air, the smoke is endothermic, early attempts to use zinc oxide in
irritating to personnel and will react witlh any HC-type smokes were only partially successful
materials affected by hydrochloric acid. since the temperature reached was not high enough
The French, during W orld W ar I, were the first to cause complete reduction o f the zinc oxide. ■
to produce a smoke mixture o f this type. Tile mix­ As the result of modifications made during the
ture known as the Berger mixture consisted of early part of W orld W ar II, HC smoke mixtures
zinc, carbon tetrachloride, zinc oxide, and kiesel- — as normally compounded for screening purposes

7-25
AMCP 706-185

— now consist of approximately equal amounts by The amount of aluminum in the foregoing reac­
weight of zinc oxide and a chlorinating agent such tion can vary from 3.6 to 10.1 percent by weight.
as hexachloroethane or carbon tetrachloride, and a With the lower aluminum content, only carbon
few percent of aluminum. The reaction might pro­ monoxide is formed; and, as the aluminum con­
ceed through the following steps, when hexachloro­ tent is increased, free carbon begins to appear
ethane is the chlorinating agent: along with the carbon monoxide until at the
2A1 + C2 C16 — » 2A1C1S + 2C upper limit all the carbon is in the form of smoke.
I f less than 3.6 percent of aluminum is used, both
This reaction is exothermic, liberating around 280
carbon dioxide and carbon monoxide are produced;
kilogram-calories of energy. The aluminum chloride
and, as the percentage of aluminum is still further
formed then reacts with the zinc oxide:
reduced, the ratio of carbon dioxide to carbon
2AlCla - f 3ZnO — *•3ZnCl2 + A12 0 8 monoxide increases. The heat evolved varies from
This reaction is also exothermic, liberating 103.0 356 gram-calories per gram of a smoke mixture
kilogram-calories. The overall reaction obtained containing 3.6 percent of aluminum to 717 gram-
by combining the above reactions i s : calories per gram of mixture containing 1 0 . 1 per­
2A 1+ C2Cla -j- 3ZnO > 3ZnCl2 -I- Al2Og 4 - 2C cent aluminum content. If carbon tetrachloride is
This reaction is highly exothermic, liberating 383.5 used (Type-E HC mixture) instead o f the hexa­
kilogram-calories or 717 gram-calories per gram chloroethane, the amount of aluminum for similar
of smoke mixture. A second reaction sequence reactions to take place ranges from 5.37 percent
leading to the same overall reaction is possible. to 10.2 percent. The variation in burning time
This sequence, which to some investigators better with aluminum content, for mixture containing
represents the actual course of the reaction, is hexachloroethane (Type-C HC mixture), is illus­
2A1 -}• 3ZnO ------> 3Zn -j- A12 0 8 trated by the data presented in Table 7-4.
3Zn 4~ C2CU > 3Zn012 4~ 2C
TABLE 7-4
Both of these reactions are exothermic, the first
VARIATION OF BURNING TIME OF TYPE-C
to the extent o f 136.6 kilogram-calories, and the
HC SMOKE M IXTURE W ITH
second to the extent of 219.8 kilogram-calories.
ALUMINUM CONTENT
The overall reaction with aluminum is similar to
the reaction:
(AN-M 8 , HC !SMOKE GRENADE)
,3CaSi2 + 15ZnO + 5C2 C1« ----- > 15ZnCl2 Burning Time,
Aluminum Content,
. + 3CaO sec
. 4” 6Si0 2 %
4- 10C 9.0 55
for the earlier smoke mixture containing calcium 8.4 64
silicide as the reducing agent. 8 .0 65
The extent of the reaction between zinc oxide 7.5 71
and carbon can be varied by changing the propor­ 7.0 84
tion of aluminum in the smoke mixture. I f the 6.5 96
aluminum content in the smoke mixture is re­ 6 .0 107
duced, while the proportions of hexachloroethane 5.5 147
and zinc oxide are kept constant, the amount of 5.5 200

free carbon in the smoke is reduced. This results

in a whiter smoke and also reduces the burning The character of the zinc oxide also has an in­
rate. The overall reaction where no carbon is pro­ fluence on the burning rate of the smoke mixture.
duced is: HC smoke grenades which were loaded with a
2A1 4~ 9ZnO 4" 3C2Cle ■"" ■■►A120 8 4”9ZnCl2 smoke mixture containing 6.25 percent aluminum,
4- 6 CO 46.9 percent hexachloroethane, and 46.9 percent

7 -2 6
 AMCP 706-185

zinc oxide were found to have a wide range of Impurities such as chlorides, sulfates and nitrates
burning 'times depending on the moisture,' car­ accelerate the reaction. ;
bonate and sulfate content, and the particle size
of the zinc oxide used. Very fine and very coarse 7-.1.3.3.3 Modified HC Smokes28
zinc oxides form slower-burning mixtures than When a shortage of chlorine appeared imminent
those of intermediate size. Fast-burning smoke during World W ar II, attention was focused on
mixtures result when moderately large-sizec. par­ the possibility of developing inorganic chlorine
ticles of zinc' oxide with a low moisture and car­ carriers derived from hydrochloric acid. It was
bonate content are used, while slow-burning mix­ found that.anhydrous ferric chloride could be used
tures are produced when very small-sized particles in place of hexachloroethane in zinc chloride smoke
of zinc oxide, or those haying a high carbonate mixtures. The following reactions involving alu-
content, are used. A blend o f a coarse and a fine minuni, ferric chloride, and zinc oxide arc thought
zinc oxide results in a faster-burning m ixtur; than to occur at high temperatures: ,
would be predicted from the burning time of the
2 A1 + 6 FeCl 3
+ 9Z n O ----- > A12 0 8 + 6 FeO
individual oxides.
-f- 9ZnCl2
The apparent density of the zinc oxide das no
2A1 -f- 2FeGls -f- 3 Z n O ----- > AI2 O3 -j- 2Fe
direct effect on the burning time of the Type-C HC
-fr 3ZnCl2
smoke mixture containing zinc oxide. F or Type-E
HC smoke mixtures, the consistency o f the filling The heats of reaction per gram of smoke mixture
varies from wet-and-doughlike to dry-and-powdery for the above reactions are 186 and 378 gram-
as the relative density of the zinc oxide decreases. calories, respectively. Because of the hygroscopic
The rate of burning o f the mixture also decreases nature of ferric chloride, compositions containing
as the relative density o f the zinc oxide decreases. this ingredient are difficult to prepare in moist
I f the aluminum content is reduced below five atmospheres. To obviate this difficulty, the use
percent, the burning time becomes erratic. As a of ferric chloride complexes such as KFeCLt has
result, other means must be employed to further been proposed.
retard the burning rate. The substitution o f basic In recent work, 29 hexachlorobenzene and
zinc carbonate for zinc oxide, in a quantity not Dechlorane (perchloropentacyclodecane, CJ0 CI1 2 )
exceeding seven percent of the zinc oxide, is one have been used instead of the more volatile hexa­
method. The stoichiometric ratio of zinc to hexa- chloroethane. The smoke volume and burning
chloroethane, however, must be maintained. Other time are comparable to the normal 'HC composi­
retarders which lengthen the burning time of tions; its stability during storage is better. No
the HC smoke mixture include urea and Mcnostral significant difference in relative toxicity was found ;
blue dye. Naphthalene was found to have a re­ both smokes are toxic and produce degeneration of
tarding action on the fast-burning mixtures but tissues in the respiratory system on long exposure.
no definite effect on the slow-burning mixtures. Plastic bonding agents80 were also successfully
Sucrose, Vinsol resin, and anthracene were tried tried allowing the smoke compositions to be loaded
but were not satisfactory. | into unusual-shaped containers. The filling and
HC smoke mixtures are relatively stable ex­ blending operations have been improved with im­
cept when there are soluble chlorides in the zinc provement in uniformity of the mixtures. Storage
oxide or when water contacts the hexachloroethane. characteristics of plastic bonded white smoke muni­
Although the sequence o f events when water gains tions were also better, although corrosion has not
access to ah HC smoke mixture containing hexa­ been completely eliminated. -
chloroethane has not been established concl usively,
it is reported2 7 that in the presence of zinc dust 7-3.3.3.4 Zinc Hexachlorobenzene-Potassium
and moisture C2 C1 « is reduced and tetrachloro- Perchlorate System
ethylene is one o f the reaction products. Zinc Zinc hexachlorobenzene-potassium perchlorate
dust is oxidized to zinc oxide and zinc chloride. systems have been used in some cases for signaling

7-27
 AMCP 706-185

Figure 7 -9 . M 5 HC F loating Smoke Pot

temperature above the transition point of potas­

sium perchlorate, reacts with the latter at the
boiling point o f hexachlorobenzene, according to
reaction 2 . The latter reaction, together with reac­
tion “ 1 to a limited extent, raises the system to a
■ Figure 7 -8 . A N -M 8 HC Smoke Hand Grenade temperature above 500°C. A t temperatures above
the melting point of zinc (419°C), the preignition
and marking purposes. Heat of combustion and reaction 3 becomes highly exothermal and propa­
differential thermal analysis have indicated that gation ensues in the range of 520°C. Therefore,
three chemical reactions are basically responsible the production of carbon by reaction 1 is an im­
for the preignition, ignition, and combustion phases portant factor in the sensitivity of this composition
o f this ternary system.3 1 These reactions are:1
3
2 to thermal ignition.
1. 3Zn + C«C16 ----- ►3ZnCl2 + 6 C
2. 4C - f KCIO*----- ►KC1 + 4CO (and C 0 2) 7-3.3.3.5 Typical Devices
3. 4Zn + KC10 4 ----- > K C 1 +4ZnO Typical devices using HC type smoke mixtures
The agreement between the measured and calcu­ are shown in Figures 7-8 and 7-9. Details and
lated heats of combustion based on these reactions specifications for these devices are contained in
is good. Table' 7-5.
The first of these reactions is a relatively slow,
exothermal reaction which takes place at, and 7-3.3.4 Sulfuric Acid Smokes
above, the boiling point o f hexachlorobenzene to Several white smokes are made up, at least
produce carbon. Carbon, which is produced at a in part, of droplets of dilute sulfuric acid result-

7-28
 AMCP 706-185

TABLE 7-5
CHARACTERISTICS OF TYPICAL DEVICES USING HC MIXTURE

Characteristic Device

HC Smoke Hand H C Floating

Grenade (AN-M8) Smoke Pot (M 4A2)
Size, in. 5.7 high 13 high
2.5 dia 12 dia
Four smoke emission Three vent
holes iii top holes in top
Charge 19 oz Type-C 23.5 to 27.5 lb
Weight HC Mixture HC Mixture
Ignition M201A1 fuze plus M207A1 fuze plus
ignition mix and first fire charge
starter mix and delay charge
Burning 105-150 sec 10-15 min
Time "
Application Thro wn 1.2-2 sec Screening
delay ■may be
launch ed from
rifle o carbine for
screen ing or marking.

ing from the reaction of the smoke-producing heat, sulfur trioxide vapors reacting with metals
chemical with water vapor in the air. In a num­ form metal sulfides and oxides. When the liquid
ber of cases, because of the presence of c hlorine comes in contact with the skin, sulfur trioxide
atoms in the original compound or mixture, dilute causes burns that heal slowly. I f water is present,
hydrochloric acid droplets are also produced. In sulfuric acid is formed which is corrosive to metals.
this category, the FS smoke mixture of chlorosul- As has been indicated, the smoke formed is cor­
fonic acid and sulfur trioxide, which is ised for rosive to anything affected by sulfuric acid.
screening, is probably the most important. Pro­
longed exposure to this type smoke can be in­ 7-3.3A2 Oleum
jurious and should be avoided. 1 Oleum is a solution o f sulfur trioxide in sul­
furic acid. The agent is dispersed in the same
7-3.3.4.1 Sufide Trioxide manner as sulfur trioxide. The sulfur trioxide
This agent is usually dispersed into the at­ reacts with water vapor in the air; the sulfuric
mosphere in fine particles either by mechanical acid thus formed and the sulfuric acid solvent ab­
atomization or thermal vaporization. The dis­ sorb water to give smoke droplets o f dilute sulfuric
persed sulfur trioxide combines with water vapor acid. ‘
in the atmosphere, resulting in the formation of
tiny droplets of sulfuric acid: 7-3.3.4.3 Chlorosulfonic Acid
This acid reacts with water similar to SOa.
SOa + H20 — H2S 0 4 Smoke is produced by dispersion of the acid into
The acid then takes on more water vapor to pro the atmosphere by mechanical atomization or
duce particles o f diluted acid which constitute thermal vaporization. When the dispersed acid
the smoke cloud. Dry sulfur trioxide does not mingles with, water vapor, sulfuric acid and hydro­
attack metals at ordinary temperatures. A t red chloric acid are produced:

7-29
 AMCP 706-185

HCISOa + H 20 ----- > H 2S 0 4 + HC1 7-3.3.5.1 Ammonium and Amine Salts of

Volatile Acids
Both acid products take on further water to give
Ammonium and amine salts of a volatile acid
droplets of dilute sulfuric and dilute hydrochloric
such as HC1 can be vaporized by heating. For
acid. The smoke produced, therefore, is corrosive
ammonium chloride the reaction is:
to anything affected by sulfuric acid or hydro­
chloric acid and is irritating to the respiratory NH 4 C1----- »N H 8 + HC1
system, eyes, and skin of exposed personnel.
On cooling, recombination occurs. Amine salts,
such as aniline hydrochloride, may be used sim­
7-3.3A4 Sulfuryl Chloride
ilarly. Ammonium or amine salts have no effect on
Sulfuryl chloride is dispersed in the same man­ metals when dry; however, the presence of water
ner as sulfur trioxide by mechanical atomization may result in some corrosion. These salts can be
or thermal vaporization. It reacts with water handled without danger to personnel.
vapor from the atmosphere to give a smoke com­
posed of dilute sulfuric acid and dilute hydro­ 7-3.3.5.2 Metal Chlorides and Ammonia
chloric acid droplets. In the presence of moisture,
Metal chlorides may also be reacted with am­
sulfuryl chloride is as corrosive to metal and flesh
monia or amines to produce smoke. The base must
as is sulfuric acid. Dry sulfuryl chloride is cor-,
combine with the metal chloride just after disper­
rosive to those materials affected by sulfuric or
sion. Other bases such as hydrazine may be used
hydrochloric acid and will cause burns to the flesh
in place of ammonia.
similar to those of sulfuric acid.
7-3.3.5.2.1 Hydrogen Chloride and Ammonia
7-3.3.4.5 FS Smoke The reaction of hydrogen chloride with ammonia
FS smoke agent consists of a mixture of 45 per­ is similar to the reaction of a metal chloride with
cent chlorosulfonic acid and 55 percent sulfur ammonia. This two-gas system produces fine par­
. trioxide, and is slightly more reactive with water ticles of solid ammonium chloride. The smoke
than FM smoke agent (Paragraph 7-3.3.3.1.1). formed is considered very visible. Gaseous hydro­
The material can be dispersed by mechanical gen chloride is not very corrosive to metal con­
atomization or thermal vaporization. For produc­ tainers when d r y ; however, when moisture is pres­
ing smoke screens, it is often disseminated from ent, it is quite corrosive. Ammonium chloride
spray tanks carried by aircraft. As the smoke smoke is not corrosive to metals. Hydrogen chlo­
consists of droplets of dilute sulfuric and hydro­ ride gas is very irritating and, in moderate quanti­
chloric acid, the smoke is corrosive to anything ties, it is toxic. Ammonia gas is also toxic in mod­
affected by these compounds. The smoke is very erate quantities; however, ammonium chloride
irritating to the nose and lungs and exposure smoke is harmless.
should be avoided. If moisture is present, FS
smoke agent is excessively corrosive, and it will 7-3.3.5.2.2 Titanium Tetrachloride and Ammonia
cause skin burns. The reaction between titanium tetrachloride
and ammonia is somewhat complex. First, an am-
7-3.3.5 Smoke-Producing Reactions Involving moniate is formed. This ammoniate is hydrolyzed
Ammonia or Amines by water vapor from the atmosphere. Ammonia
Most of the reactions described in this sub­ reacts with the hydrochloric acid gas released dur­
paragraph were at one time used to produce ing hydrolysis of TiCl4 to give NH 4 C1. Therefore,
screening smoke. For many reasons they are not the system without water vapor is less effective.
presently so used. Some of these systems do not The reactions for this process are as follows:
require atmosphere constituents (such as water TiCL, + 4NHa----- » TiCl, • 4NHa
vapor) to be effective smoke producers and, there­ TiCU • 4NHg + 5H20 ----- > T i(O H )« • H20
fore, may be useful at high altitudes. ' + 4NH 4 C1

7-30
 i

AMCP 706-185

The smoke is a mixture of Ti ( O H ) 4 • H 2 0 , iiter- trioxide; other bases such as hydrazine, hydrox-
mediate hydroxy chlorides of titanium, and am­ ylamine, etc., probably could be substituted. The
monium chloride particles. basic reaction is as follows:

HC1S03 + 3NH3 -----» S02(NH2)2 • NH4C1

7-3.3.5.2.3 Silicon Tetrachloride, Ammonia,
+ H2O
and Water
The best proportions are two parts silicon tetra­ Other reaction products might be formed in addi­
chloride, one part ammonia, and one part ■water, tion to the products indicated by this reaction.
by weight. The reactions are quite complex; first,
an ammoniated silicon tetrachloride is formed 7-3.3.5.3.3 Sulfuryl Chloride and Ammonia
while at the same time hydrolysis of the silicon or Amines
tetrachloride occurs to give S i02, 2H 2 0 , and HC1; Sulfuryl chloride will react with bases such as
and finally, NH 3 combines with the HC1 to give ammonia and amines to give a better smoke than is
NH 4 CI.. The reaction sequence is : formed with water vapor. The following reactions
are for sulfuryl chloride and ammonia:
SiCl4 + 4NH 3 ----- » SiCl4 •4NH 3
SiCli + 4H20 ----- > S i0 2 -2H20 + 4HC1 S02C12 + 4NH3-----►S02(NH2)2 + 2NH4C1
SiCl4 • 4NH 3 + 4H20 ----- > S i0 2 • 2H20 2S02C12 + 7NH3-----» 4NH4C1
- f 4NH 4 C1 + NH(S02NH2)2
HC1 + NH 3 ----- > NH 4 C1 3S02C12 + 9NH3----->6NH4C1 + (NH)»(SOj)s
The first reaction gives sulfamide; the second,
7-3.3.5.3 Sulfur Compounds and Ammonia
aminosulfamide; and the third, trisulfamide.
Sulfur compounds will also react with basees m-
Whether the smoke particles are those products
eluding ammonia and amines. These smoke-pro­
or further reaction products is not known.
ducing systems do not require atmospheric con­
stituents to form the smoke particles and, there-
fore, may be useful at high altitudes. ' 7-3.3.6 Sulfur Smokes
Sulfur smokes consist of small particles of ele­
7-3.3.5.3.1 Sulfur Trioxide and Ammonia mental sulfur suspended in the air. Sulfur smokes
. or Amines can be produced by methods similar to those used
The smoke is formed by supplying a reactive for the production of oil smokes. In addition,
gas to sulfur trioxide at the time of dispersion. sulfur smokes can be made by intimately mixing
Ammonia and amines have proved successful, and sulfur and a suitable fuel. Mixtures which have
other basic substances, such as hydrazine, hy- been used include sulfur, sodium nitrate, and char­
droxylamine, etc., might be satisfactory. In the coal; sulfur, potassium nitrate and charcoal; and
case of sulfur trioxide and ammonia, the reactions sulfur, ammonium nitrate, and charcoal. The sul­
a re: fur is present in much larger quantities than in
S 0 3 + 2NH 3 ----- » S 0 2 (NH 2 ) 2 + HaO black powder ; the latent heat of vaporization and
S 0 3 + n h 3 ----- » H S 0 3 NH 2 fusion of the sulfur absorbs the heat produced by
S 0 3 + 2NH 3 ----- > NH 2 S 0 3 NH 4 the reaction and, hence, slows the burning rate.
The burning rate for this type of mixture depends
A ll three reactions occur more or less simulta-
on the percentage of sulfur.
^ neously. As far as can be determined, the smoke
consists of particles of these products.
7-3.3.7 Organic Metallic Compounds j
7-3.3.5.3.2 Chlorosulfonic Acid and Ammonia Certain organic metallic compounds can be used
or Amines for the production o f smoke. These compounds are
Ammonia and the amines react readily with reactive and will burn spontaneously in moist air.
HCISOs in much the same manner as with sulfur The sequence of reaction between an organic metal-

7 -3 1
 AMCP 706-185

lie compound, water, and oxygen is a highly exo­ TABLE 7-6

thermic reaction between the organic metallic com­ TOTAL OBSCURING POW ER OF
pound and water vapor, yielding a hydrocarbon W H ITE SMOKES
and metal hydroxide; the heat of this reaction re­
sults in the hydrocarbon’s burning to form carbon Chemical TOP, f t 2/lb
dioxide and water. This reaction for dimethyl
zinc is : White Phosphorus 4600
TiCl4 + NH 3 3030
(CHs) 2Zn + 2H20 ----- >■2CH 4 + Z n (O H ) 2 S03 3000
CH 4 -{- 2 0 2 > C 0 2 -}- 2H20 FS 2550
In this case the white particles consist of solid HC1 + NHS 2500
zinc hydroxide particles. HC Mixture 2 10 0

SiCl4 + NH 3 1960
7-3.3.8 Comparison of White Smokes FM 1900
Oleum 1890
The total obscuring power, TOP , 82 of a smoke
SnCl4 1860
is obtained by multiplying the product of volume,
PC13 + n h 3 1600
in cubic feet of smoke produced per pound of ma­
PC13 + n h 3 1800
terial, and the reciprocal of the smoke layer, in
HCISOs + NH 3 1600
feet, necessary to obscure the filament of a 40-watt
SiCl4 1500
Mazda lamp. The TOP for some white smoke
HC1S0 3 1400
agents, at low altitudes where atmospheric con­
BM Mixture 1400
stituents are plentifiul, is given in Table 7-6.
Berger Mixture 1250
The so-called “ standard smoke’ ’ is a smoke of
FM - f 1,2-Dichloroethane 1235
such a density that a 25-candlepower light is just
S 0 2 C12 12 0 0
invisible when observed through a layer 1 0 0 feet
Cl2 + n h 3 750
thick. A comparison of some white smoke agents at
A sC13 460
low altitude, where atmospheric constituents are
Type - 8 Mixture 460
plentiful, in terms of the amount of smoke agent
Crude Oil 200
required to produce 1 0 0 0 cubic feet of standard
smoke, is given in Table 7-7. ‘
All of the TOP and standard smoke measure­
ments were made at low altitude, where atmo­
spheric constituents available for reaction with the
TABLE 7-7
primary smoke particles were plentiful. The im­ AMOUNT OF SMOKE AGENTS REQUIRED TO
portance of atmospheric constituents is illustrated PRODUCE 1,000 CUBIC F E E T OF
in Table 7-8 where the number of grams of smoke STANDARD SMOKE
formed per gram of smoke agent used is tabulated.
It is evident, for the agents compared, that WP Compound Amount Required, oz
yields the greatest weight o f aqueous solution in
equilibrium with air at 75 percent relative humidity Phosphorus 0.060
per unit-weight of the smoke agent. The ratio for FM + NH 3 0.090
fog oil is unity ( 1 .0 ) since the fog oil is not hygro­ 80s 0.094
scopic and only the agent is available to form the F8 0 .1 1 0

smoke particles. The values do not take into ac­ HC Mixture 0 .1 2 0

count ingredients which remain behind as residues FM 0.150

or otherwise contribute little to the obscuring Oleum 0.151
power. The absolute values will vary with the Crude Oil 2 .0 0 0

relative humidity, but change very little with air

7 -3 2
AMCP 706-185 AMCP 706-185

• TA B LE 7-8 the requisite purity of color when disseminated

AMOUNT OF SMOKE PRODUCED PER UNIT as a smoke. These properties are closely related
W E IG H T OF SMOKE AGENT AT to the chemical constitution of the dye. No dye
75% R E L A T IV E H UM IDITY was ever specifically developed for smoke appli­
cation; only those available were considered and
Agent Amount tested. In an early investigation of the thermal
stability and volatility of dyes, it was concluded
Fog Oil 1 .0(does not produce that dyes containing amino or substituted amino
aqueous solution) groups, but not sulfonic groups, were suitable for
Zinc Chloride 2.5 (water vapor absorbed) the production of colored smokes. These conclu­
Ferric Chloride 3.1 (water vapor absorbed) sions were confirmed and amplified by British in­
Aluminum Chloride 5.0 (water-vapor absorbed) vestigators in a systematic survey of common dye­
Phosphorus 7.11 stuffs. The constitutional characteristics which
render a dyestuff suitable for the production of
temperature at any one value of the relative colored smoke were found to be as follow s:
humidity. Also, the relative results ane not a. The molecular weight of the dye should pre­
changed. It is important to note that these m easure- ferably be less than 400, but in no case
ments chiefly concern the obscuring or scxeening greater than 450.
power of the smoke and no consideration is given b. The dye should be a member of one o f the
to other factors which might be important for a following series: anthraquinone, azine, azo,
signal smoke, tracking aid, or tracking and ac- quinoline, xanthene, or anthrone.
quisition smoke. c. The following groups must be absent: sul­
fonic, hydrochloride, nitro, nitrose, quar­
7-3.4 COLORED SMOKES88 ternary ammonium, and oxonium.
Colored smokes, like other smokes, can be pro­ d. The following groups may be present:
duced by four basic methods: amino and substituted amino, alkyl, aryl,
a. Dispersion of finely powdered, colored ma­ chloro, bromo, hydroxy, and alkoxy.
terials e. The dye must not tend to undergo auto-con­
b. Chemical reactions resulting in the forma- densation.
tion of colored particles
Not all dyes which have the above characteristics
c. Detonation o f an explosive, thereby scat­
will produce satisfactory colored smokes, but some
tering colored material, or
of the many dyes which have been evaluated will
d. Volatization and condensation of a colored
produce “ excellent” colored smoke clouds. Some
material.
of the more satisfactory dyes are listed in Tables
The first two methods have been found to give 7-9 and 7-10.
smokes of only small volume and dull color. The In general, the anthraquinone dyes have proved
last two methods, both o f which involve the vapori­ to be superior to all others in producing colored
zation and condensation of a colored material, have smoke clouds. The azo derivatives have furnished
been found feasible only when volatile organic only a few suitable dyes, despite the fact that
dyes are used as the coloring material. As a result, they constitute the largest class investigated. In
all colored smoke signals (except black) are based, no case have the azo dyes been superior to the
at present, upon the use of an organic dye. anthraquinone dyes. The undesirable qualities of
the azo dyes are their tendency to flame and their
7-3.4.1 transparency. Among the azine dyes, rosindone and
Since colored smokes involve vaporization and its derivatives give excellent, bright smoke clouds
condensation, constituent dyes are required to be without flaming. Their color range, however, is
thermally stable and fairly volatile, and to possess limited to red and orange. This class of dyes offers
 AM CP 706-185

TABLE 7-9
SOME DYES W HICH HAVE BEEN USED IN BURNING-TYPE
COLORED SMOKE MUNITIONS

Red Smoke: D ye(s)

9-diethylamino-7-phenyl-5-benzo (a) phenazinone.

Also known as 9-diethylamino rosindone
1-methylaminoanthraquinone
1- (2-methoxyphenylazo)-2-naphthol
2- quinolyl-2-indandioue-l,3 (Ithodamine B) plus
1- (4-phenylazo)-2-naphthol
2-aminoanthraquinone plus 1-methylaminoanthraquinone
0 - tolylazo-o-tolylazo-P-naphthol (Sudan I V ) ; plus
2- quinolyl-2-indandione-l,3 (Rhodamine B ) ;
plus auramine hydrochloride '
1- (tolylazoxylylazo)-2-naphthol

Green Smoke: -
1,8-di-p-toluidinoanthraquinone
1.4- di-p-toluidinoa n? hraquinon-
1-methyl amino-4- p -1_•1uid i noant hraquinone plus
auramine hydrochloride
1.4- di-p-toluidinoanthraquiuone plus
dimethylaminoazobenzene
1.4- di-p-toluidinoanthraquhiOiie plus
auramine hydrochloride
1.4- di-p-toluidinoanthraquinone with quinophthalone
(quinoline yellow)

Orange Smoke:
1-aminoanthraquinone
l-amino-8-chloroanthraquincne plus quinizarin
l-(4-phenylazo)-2-naphthol
9,10-dianilinoanthracene plus phthaloperinoue
l-(4-phenylazo)-2-naphtho! plus 9,10-dianilinoanthracene

Orange-Red Smoke:
1 -(4-nitrophenylazo) -2-nap: hoi

Yellow Smoke:
Auramine hydrochloride
1- (4-dimethylaminophenylazo) -2-naphthol
l-(4-phenylazo)-2-uaphthol (Sudan 1) plus either auramine
hydrochloride or quinophthalone (quinoline yellow) ‘
N,N-dimethyl-p-phenylazoaniline

7-84

\
 • vM
' ±u • 4 . ^ - - . ■- '1

AMCP 706-185

• ,
TABLE 7-9 (cont’ d)

Blue Smoke: D ye(s)

l-hydroxy-4-p-toluidhiojinthraquinone
; Indigo
l-amino-2-bromo-4-p-tolijidinoanthraquinone
l-amino-2-methyl-4-p-to' lidinoanthraquinone
(Alizarin Sapphire, Blue R. Base)
1,4-dimethylaminoanthr aquinone
l-hydroxy-4-p-toluidinoiinthraquinone
s l-methylamino-4-p-tolui linoanthr aquinone
N-(p-dimethylaminophe iyl)-l,4-naphtholquinonimine

Violet Smoke: '

1.4-diaminoanthraquino le • ■ . ■• , . ..
1.4- dianrino-2,3-dihydroi
.nthraquinoEie
1.5- di-p-toluidinoanthra
luinone
l-methylamino-4-p-tolui linoanthraquinone plus
2-quinolyl-2-indandi >ne-l,3 (Rhodamine B)
l-methylamino-4-p-tolui linoanthraquinone plus
1,5-di-p-toluidinoant iraquinone

• .

TA BLE 7-10
SOME D YES W H IC H H A V E BEEN USED IN E X PLO SIV E -T Y PE
COLORED SI 10K E MUNITIONS

Red Smoke: D ye(s)

1- ( 2-methoxyphenylazo -2-naphthol
1-methylaminoanthraqii inone (Celanthrene Red) .

YeUow Smoke:
2,4-diaminoazobenzene (Chrysoidine G, base)
Auramine Hydrochloricle

, Green Smoke:
l,4-di-p-toluidinoanthr> quinone (Quinizarin Green) . .
plus quinophthaloc (Quinoline Yellow, base) .
in the ratio o f 65/3 5 '
1-4-di-p-toluidinoanthra quinone plus auramine hydrochloride

•
7-85

L ■ ' ' ' .X'..

 AMCP 706-185

N O T E : X - A X IS TEMPERATURE REPRESENTS SAM PLE

TEMPERATURE FOR THE DTA CURVE AND
FURNACE TEMPERATURE FOR n c TG A CURVE

Figure 7-11. D iffe re n tia l Thermal Analysis a n d Thermo­

gra vim e tric Analysis Curve fo r 1,4-d i-p -to lu id in o a n th ra -
N O TE : X -A X IS TEMPERATURE REPRESENTS SAMPLE quinone
TEMPERATURE FOR THE DTA CURVE AND
FURNACE TEMPERATURE TOR THE TGA CURVE

Figure 7-10. D iffe re n tia l Thermal Analysis and Thermo­ ture and decrease the quantity of smoke available.
gra vim e tric Analysis Curve fo r 1,8-dih yd ro xya n th ra - Although organic dyes have been widely used
quinone
in burning- and burst-type colored smoke markers
and signals, very little is known about their chem­
the most promise for future investigation. Several ical, physical, and thermodynamic properties at
dyes containing sulfonic groups have been tested elevated temperatures. In making a choice of
and, with only one exception, found to be non­ dyes, the thermodynamic properties of the com­
volatile ; this exception is the ammonium salt pounds— such as heats of fusion, vaporization or
of 2- ( 2-hydroxy-l-naphthylazo) -1-naphthalenesul- sublimation, decomposition, equilibrium vapor pres­
fonic acid which gives a fair red smoke. Lakes and sures, rates of vaporization, and the temperatures
other pigments have been found to give no smoke at which these phenomena occur— are important.
when used in pyrotechnic mixtures. For satisfac­ For example, if the compound is thermally stable
tory results, the purity of dyes used must be high, but has a relatively low vapor pressure so that
since organic impurities are usually volatile and relatively high temperatures are required for its
tend to give a muddy-colored smoke. Inorganic vaporization, the fuel-oxidant to dye ratio required
impurities are generally either sodium chloride for optimum vaporization of the dye will not allow
or sodium sulfate and, while they in themselves the munition to contain the amount of dye neces-.
do not change the color of the smoke, large quanti­ sary to produce an acceptable volume of colored
ties slow down the burning rate of the smoke mix­ smoke. I f the dye can be vaporized at a low tem-

7-36

N
 AMCP 706-185

perature but the differential between the tempera 30 percent initial weight loss during which a point
ture for vaporization and the temperature for of inflection occurs. It is postulated that this ma­
decomposition is not large, the dye to fue ratio terial reacts to form an effective color product in
increases but the possibility of decomposit ion of the temperature region o f 350°C to 440°C. If,
the dye is also greatly increased. In general, there- however, the temperature of the dye is not care­
fore, tbe dyes utilized must be thermally stable and fully controlled, it decomposes further to form a
vaporize without decomposition at intermediate volatile red product. In general, the dyes in
temperatures. Groups 2 and 3 do not perform satisfactorily.
The volatilization properties of organi dyes They fail to vaporize appreciably and the irregu­
proposed for use in pyrotechnic smoke m xtures larities in the differential thermal analysis curves
were studied by differential thermal a ralysis indicate the occurrence of reactions and/or de­
(D T A ) and thermogavimetric techniques.3*136 The composition. The temperature produced by the
dyes evaluated by these techniques can be classi- reaction must be sufficiently high to rapidly
lied into three groups. vaporize the dye but not excessive so as to cause
The materials in Group 1 exhibit an initial decomposition of the dye, or flaming. A cooling
weight loss, the rate of which increases as i, func agent such as sodium or potassium bicarbonate
tion of temperature. They do not have an inflec- may be added to the fuel mix to regulate the burn­
tion in their thermogravimetric curves unt 1 they ing rate. Binders are sometimes used to produce
have undergone a weight loss of 65 to 100 p ercent. a composition that is easier to handle and process.
An examination o f the D T A curves for these ma- The properties and structures o f certain se­
tcrials generally indicates an endotherma! reac- lected dyes are as follow s:
tion followed by an exothermal trend, and, finally,
an eiidothernial region. Over these temperature
Dyes Selected by the British as the Best Agents
; -nges the following phenomena were observed:
Available for the Production of Colored Smokes
fusion, the evolution o f small quantities of vapor,
by Explosion, Using PETN (pentraerythritol
and boiliug.
tetranitrate) for the Explosive:
Compounds in Group 2 show an initial weight
B ed: o-methoxybenzene-azo-jJ-naphthol (Brilliant
loss of from 30 to 50 percent, followed by n sharp
Fat Scarlet)
break in the thermogravimetric curve, after which
Molecular W eight: 278
the rate of. weight loss is generally slower. The
Components: o-Anisidine - * (S-naphthol
thermogravimetric curves for Group 3 materials
CnHuNsO*
indicate an initial weight loss o f only 2 to 20 per-
cent prior to an inflection.
In general, the materials in Group 1
OCM,
the thermal properties of stability and volatility
required for satisfactory functioning in pyrotech­
nic smoke items. For most of these materials, as
shown in Figure 7-10 for 1,8-dihydroxyianthra-
<zz>
quinone, no weight loss occurs before fusion; once
the boiling point is approached the rate o f weight
Properties, Description: Bed paste; separates from
loss increases uniformly with temperatur e. Tht
glacial acetic acid in red crystalline powder,
absence of a break or point o f inflection in the
m.p. 180°C. II20 — insoluble. Alcohol— red so­
thermogravimetric curves for the Group 1 ma-
lution on boiling. H2SO«— bluish-red solution,
terials, is indicative in this case, o f vaporization.
red precipitate on dilution.
Group 2 materials do not vaporize appreciably.
Commercial Names: Oil Vermilion (W ), Sudan R
As shown in Figure 7-11, 1,4-di-p-toluiidinoan-
(A ), Brilliant Fat Scarlet B (S G I), Pigment
thraquinone, a standard dye used for the pro­
Purple (M LB ).
duction of blue smoke, exhibits approxin ately a

7-87

J
AMCP 706-185

Yellow; 2,4-Diaminoazobenzene (Chrysoidine 6 , and paste (B y ), Alizarin Brilliant Green EF,

• base) G cone. (L B H ), Solway Green E, EF, GM
Molecular Weight: 212 (SD C), formerly Kymric Green E, G extra
Components: Aniline— m-Phenylenediamine (SD C). .
C1 2 H 1 3 N4 C1 A mixture of 55% 1,4-dimethylaminoan-
thraquinone (Brilliant Blue G, M.W. 266) and
45% Quinophthalone (Quinoline Yellow Base)
is also used to produce green smokes of an emer­
ald green color. The mixture of Quinzarin
Green and Quinoline Yellow (base) produces a
Properties, Description; Reddish-brown crystalline color approaching the green of the spectrum.
powder or large black shining crystals with a
green luster (latter contain the homologs from Quinoline Yellow.- Mixture of symmetrical quin­
o- and p-toluidine). H 2 0 — orange-brown solu­ ophthalone or 2 -quinolylindandione, with small
tion. Alcohol— orange-brown solution. Ether— quantities of iso-quinophthalone, or unsym­
insoluble. HCl to aqueous solution: brown-yel­ metrical quinophthalone or 2 -quinaldyleneph-
low gelatinous precipitate consisting of hair-like thalide.
needles. NaOH— red-brown precipitate of chrys- Molecular Weight; 273
oide base. m.p. 117°C, sparingly soluble in H 2 0, Components: Quinaldine and phthalic anhydride.
soluble in ether, alcohol, or benzene. H 0 SO 4— C1 8 H u N 0 2
brown-yellow solution, cherry-red to orange so­
lution on dilution.
Commercial Names: Chrysoidine G (C A C ), (D uP),
fYN / \ j

(G y), (SC I), (M Ly), (B y ), (G rE ), Chrys­

oidine Base (C H C ), (C V ), (J W L ), (L B H ), \ / c=CH- \ ^ y
(W ), (N A C ).
Quinophthalone iso-Quinaphthalone
Green: Mixture of 1,4 di-pi-toluidinoamino-an-
thraquinone (Quinzarin Green) and quin­ Properties, Description: Yellow powder, crystal­
ophthalone (Quinoline Yellow, base) in the lizes from boiling alcohol in thin golden-yellow
ratio of 65/35. needles, m.p. 240°C; iso-quinophthalone is more
Molecular Weight: 418 (Quinzarin Green) soluble in alcohol and crystallizes in orange-
Components: leuco-Quinzarin (or 1,4-Dichloroan- yellow prisms, m.p. 187°C. H 20 — Insoluble.
thraquinone) and p-Toluidine. Alcohol— sparingly soluble with a yellow color.
C2 8 H 2 0 N2 O2 Na2 H 2 S 0 4 — yellowish-red solution, yellow flocculent
precipitate on dilution.
/ y 'V / r --------< > ch3 Commercial Names: Quinoline Yellow spirit-soluble
(H ), (S ), (R F ), (A ), (B ), (B y ), (K ), Bril­
liant Fat Yellow C (S C I). Quinophthalone
^ CH3
Dyes Selected by the U.S. as Satisfactory Agents
Properties, Description: Bluish-green powder.
for Producing Burning Type Smokes:
H 2 0 — bluish-green solution. HCl— dark soluble
precipitate. NaOH— dark soluble precipitate. Yellow: Auramine— Hydrochloride of tetramethyl-
H 2 S 0 4 — dull reddish-blue solution, bluish-green diamino-diphenyl-ketonimine.
solution on dilution. Molecular Weight: 267
Commercial, Names: Alizurol Cyanine Green E, G Components: Tetramethyldiamino-diphenyl meth­
extra, K (B A C ), Alizarin Cyanine Green F ane, ammonium chloride, and sulfur.
paste and powder, EF, G extra, 3G, K powder CnH^NsCl + H 20

7-38
 • 'iiyr ‘r* i

I
AMCP 706-185

Yellow: Beta-naphthalene-azo-dimethylaniline and

HCIHN = C
x z 3
NtCHjJg
H20
Auramine
Molecular Weight: 275
C1 8 H 1 7 N 3

V<( > n<ch3)2 7-3.4.2 Fuels83-87

The number of combustibles that are satisfac­
Properties, Description: Sulfur-yellow powder. tory in colored smoke mixtures is very limited and
H 2 0 —bright yellow solution, readily decom­ includes sulfur, thiourea, and sugars such as
posed on boiling. Alcohol—yellow solution. lactose, sucrose, and dextrose. Dextrin, starch, and
NaOH— white precipitate of Auramine lampblack can be used, in part, to replace the
m.p. 130°C, soluble in ether. H 2 SO 4— colorless above materials but results have not always been
solution, pale yellow color on dilution. satisfactory. Among the sugars, lactose has been
Commercial Names: Auramine (H ), (G y), (S), found to be the most desirable. Sucrose and dex­
(S C I), ( StD ), (A ), (B ), (B y ), (C ), ( L ) , trose (corn sugar) have the disadvantage of being
(M LB ), (tM ); somewhat hygroscopic, and a small percentage of
Auramine 0 (B D C ), (D uP ), (Gy), ( S ) , starch is usually added to enable their handling
(SC I), (StD ), (B ) under renditions of high humidity. Potassium
0 cone. (L B H ), DuP) NO(CN chlorate and sugar are usually mixed in about
II (B D C ), (L B H ), (S ), equal parts. Although such a fuel mixture con­
(A ), (B ) ' 2 (StD) tains an excess c f sugar, the excess has been found
OE ( i necessary to secure proper action of the smoke
NAC (N AC)
ingredients. For slow-burning colored smoke mix­
0 0 extra cone. (S C I), (StD ) extra cone.
tures, a fuel composed of sulfur and potassium
(M LB)
chlorate, in stoichiometric proportions, has been
Fat Yellow A (SCI)
found to be highly satisfactory.
Canary Yellow (Gr E )
With either sucrose or lactose as fuel, the
gaseous products formed are carbon dioxide and
Green: 1,4-di-p-toluidinoanthraquinone with aura­ water vapor:
mine hydrochloride
C, 2 H 2 2 0 „ + 8 KCIO 3 ----- » 8KC1 + 12C0 2
Red: 1-Methylaminoanthraquinone (Celanthrene + HHaO
Red) Lactose would yield an additional mole of water
Molecular Weight; 237 when oxidized by potassium chlorate..

. ^ nhch,
7-3.4.3 Oxidants33-87
/ V - co^ \
A large number of fuel-oxidant mixtures have
been investigated. The oxidizing agents studied in­
\ A c :< r \ / clude chlorates, perchlorates, permanganates, ni­
trates, nitrites, peroxides, and oxides. However,
Commercial Name: Duranol Red B (B D C ) the only satisfactory oxidizing agent found thus
far, despite its friction-sensitivity, has been po­
Products Currently Used for Colored Smoke Com­ tassium chlorate. Potassium nitrate might be used
positions: to replace potassium chlorate in colored smoke
Green: 1-4-di-p-toluidinoanthraquinone and Aura­ mixtures if a very stable dye such as 1 -methyl-
mine aminoanthraquinone is used. Even with this dye,
only slow-burning grenades have been produced
using potassium nitrate. With most dyes, a ni­
Red: 1-Methylamino anthraquinone
trate is always less desirable than a chlorate, and

7-39
AMCP 706-185

nitrates have been found unsatisfactory with aura- easily handled, (5) it is available at low cost and
mine hydrochloride and indigo. Nitrates, there­ in quantity, and ( 6 ) it eliminates the necessity for
fore, should not be substituted for the chlorates consolidation under pressure. Other plastics which
in colored smoke munitions unless a special condi­ have been considered include various monomers
tion, such as a shortage of chlorate, makes it neces­ and polymers of acrylic and vinyl plastics, poly­
sary. amines, and epoxy-type resins.

7«3.4.4 Cooling Agents88,87

7-3.4.6 Evaluation of Colored Smokes
Cooling agents may be added to regulate the
Of the original colored smokes used; red, green,
burning rate of the fuel and to lower the tempera­
yellow, and violet were found to be the most suit­
ture sufficiently to prevent excessive decomposition
able. These colors were most perceptible against
of the dye with resultant decolorization or strong
the various backgrounds and displayed optimum
flaming. The best cooling agents have been found
visibility at a considerable distance. Further, they
to be sodium bicarbonate or potassium bicarbonate.
were least affected by the light-scattering proper­
Potassium bicarbonate decomposes at a higher tem­
ties of the atmosphere. Blue was found unsuitable
perature than sodium bicarbonate and is, therefore,
for signaling purposes because of excessive effect
more suitable for fast-burning types of colored
of light scatter.
smoke mixtures. Sodium bicarbonate has been
A number of different methods have been used
found better for the slower-burning mixtures.
to measure the quality of a colored smoke. In
Other cooling agents which have been investigated
many cases, they were merely observed at various
are the ammonium salts such as the chloride,
distances. More quantitative methods involve the
bromide, oxalate, carbonate, sulfate, sulfite, thio­
use of Munsell color charts40 and colorimeters. Ex­
cyanate, and tartrate. These have, been found to
tended chroma Munsell color charts developed by
work with varying degrees of success but most of
the National Bureau of Standards were success­
them have the disadvantage that, upon condensa­
fully used in measuring the color of colored smoke
tion, they form white smokes which dilute the
clouds. 4 1 Munsell color cards- were designed and
color of the dye smoke. Inert diluents—such as
used in field measurements. The. Munsell color
Fuller’s earth, calcium carbonate, and k a o lin -
data were converted to the internationally accepted
have often been added to smoke mixtures to retard
C.I.E. system of color representation for evalua­
the burning rate. and reduce flaming. tion. ,

7-3.4.S Binders
Graphite, zinc oxide, and linseed oil have been 7-3.4.7 Sensitivity of Colored Smoke Mixtures42
used for some applications but in most cases no Most of the colored smoke mixtures which have
binder has been used and the composition has been been used, with the exception of the yellow smoke
consolidated under pressure. Because of the prob­ mixture containing auramine, may be considered
lems associated with the loading of smoke m ix­ satisfactorily insensitive to friction and impact
tures, some work has been directed toward the de­ under the conditions encountered in normal load­
velopment of a plastic-bonded smoke mixture.88 ing operations. Yellow smoke mixtures containing
None of the plastic-bonded, smokes have been stan­ auramine are impact-sensitive, and require more
dardized. The use of a binder such as polyvinyl care in handling and loading. Smoke mixtures con­
acetate89 would be advantageous because: ( 1 ) it taining 1 - ( 4 -dimethylaminophenylazo) -2 -naphthol
contributes few undesirable qualities to the smoke, are markedly less sensitive to impact and friction
( 2 ) it binds smoke mixtures into a hard, tough, than mixtures containing auramine. Ignition test
nonbrittle mass having excellent water and shock results show that colored smoke compositions can
resistance, (3) it produces a formulation which be ignited by hot surfaces— and no doubt by open
withstands high and low temperature surveillance flames and other direct heat sources— of compara­
with negligible change, (4) it is safe, nontoxic, and tively low temperature. Following ignition, dust

7-40
 .-vyitpr^-rb

AMCP 706-185

SMOKE CANISTERS

SMEAR- EJECTION CHARSE

thrcaoN^-
FUZE

Figure 7-12. 105 mm M84 Colored Smoke Projectile

clouds or dispersions of these powders are capable Diethylamino Rosindone might undergo metabolic
o f producing dust explosions. reduction in the body to yield carcinogenic P-
naphthylamine. Green smoke dye 1 ,4 -di-p-toluidino*
7-3.4.8 Toxicity o f Colored Smoke Mixture anthraquinone is on the current approved list for
As standardized, the colored smoke clouds are drugs and cosmetics (Food and Drug Administra­
nontoxic in ordinary field concentrations. Ir gen­ tion).
eral, toxic materials should not be employed as Before experimentation with a particular dye is
ingredients in' signaling and screening munitions. undertaken, it is important to gain all available
It has been reported 43 that certain dyes exhibit information pertaining to the potential hazards in­
carcinogenic characteristics which should be volved in its use.
guarded against when they are used. The prob­
lem in determining whether or not a dye is a 7-3.4.9 Typical Devices
carcinogenic hazard is complex because the products
Colored smoke mixtures have been used in hand
of metabolism of the dye must also be considered
and rifle grenades, mortar and artillery projec­
for carcinogenic activity even though the original
tiles, float signals, rockets, smoke bombs, and similar
dye may be harmless. The hazards involved in
munitions. As shown in Figure 7-12, a smoke com­
handling carcinogenic materials are not in the
position is often contained in a canister which is
quantities involved but in the frequency of ex­
ejected from the projectile when the fuze func­
posure no matter how small the dosage.
tions. The ejection charge ignites the starter mix­
One of the smoke dyes of great interest to the
ture which, in turn, ignites the smoke mixture.
Army, Indanthreue Golden Yellow GK, hat been
This device contains three canisters which are
tested and found to be not carcinogenic but it is
ejected from the base o f the projectile on air hurst.
closely related to 3,4,8,9-dibenzpyrene (Idanthrene
Each canister contains from 380 to 410 grams of
Golden Yellow without the two oxygens) which is
either yellow, red, green, or violet smoke mixture.
known to be a Very potent carcinogen I f thiL com­
Many other smoke-producing items, such as gre­
pound should be present or formed by a process of
nades, etc., are also based on the canister as Shown
reduction as an impurity in even as small a quantity
in Figures 7-13 and 7-14. Characteristics o f these
as .0 1 % it would present a considerable hazard.
devices are given in Tables 7-11 and 7-12.
Red dye, 1-methyiaminoanthraquinone, has not
been tested for carcinogenicity but has the possi­
bility of being a potential liver carcinogen. Two 7-3.4.10 Direct Volatilization o f Dye
other smoke dyes, Sudan Orange R ( 1-phenylazo- Colored smoke clouds are also produced by
2 -naphthol) and l - ( 2 -methoxyphenylazo)- 2 -naph- direct volatilization of dye in the thermal genera­
thol are reported as carcinogenic. Blue dye, ] ,4-dia- tor-type munitions (separate dye And fuel com­
mino-2,3-dihydroanthraquinone, has not been tested partments). The dye should preferably be a
but is expected to be relatively safe by its stricture. crystalline compound and have a melting point

7 -4 1
 AH CP 706-185

/ TABLE 7-11 . ,
CH ARACTERISTICS OF T Y PIC AL EJECTION-TYPE COLORED SMOKE DEVICES

Characteristic 4.2-in. Colored M18 Colored Smoke

Smoke Projectile Band Grenade

Dimensions, in. Overall—4.2 dia by 20 long 2.5 dia by 4.5 high .

(approx.)
Canister— 3.7 dia by 9.3 long Six smoke emission holes
(approx.) ;
Weight Projectile— 23 to 24.5 lb 11.5 oz make mixture
Ejection charge— 25 g Grade
A black powder
35 g infallible
powder .
Fuze . ' / . M54 Time and S.Q - M201A1 . • .
1 . 2 to 2 sec delay
Propellant M6
Loading Pressure 18000 lb/in . 2
Smoke Duration 50-90 sec
Applications Time-fuzed for air-burst sig- Grenade is , thrown or
haling and/or base-ejected for launched from a rifle or car-
marking ground positions. bine by using a M2A1 gre-
Uses red, yellow, green or nade projection adapter.
violet colored smoke for sig- Uses red, yellow, green, or
naling, spotting, or outlining violet colored smoke for sig-
a position . naling ‘
Visibility Very good Easily identified at altitude
of 1 0 , 0 0 0 feet against back­
ground of green and brown ;
clearly seen at a distance of
three miles.

under 150°C, or a melting point of 100°C, when Yellow, N (N, N-dimethyl-p-phenylazoaniline) gives
mixed with a small proportion of a melting-point a satisfactory color. The dye duPont Oil Yellow
depressant such as diphenylamine (less than 25 N produces, a brilliant yellow colored smoke. Mix­
percent is necessary). The dye should be stable tures of blue and orange dyes, such as Calco Oil
for three to four minutes at temperatures of 50°C Orange Y-293 and Calco Oil Blue .NA (1,4-di-
to 100°C above its melting point. The dye l-(4 - amylaminoarithraquinone), give a brown-orange or
phenylazo)-2 -naphthol—called commercially by a brown-rose cloud. Blue smoke results from using
- variety of names, i.e., duPont Oil Orange, Sudan only 25 percent Calco Oil Orange Y-293. With a
Orange, Federal Smoke Orange-E, and l - ( 0 - 75 percent mixture of National Oil Scarlet 6-0
tolylazo)-2-naphthol (Calco Oil Orange Y-293)— and Calco Oil Blue NA, the color has the appear­
produces good orange smoke clouds but varies in ance of a mixture of orange and violet or tan and
quality depending upon the commercial source. violet. Larger percentages of scarlet result in a
The dye l-xylylazo-2-naphthol (Calco Oil Scarlet rose-colored cloud and smaller percentages result
II, National Oil Scarlet 6 -0 ) gives a much redder in blue smoke. A mixture of the dye l-(2-methoxy-
cloud but the addition o f 20 percent duPont Oil phenylazo)-2-naphthol (Federal Signal Red A )
 AMCP 706-185

with Calco Oil Blue NA gives a blue-gray cloud

for all proportions tried. The dye Monoazo Red
(duPont) gives much the same result.

7-3.4.11 Colored Smoke from Solution of Dyes82

A third method of producing colored smoke
clouds is by volatilization of the dyestuff from
solution, usually by means of the hot exhaust of a
motor. Early attempts to use colored smoke trails
from the exhaust of an airplane engine employed
a mixture of SAE-10 oil (flushing oil) and dye.
Carbon tetrachloride has also been used in place
of the oil, but is not recommended. Ten pounds
of dye are mixed with two gallons of the oil to a
smooth, pasty solution and then diluted with an
additional five gallons of flushing oil. The dyes
recommended are Oil Purple AB, Oil Blue-Oreen
0, Oil Red EGN, and Oil Orange .2311 [ 1-(4-
phenylazo)-2-naphthol]. ■,
The principal difficulty is the low solubility of
the dyes in oil. A solvent composed of one part
of carbon tetrachloride to four parts of SAE-10
oil is not satisfactory due to congealing of the so­
lution. The use of hexachlorobutadiene as solvent,
however, is considered successful in that the result­
ing mixture of dyestuff and solvent- is extremely
fluid and has no tendency to congeal. Azo dyes are
found to be the most satisfactory. These are Gil
Yellow (4-(0-tolylazo)-2-methylaniline), Qil Scarlet
6-G (l-xylyiazo-2-naphthol), Oil Red 0 , and Oil
Green Q-261.
Further tests indicate that solutions of dye in
hexachlorobutadiene, diluted with SAE-10 oil, are
unsatisfactory due to the gelling of the mixture
within a few hours after mixing. Solutions pre­
pared with fifteen to eighteen pounds of dye, two
to three gallons of trichlorobenzene, and three gal­
lons of SAE-10 oil are found to be satisfactory.
No gelling of the solution is noted after six to eight
days.
Oil smoke is also produced in a wide variety of
colors and shades using the following oil-soluble
dyes either as such or in admixture:
Oil Blue NA (1,4-diamylaminqanthpaquinone)
Oil Blue R A [N-(p-dimethylaminophenyl)-l,4-
naphthoquinonimine] ,
Oil Red N-1700 [ 1- ( tolylazoxylylazo) -2-naph-
thol] /

7-48
 AMCP 706-185

SMOKE MIX
PRESSED AT 16,000 PSI

EJECTION CHARGE
25 G. GRAOE A4 SLACK POWDER
35 G. INFALLIBLE POWDER

-STRAWBOARO WASHER
•PRESSURE PLATE
■FELT PAD
FIBER WASHER
■STARTER MIX

Figure 7-14. 4.2-in. Colored Marker Projectile, Colored Smoke, E75

Oil Orange Y-293 [ 1-(o-tolylazo-2-naphthol] basic smoke. All the dyes, with the exception of
Oil Yellow 7463 [N, N-dimethyl-p-phenylazo- Oil Blue RA and Oil Red N-1700, are found to
aniline] produce the best results between 450°C ancl 700°C.
Gas Green CG (1,4-di-p-toluidinoanthraquiu- Oil Blue RA is used successfully at 400°C to
one) 550°C but shows a complete loss of color at 560°C.
Oil Red N-1700 produces the best results between
The maximum effect with the minimum quantity
550°C and 625°C. Water solutions of Auramine
o f dye is obtained by adding about five percent
and Red Y Supra Cone. (Safranine) are used effec­
o f the dye dissolved and/or suspended in oil
tively to produce colored oil smokes. Water spray
dispersed through a point-type spray nozzle. The
added to ’ie oil cloud does not appear to have any
dye is added at a point in the oil smoke exhaust
injurious effect. Water solutions o f Blue FFB,
where the temperature can be varied between 400°C
New Blue N (Methylene Blue), and Magenta X X
and 800°C. By controlling the temperature within
fail to produce color under the conditions o f these
approximately 50° C limits, a fairly constant shade
experiments.
is obtained with each dye. B y using different tem­
perature bands, variations are obtained in the
shade of smoke produced from a given dye. The 7-3.4.12 Black Smoke88-44
efficiency of color production, however, appears to Black dyes do not, in general, give satisfactorily
be equivalent in all cases. The shade changes dense black smokes. Such smokes are generally
which result from variations o f temperature are produced by burning of hydrocarbons such as
due, at least in part, to the changes in color o f the phenanthrene or anthracene. The addition o f an-

7-44
 AMCP 706-185

FUZE
W/OOOSTER

Figure 7-15. 105 m u M l C o lo re d M a rk e r Projectile

lABLE 7-12
BASIC D IFFEREN CES B E T w EEN THE COLORED M ARK ER AND
BASE-EJECTION SMOKE PROJECTILES FOR 105 mm GUN

HE Color ed Marker Base-Ejection Colored Smoke

Build-up period of Effective instantaneous Over a period of from 1-2 min

colored cloud
Density of cloud Highly SE turated Wispy .
Duration of cloud Average (15-85 sec 75-120 sec
Size of cloud Approx. <0 X 60 ft Streamer approx. 4 ft across
Lethality of round May be lethal (fragments) Nonlethal
Fuzing of round MTSQ & VT fuzing MTSQ .fuzing only
Weight of round Equal to 105 mm HE round Lighter than 105 mm HE
round
Ranging of round Similar to 105 mm HE round Canister impacts up to 150
ft away from impact point of
projectile body

thracene or naphthalene to HC smoke mixtures E:lso with an appropriate detonator or booster charge,
produces black smoke. The oxidizing agent gen­ the resulting explosion giving a large puff of
erally used is potassium perchlorate. colored smoke. Colored smoke clouds are also ob­
tained from a mixture of a salt and a dye dis­
7-3.4.13 Explosive-Type Colored seminated by a central high-explosive burster of
Smoke Bursts46,46 baratol, amatol, 60 mm ignition potoder, Composi­
In addition to the colored smoke dissemination tion B, or others. The use o f a salt dilutent is one
methods discussed in the previous paragraphs, procedure for producing controlled nuclei on which
there is the method that produces its effect through the dye may condense. Cast or pressed dye, along
the Eiction of an explosive burster. Both propellants with a central burster, is also used to produce col­
and high explosives are used for this purpose. '?or ored clouds. The basic performance differences
example, a colored smoke burst can be obtained by between dissemination of colored smoke by an
using a mixture o f approximately equal parts of item using an explosive burster and by a munition
dye and EC powder. This mixture is detonated using burning-type smoke mixtures are tabulated

7 -4 5
AMCP 706-185

in Table 7-12. The 105 mm Colored Marker Pro­ acidity. For many dyes baratol has proved to be
jectile, referred to in the table, is shown in Figure satisfactory. The method for determining the
7-15. ' weight of a burster used in colored marker pro­
The dyes that are satisfactory for dissemination jectiles was derived by assuming that the energy
by an explosive charge include the same dyes as of the explosive charge is proportional to the strain
those used in the burning-type colored smoke energy required to burst the projectile. In order to
munitions. Also, many azo-type dyes which do not simplify calculations, conversion factors and con­
perform well in burning smoke munitions give very stants are included in a dimensionless factor K. The
good smoke clouds when disseminated l>y EC pow­ weight of burster required is given by the empirical
der. Among the best dyes for explosive munitions formula:
are l-(2-methoxyphenylazo)-2-naphthol for red,
wc = K W (Y + V ) e K ' (7-7)
l-(4-nitrophenylazo)-2-naphthol and l-(4-phenyl-
azo)-2-naphthol for orange, and 4-phenylazo-m- where
phenylenediamine for yellow.
we = weight of explosive required (including
initiator), g
7-3.4.13.1 Propellant Bursters47 K == a constant, 11.4 X 10-e to 11.4 X 10~B,
Several propellants have been studied for use depending on caliber and explosive used
as bursters, the EC powder mentioned above show­ (the exact" K can be found by empirical
ing the greatest promise. Various methods of load­ evaluation only)
ing EC powder and dye in a projectile have been IV — weight of steel components of projectile
tried as follows: (excluding fuze and base), lb
a. Mixing the dye and EC propellant powder Y = yield stress of projectile steel, psi
intimately before loadirg the projectile, e = strain elongation at fracture, %
b. Coating the projectile wall with melted dye V = ultimate strength of projectile steel, psi
and placing the EC powder in the central K' = ratio of calo: ,e value of a standard ex­
cavity, plosive to explosive to be used. For in­
c. Filling the projectile with melted dye and stance, if value of tetryl is 1,100 cal/g
then drilling out a core for EC powder, and and baratol is 900 cal/g the formula
a. Loading the projectile with approximately would be:
equal increments of dye and EC powder in to; = 7HV(F + E 0 e (ll/9 )
alternate layers. Burster charges designed by this method have
The last method, in which alternate layers of dye functioned favorably. The quantity (F + TJ)e is
and EC powder are used, was found to be the best. roughly equal to twice the strain energy absorbed
The alternate-layer method of loading with EC by one cubic inch of steel.
powder was found to be superior to bursters of
either TNT or tetryl. The burster explosive used 7-3.4.14 Typical Mixtures
is a mixture similar to amatol loadings, consisting Typical colored smoke mixtures, including a
of 27.8 percent ammonium picrate and 72.2 percent few white and black smokes, are shown in Table
ammonium nitrate. 7-13. ;

7-3.4.13.2 High Explosive Bursters 7-3.5 AGENT AEROSOLS

Sufficient explosive must be included in the Because of their nature, a detailed discussion
burster charge so that when it is detonated, it will of the dissemination of agent aerosols is beyond the
break the projectile apart without causing exces­ scope of this handbook. In general, the principles
sive dispersion and/or burning of the filler. The and methods applicable to the dissemination of a
products of explosion must be compatible with the colored smoke agent are applicable to the dis­
dye used. The color of many dyes is influenced by semination of an agent aeroSol.

7-46
 AMCP 706-185

TABLE 7-13
TY P IC A L SMOKE COMPOSITIONS

Typical
Type Composition, % Application Devices

W H IT E :
HC-Type C Hexachloroethane 45.5 Screening Smoke pots
Zinz Oxide 47.5 and Smoke bombs
Aluminum (graine a) 7.0 Signaling Grenades
Modified HC Hexachlorobenzene 34.4 Screening Smoke
Zinc Oxide 27.6 and projectiles
NH 4 CIO4 24.0 Signaling
Zinc Dust 6 .2

Laminae w/catalys t 7.8

Modified HC Dechlorane 33.9 Screening Smoke
Zinc Oxide 37.4 and projectiles
NH 4 CIO4 20.5 Signaling
Laminae w/catalys 8.2
Plasticized White White Phosphorus 65.0 Screening Chemical
Phosphorus (P W P ) Plasticizer 35.0 (antipersonnel) mortar projectiles
(Neoprene 100 parts)
( Carbon 75 parts)
(Zylene 44 parts)
(Litharge 15 parts)

BLACK:
KCIO 3 (200 mesh) 52.0 Screening Grenades, etc.
Anthracene (40 me sh) 48.0

COLORED:
Red Dye-MIL D-3718 40.0 Signaling Navy floating
KCIO 3 ' 24.0 drift signal
NaHCOa 17.0
Sulfur ; 5.0
Polyester resin 14.0
Red 1-methylamino (AQ )* 45.0 Signaling Rocket type
1,4-di-p-toluidino ( jM i)* 3.0 parachute
KClOs (23p) 35.0 ground
Sugar, fine ( l i p ) 17.0 signals
Red l-(methoxyphenyla 5 0 )- A ir marker 90 mm Red
2-naphthol 80.0 Marking marker
NaCl 20.0 ground targets projectile

• (A Q )— Anthraquinone
AMCP 706-185

TABLE 7-13 (cont’ d)

Typical
Type Composition, % Application Devices

Red Dye (R ) 40.0

KClOs 28.0 Signaling Improved
(plastic) NaHCOa 23.0 grenade
Sulfur 5.0 fillings

Polyvinyl acetate in
ethyl acetate 3.0

Yellow Benzanthrene 32.0 Signaling Rocket type

Indanthrene GE 15.0 parachute
EClOa ( 2 3 ( a ) 30.0 ground
Sugar, fine (lip.) 20.0 signals
NaHCOs ( 2 0 ( a ) 3.0
Yellow Auramine.Hydrochloride 40.0 Air marker, etc. 90 mm yellow
NaCl 60.0 marker projectile
Yellow Dye (Y ) 40.0 Signaling Improved
(plastic) EClOa • 29.8 grenade
NaHCOa 23.2 fillings
Poljrvinyl acetate in
ethyl acetate 7.0
Green 1,4-di-p-toluidino (A Q )* 28.0 Signaling Rocket type
Indanthrene GE parachute
(golden yellow) 12.0 ground
EClOa (23(i) 35.0 signals
Sugar, fine (lip.) 23.0
NaHCOa ( 2 0 ( a ) 2.0
Green Dye (G ) 40.0 Signaling Improved
(plastic) EClOa 26.0 grenade
NaHCOa 24.0 fillings
, Sulfur 6.0
Polyvinyl acetate
w/ethyl acetate 4.0
Violet Violet dye, Signaling Rocket type
Spec. MIL-D-3691 47.5 parachute
EClOa ( 2 5 ( a ) 28.0 ground
Sugar, fine ( I O ja ) 18.0 signals
NaHCOa ( 2 0 ( a ) 4.5
Asbestos 2.0
Orange 8-chloro-l-amino (A Q )* 39.0 Signaling Grenades
Auramine 6.0
EClOa 22.3
Sulfur 8.7 * \

NaHCOa . 24.0
* (AQ)— Anthraquinone

7 -4 8
 AMCP 706-185

REF RENCES
1. A. M. Prentiss, Chemicals in War, McGrav - Bureau of Naval Weapons, Washington, D. C.,
Hill Book Co., Inc., N. Y „ 1937. May 1959.
2. K. F. Sawyer, “ Screening Smokes,” Thorpe's 16. N. Irving Sax, Dangerous Properties of In­
Dictionary of Applied Chemistry, V o l.'X , 4th dustrial Materials, 2nd Ed., Reinhold, 1963.
Ed., Longmans, GreeD, London, 1950, p. 781. Library of Congress Catalog Card No. 63­
3. H. L. Green and W. R. Lane, Particulate 20370.
Clouds: Dusts, Smokes ana Mists, D. Van Noii- 17. David W . Fassett, Don D. Irish, Eds., In­
trand Co., London, 1957. dustrial Hygiene and Toxicology, Vol. II,
4. History of Research and Development of the Interscience Publications, 1963.
Chemical Warfare Service in World W ar L r, 18. AN-M7 Fuel Block Program, Report 0-2148U,
Olin Mathieson Chemical Corporation, New
Reinhold, N. Y., 1948.
Haven, Connecticut, April 15, 1961 (DDC-
5. L. P. Brophy, D. M. Syndham, R.)C. Cochrane,
■AD 271 (878).
The Chemical Warfare Service: From Laborc-
19. L. F. Young, W. M. Conway, The T36E1 Steel-
tory to Field, Department of Army, Wash­
Wool White Phosphorus ( S W P ) Smoke Gre­
ington, D. C., 1959.
nade, Picatinny Arsenal Technical Report
6. W. A. Noyes, Jr., Ed., Chemistry, Science in
2618, Picatinny Arsenal, Dover, N. J,, Novem­
World War II Series, Little, Brown and Co.,
ber 1959.
1948.
20. R. D. Kracke, Improved Phosphorus Smoke,
7. John A. Martin, “ Combat Smoke in Korea, ’
TCR-13, Technical Command, Arm y Chemical
Armed Forces Chemical Journal, 7 October
Center, Edgewood Arsenal, Maryland, March
1953.
1949.
8. B. E. Kleber and E. I. Byrnes, “ Make
21. H. Zislin, Stabilization of Red Phosphorus,
Smoke,” Armed Forces Chemical Journal, 6
Frankford Arsenal Report 660, Frankford
April 1943.
9. Arsenal, Philadelphia, Pa., October 1945.
S. L. A. Marshall, Infantry Operations a n i
22. M. S. Silverstein, G. Nordblom, Stabilization
Weapons Usage in Korea During the Winter
of Commercial Red Phosphorus, Frankford
of 1950-51, Report ORO-R-13, Department of
Arsenal Report 206, Frankford Arsenal, Phila­
Army, Washington, D. C., 27 October 1953
delphia, Pa., April 1943.
10. W. W, Cavell, T. Stevenson, Smoke Tracer,),
23. M. S. Silverstein, G. F. Nordblom, C. W. Dit­
Caliber .50, Frankford Arsenal, Philadelphia,
Pa., November 1951. trich, and J. J. Jackabein, “ Stable Red Phos­
11. B A T Antitank Weapon and Ammunition, phorus,” Industrial and Engineering Chem­
Frankford Arsenal Report 1080, Frankford istry 40, 301 (1948).
Arsenal, Philadelphia, Pa. 24. D. L. Elkstedt, Laboratory and Flight Tests
12. W. A. Noyes, Jr., Military Problems with Aero of Chemical Tracking Aids, AFMDC-TR-58-2,
sols and Non-Persistent Oases, Summary Tech­ Air Force Missile Development Center, Hollo-
nical Report Of Division 10, Department of mon Air Force Base, New Mexico* July 1958
Army, Washington, D. C., 1946. (DDC-AD 23 736).
13. G. Mie, Ann der Phys. 25, 377 (1908) 25. H. B. Elkins, HC Smoke: Properties of Zinc
14. M. H. P. P. Yevick, The Toxicity of Combus Oxide Affecting the Burning Characteristics
tion Products o f Pyrotechnics, CWL-TM-21!- of HC Smoke Mixtures, TDMR-729, Edgewood
12, Arm y Chemical Warfare Laboratories, Arsenal, Md.
Edgewood Arsenal, Maryland, May 1960. 26. L. Finkelstein, The Chemistry o f HC Smoke
15. Toxic Hazards Associated with Pyrotechmc Mixtures, Army Chemical Laboratories, Edge-
Items, OP 2793, Naval Ordnance Laboratory, wood Arsenal, Md.

7-49
AMCP 706485

REFERENCES (cont’ d)
27. G. Weingarten, Long Range Research on P y­ metric Analysis of Organic Dyes, Picatinny
rotechnics Development of an Improved Smoke Arsenal Technical Note 25, Picatinny Arsenal,
Composition for Activator, Practice, M l, Pica- Dover, N. J., 1958.
tinny Arsenal Technical Report 1799, Pica- 37. ORDWES Quarterly Report 1948-8, Wes­
tinny Arsenal, Dover, N. J., November 1950. leyan University, Middletown, Connecticut,
28. Jack DeMent, Composition for Smoke Produc­ May 1948.
tion, U.8. Patent 2,995,526, August 1961. 38. W. W. Reaves, J. H. Hassmann, Investiga­
29. J. E. Andrews, Jr., B. Werbel, Smokes, Pica- tion of a Long Burning Plastic-Bonded, Col­
ored Smoke Mixtuie, CW LR 2339, Army
tinny Arsenal, Dover, N. J., May 1962.
Chemical Laboratories, Englewood Arsenal,
jO. J. E. Andrews, Jr., K. G. Carlon, W. W.
Maryland, January 1960 (DDC-AD 233 750).
Reaves, Evaluation of a Plastic-Bonded HC
39. N. J* Wilkaitis, Research and Development of
Smoke Composition for the M8 Grenade,
Flammable Plastic for Colored Smoke Use,
CRDLR-3065, Army Chemical Laboratories,
Army Chemical Laboratories, Edgewood A r­
Edgewood Arsenal, Maryland, April 1961.
senal, Maryland, October 1956 (DDC-AD 137
31. S. Gordon and C. Campbell, ‘ ‘ Preignition and
748).
Ignition Reactions o f the Pyrotechnic System
40. Munsell Book of Color, Munsell Color Co., 10
Zn-CeCls-KClOi, ” F ifth Symposium on Com­ East Franklin St., Baltimore, Maryland.
bustion, Reinhold Publishing Co., N. Y., 41. Chemical and Radiation Laboratories Report
1955. 610. Edgewood Arsenal, Maryland.
32. S. Grundemeier, Survey of Literature of 42. S. J. Magram, Sensitivity of Colored Smoke
Chemical Tracking Aids, HADC-TR-57-7. Air Mixtures, TDMR-547, Ldgewood Arsenal,
Force Missile Development Center, Holloman Maryland.
Air Force Base, New Mexico, August 1957 . 43. A. F. Talyrek, The Toxicity of Certain Dyes in
(DDC-AD 135 001). . Current Use, Picatinny Arsenal, Dover, N. J.,
33. L. Finkelstein, Colored Smokes, Vol. 12 of His­ May 1964.
tory of Research and Development of the 44. Development of a Black Smoke Candle for
Chemical Warfare Service in World War II, Signal Purposes, EAOD-376, Edgewood A r­
Army Chemical Center, Edgewood Arsenal, senal, Maryland, March 1926.
Maryland, 31 December 1945 (D D C -ATI 207 45. T. Advokat, Colored Marker Shell M107 (155
451). mm), Picatinny Arsenal Technical Note 140,
34. G. D. Heath, Formation of Coloured Smoke Picatinny Arsenal, Dover, N. J., September
Clouds, Part 1 o f Review of Suitable Organic 1956 (DDC-AD 108 297).
D ye Stuff, PR 2547, Great Britain, April 1943. 46. T .' Advokat, H E Colored Marker Shell for
35. D. Anderson, S. Gordon, D. Edelman, Thermo­ M29 and T72 Mortars (81 mm M.362), Pica­
gravimetric Determination of the Energies of tinny Arsenal Technical Report 2664, Pica­
Activation Volatilization, Picatinny Arsenal tinny Arsenal, Dover. N. J., January i960
Technical Not" 16, Picatinny Arsenal, Dover, f DDC-AD 314 621).
N. J., 1948. 47. G. D. Heath, Production of Colored Smokes
36. D. Anderson, S. Gordon, D. Edelman, D if­ by Explosive Dispersion, PTP-147, Great
ferential Thermal Analysis and Thermogravi­ Britain. January 1950,

7-50
£U.8. GOVERNMENT PRINTINQ OFFICE: 1 9 8 5 529 8 $9 31110
 ENGINEERING DESIGN HANDBOOK SERIES
Listed below are the Handbooks'which have been published or are currently being printed. Handbooks with publication
dates p rio r to 1 August 1962 were publish ed as 20-ser1es Ordnance Corps pamphlets. AMC C ircu lar 310-38, 19 July 1963,
redesignated those publications as 706-se rles AMC pamphlets ( l . e . , ORDP 20-138 was redesignated ANCP 706-138). A ll new,
rep rin ted , or revised Handbooks are being published as 706-series AMC pamphlets.

General and Miscellaneous Subjects B a llistic M issile Series (continued)

No. T it le no^ n il* .
106 Elements of Armament Engineering, Part One, 283 Aerodynamics
Sources of Energy I 284(C) Trajecto ries (U)
107 Elements of Armament Engineering, Part Two, 286 Structures
B a llis tic s
108 Elements of Armament Engineering, Part Three, B a llistics Series >

Weapon Systems and Components 140 ’T ra je c to rie s , D iffe r e n tia l E ffe c ts , and Data
110 Experimental S ta tis tic s , Section 1, Basic Con­ fo r P ro je c tile s
cepts and Analysis of Measurement Data 150 In te rio r B a llis tic s of Guns
111 Experimental S ta tis tic s , Section 2, Analysis 160(S) Elements of Terminal B a llis tic s , Part One,
of Enumerative and C la s s ific a to ry Oata Introduction, K1U Mechanisms, and
112 Experimental S ta tis tic s , Section 3, Planning V u ln e ra b ility (U)
and Analysis of Comparative Experiments 161(S) Elements of Terminal B a llis tic s , Part Two,
113 Experimental S ta tis tic s , Section 4, Special C ollection and Analysis of Data Concerning
Topics I Targets (U)
114 Experimental S ta tis tic s , Section 5, Tables 162(S-RD) Elements of Terminal B a llis tic s , Part Three,
121 Packaging and Pack Engineering! Application to M issile and Space Targets (U)
134 M a in ta in a b ility Guide fo r Design
135 Inventions, Patents, and Related Matters Carriages and Mounts Series
(Revised) I
136 Servomechanisms, Section 1, Theory 340 Carriages and Mounts--General
137 Servomechanisms, Section 2, Measurement and 341 Cradles
Signal Converters I 342 Recoil Systems
138 Servomechanisms, Section 3, Am plification 343 Top Carriages
139 Servomechanisms, Section 4, Power Elements 344 Bottom Carriages
and System Design 345 E g uilibrators .
170(C) Armor and Its Application to Vehicles (U) 346 Elevating Mechanisms
270 Propellant Actuated Devices 347 Traversing Mechanisms
290(C) Warheads--General (U)
331 Compensating Elements (F ire Control Series) Guns Series
250 Guns--General
A/munition and Explosives Series 252 Gun Tubes
175 Solid Propellants, Part One
176(C) Solid Propellants, Part Two (U) Military Pyrotechnics Series
177 Properties of Explosives of M ilita ry In te re s t, 186 Part Two, Safety, Procedures and Glossary
Section 1 I 187 Part Three, Properties o f M aterials Used in
178(C) Properties of Explosives o f M ilita ry In te re s t, Pyrotechnic Compositions .
Section 2 (U) 189 Part F ive, Bibliography
179 Explosive Trains (
210 Fuzes, General and Mechanical Surfaoe-to-Air M issile Series
211(C) Fuzes, Proxim ity, E le c tr ic a l, Part One
212(S)
213(S)
Fuzes, Proxim ity,
Fuzes, Proxim ity,
IS
E le c tr ic a l, Part Two
E le c tr ic a l, Part Three (U)
291
292
Part
Part
One, System Integration
Two, Weapon Control
214(S) Fuzes, Proxim ity, E le c tric a l, |Part Four (U) 293 Part Three, Computers
215(C) Fuzes, Proxim ity, E le c tr ic a l, Part Five (U) 294(S) Part Four, M issile Armament (U)
242 Design fo r Control of P rojectille F lig h t 295(S) Part Five, Countermeasures (U)
Characteristics 296 Part S ix , Structures and Power Sources
244 Section 1, A r t ille r y Anmun1t1on--General, 297(S) Part Seven, Sample Problem (U)
with Table of Contents, Glossary and
Index fo r Series Materials Seriee*
245(C) Section 2, Design fo r Terminal Effects (U) 149 Rubber and Rubber-Like M aterials
246 Section 3, Design fo r Control of F lig h t 212 Gasket M aterials (Nonmetalllc)
Characteristics (out o f print) 691 Adhesives
247 Section 4, Design fo r Projectipon 692 Guide to Selection of Rubber 0-Rings
248 Section 5, Inspection Aspects of A r tille r y 693 Magnesium and Magnesium Alloys
Ammunition Design 694 Aluminum and Aluminum Alloys
249 Section 6, Manufacture Of M e ta llic Components 697 Titanium and Titanium Alloys
of A r t ille r y Anrnunition ' 698 Copper and Copper Alloys
699 Guide to Specifications fo r F lexib le Rubber
Automotive Series Products
355 The Automotive Assembly 700 Plastics
356 Automotive Suspensions 721 Corrosion and Corrosion Protection of Metals
722 Glass
ba ilie tie M issile Geriee
28MS-RD) Weapon System Effectiveness (li)
282 Propulsion and Propellants
♦The M aterials Series is being published as M ilita ry Handbooks (MIL-HDGK-) which are availab le to Department o f Defensi
Agencies from the Naval Supply Depot, 5831 Tabor Avenue, Philadelphia, Pennsylvania 19120.
 1

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