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AMC PAMPHLET AMCP 706-185

ENGINEERING DESIGN
HANDBOOK

MILITARY PYROTECHNICS SERIES

PART ONE

THEORY AND APPLICATION

HEADQUARTERS, U.S. ARMY MATERIEL COMMAND APRIL 1967


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AD817071

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as directed by Army Material Command,
Attn: AMCRD-TE, Washington DC 20315 and 28
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HEADQuARITERS
UNITED STAlES ARMY MATERIEL COMMAND
WASH1[NGTON,ID. C. 20315
AMC PAMPHLET 28 April 1967
No. 706-185
ENGINEERING ID~SIGN HANDBOOK
i
MILITARY PYROTECHNICS SERIES
PART ONE·,-THEORX ~ND APPLICATION,
This pamphlet' is 'publ iShe~ fdr; the' ihfonnation', and guidance
of a 11 concerned. . ' I • ,,'

(AMCRD~R)

FOR THE ~PMMANDER:

K. H. BAYER
Maj()r. General, USA
Acting Chief of ,Staff

OFFICIAL:

'0 ISTR I BUT IOff:


Special
AMC P AMPHLE T 23 August 1968
No. 706-185
CHANGE 1

ENGINEERING DESIGN HANDBOOK

MILITARY PYROTECHNICS SEIRIES PART ONE- -THEORY AND APPLICATION

AMCP 706-185, 28 April 1967, is changed as follows:

Remove page-- Insert page--

6-14 6-14

( AMCRIJ)-R)
I

FO~ THE COMMANDER:·


I

OFFICIAL : CLARENCE J. LANG·


I
Major General, USA
I . Chief of Staff

~~EGO~·~
I
Colonel, GS
Ch~ef,Adminlstrative Office.

nrSTR
I
IBUTION:
.
SPlecial
AMCP 706·185

PREFACE

The Engineering Design Handbook Series of the Army Materiel Comman.d


III a coordinated series of handbooks containing basic information and funda-
mental data useful in the design and development of Army materiel and systems.
The handbooks are authoritative referen~e books of practical information und
quantitative facts helpful in the design and development of Army materiel so
tha.t it will meet the tactical and the technical needs of the Armed For.ces. The
present handbook is one of a series intended to fill a longfelt need for an au-
thoritative and comprehensive source of information on military pyrotechnics.
It is a common misconception to regard military pyrotechnics as being
synonymous with fireworks. Militar-y pyrotechnics is rapidly developing into a
science which exploits all applic&ble scientific and engineering prineiples and
practices.
This handbook, Military Pyrotechnics, Part Ont', Theory arki Applica.tion,
includes a chapter on the history of the pyrote~hnic art, a chapter giving a
general introO'lction to the application of pyrotechnic devie,'3 to military prob-
lems, and chapters on Physical-Chemical Relationships, Visibility, Production
of Heat, Production of Light, and Production of 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 fo~ Chapter 1, History of Military Pyrotechnics,
Wfil> prepared by the McGraw-Hill Book Company Technical Writing Service.
All material was prepared for the Engineering Handbook Office of Duke Uni-
versity, prime contraetor to the Army Research Offi('c-Durham. The prepara-
tion of this handbook was under the technical guidance of an interservice com-
mittee with l·epresentr.tioll from the Army Chemical Center, Ballistic Research
I,aboratories, Frankford Arsenal, Harry Diamond Laboratories and Picatinny
Arsenal of the .Army Materiel Command; the Naval Ammunition Depot (Crane),
Naval O"dnance l;!\boratory ahd the Naval Ordnance Tfst Station. 'I'he chair-
man of this ~ommitte€ was Garry Weingarten of Picntinny Arsenal.
Elements of the U. f1. Army Materiel Command h8\; ng need ror handbooks
may submit requisitions or offieial requests directly to ,blications and Reprl.i.
duction Agency, I.. etterkenny Army Depot, Chambersburg, Pennsylvania 17201.
Contractor's should submit such requisitions or requests to their contracting
officers.
C0mments and suggestiuns on this handbook firl' welcome and should be ad··
dressed to Army Research Offiee-DurIlam. Box CM, Duke Station, Durham,
North Carolina 27706.
AMCP 706·185

ii
AIICI' 706-185

T ABLE OF CON' TENTS

Paragraph Page
PREPACE ........................................... i
LIST OF ILLUSTRATIONS.......................... xii
LIST OF TABLES .................................. xvi

CHAPTER 1
HISTORY OF MILITARY PYROTECHNICS

1-1 Introduction ............... _. . . . . . . . . . . . . . . . . . . . . . . . . . 1·1


1-~ Early History .................................... ,... 1-1
1-2.1 Greek Firf) ....................................... 1-1
1-2.2 Chinese Pyrotechnics ................... ,.......... 1-2
1-2.a Gunpowder . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-2
1-2.4 Miscellaneous Uses ................................ 1-2
1-3 18th and 19th Centurie£ ......................... , . . . . . 1-2
1-4 Early 20th Century ................................... 1-3
1-4.1 World War I .................................... 1-3
1-4.2 Between the Wars ................................ 1-4
1-4.3 World War E ................................... 1-4
1.. 5 Post W<'rld War II Period. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1-5
REFERENCEB ...................................... 1-6

CHAPTER 2
INTRODUCTION TO MILITARY PYROT:CCHNICS

2-1 Introduction ................ " ......... ' .............. . 2-1


2-1.1 Pyrotechnic Devices and Uses ..................... . 2-1
2-1.2 Characteristics of Pyrotechnie Compositions ....... . 2-3
2-1.2.1 Performance Characteristics .................. . 2-3
2·1.2.2 P ....ocessing and I:lensitivity Characteristics ...... . 2-3
2-1.2.3 General Funetioning Characteristics ........... . 2-3
2-1.3 Constituents in Pyrote~hnic Compositions .......... . 2-4
2-1.4 Comparison of Pyrotechnie Mixtures and Explosives 2-5
RBFERENCES ..................................... . 2-6

iii
Preceding page blank
AMCP 706·185

TABLE OF CONTENTS (cont'd)


CHAPTER 3
PHYSICAL-CHEMICAL RELATIONSHIPS
Paragraph Page
3-1 State of a System .................................... . 3·1
:3-1.1 The Gaseous State ............................... . 3·1
3-1.1.1 Ideal Gases ........................•......... 3·1
:J-1.1.2 The Universal Gas Constant and Standard Con-
ditions .................................. . 3·2
3-1.1.3 Real Gasel"! .................................. . 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 ..................................... . 3·7
3-2.1 Thermodynamic Relationships ..................... . 3-7
:J-2.1.1 First Law of Thermodynamics ................. . 3·7
3-2,1.1.1 Heat Effects at Constant Volume and Constant
Pressure ............................ . 3-7
:J-2.1.1.2 Heat Capacity ........................... . 3·8
:3-2.1.1.2.1 Heat Capacity of Gases ............... . 3·9
3-2.1.1.2.2 Heat Capacity of Liquids and Solids ... . 3-9
:3-2.1.2 Second I.,aw of TheI·modynamics .............. . 3-9
3-2.1.3 Third Law of Thermodynamics ................ . 3-10
:3-2.2 Thermochemistry ................................ . 3-11
:3-2.2.1 Heats of Reaction ............................ . 3-11
:~-2.2.2 Effect of Temperature on the Heat of Reaction 3·12
:3-2.2.3 Enthalpy Tables ............................. . 3-13
:\-2.2.4 Bond Energies .............................. . 3-13
~~-2.3 Free Energy and EquiEbrium ..................... . 3-13
.3-2.3.1 Chemical Equilibrium ........................ . 3-14
3-2.3.2 The LeChatelier Principle .................... . 3-16
a-2.3.3 Free Energy and the Equilibrium Constant. .... . 3-16
3-2.3.4 Free Energy Calculations ..................... . 3-17
:J-2.3.5 Tabulated Free Energy Values ............... . 3-19
Adiabatie Flame Temperature .................... . 3-19
:J-2.5 Sample Thermodynamic Calculations .............. . 3-20
a-2.6 Summary of Thermo('hcmieal Calculations .......... . 3-23
:J-:3 ('hemical Kinetics .................................... . 3-23
:3·3.1 Moleclllarity of Reactions ......................... . 3-24
:J·3.2 Order of Reaction ....... ............. . ......... . 3-25
:!-3.3 Influence of Trmperaturp 011 ReactiGII Rates ........ . 3-26
:J-~H Chain Reactions ................................. . 3-27
:{·3.5 Heft'rog-cnpons Hpal'tions .......................... . 3-27
:1·3.6 Ignition and Propagatiw Burning ................ . 3-27

IV
AKCP 706-185

TABLE OF CONTENTS (cont'd)


ParagrGph Page
3-3.6.1 Ignition ..................................... . 3-28
3-3.6.2 Burning of Metal Particles .................... . 3-29
3-3.6.3 Burning of Solid Propellants ................. . 3-29
3-3.6.4 Rate of Propagative Burning .................. . 3-30
3-4 Thermoanalytical Techniques .......................... . 3-32
REFERENCES ..................................... . 3-36

CHAPTER 4
VISIBILITY

4-1 Introducti;"'ll 4-1


4-2 Vision .............................................. . 4-1
4-2.1 Brightness Contrast .............................. . 4-1
4-4.2 Overall Contrast ................................. . 4-2
4-3 Attenuation of Contrast ..................... . ....... . 4-2
4-3.1 Attenuation of Contrast by the Atmosphere ......... . 4-3
4-3.2 Obscuration of Vision by Artificial Smoke Clouds .... . 4-4
4-4 Visibility of Targets and Signals ...................... . 4-6
4-4.1 Visibility of Targets 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 Light Sources .................... . 4-9
4-4.3 Estimation of Visibility .......................... . 4-10
4-4.4 Illustrative Examples ............................ . 4-15
REFERENCES .................... . ............... . 4-18

CHAPTER 5
PRODUCTION OF HEAT

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


5-2 Introduction ......................................... . 5-5
5-~~ Theory ............................................. . 5-5
5-:U Amount of Energy Released ....................... . 5-6
5-3.2 Heat Transfer ................................... . 5-7
il-3.2.1 C<>n:luction .................................. . 5-9'
5·3.2.2 Convection and Radiation ..................... . 5-10
5·3.3 Heat Effect.s .................................... . 5-10
:,·4 f ncendiaries ......................................... . 5-11
f1·4.1 Small Arms Incendiary Ammunition ............... . 5-11
5·4.1.1 Ignition and Combustion of Aircraft Fuels ..... . 5-13

v
AMCP 706-185

TABLE OF CONTENTS (cont'd)


Paragraph PGg6
5-4.1.2 Nature of a Small Arms Incendiary Burst ...... . 5-14
5-4.1.3 Small Arms Incendiary Fillers .... ' ........... . 5-16
5-4.1.3.1 Fuels ................................... . 5-17
5-4.1.3.2 Oxidizers ................................ . 5-17
5-4.1.3.3 Binders, Lubricants, and Other Incendiary
Mixture Additives .................... . 5-19
[,-4.1.3.4 Typical Compositions .................. ~ .. . 5-20
5-4.1.4 Typical Small Arms Incendiary Bullets ........ . 5-20
5-4.2 Incendiaries for Gr0unJ Application ...... . ...... . 5-21
5-4.2.1 Ignition and Combustion of Ground Targets .... . 5-21
J-4.2.2 Incendiary Compositions ..................... . 5-22
3-4.2.2.1 Metal-Based Ground Incendiaries .......... . 5-22
5-4.2.2.2 Liquid Fuel-Based Incendiaries ........... . 5-:14
5-4.2.2.2.1 Liquid Incendiaries .................. . 5-25
5-4.2.2.2.2 Solidified Liquid Incendiaries ......... . 5-25
5-4.2.2.2.2.1 Rubber Thickeners ............... . 5-26
()-4.2.2.2.2.2 Napalm Thickeners .............. . 5-26
5-4.2.2.2.2.3 Methacrylate Thickeners .......... . 5-27
5-4.2.2.3 Othrr Incendiaries ....................... . 5-28
;'-4.2.3 Typical Incendiary Devices ................... . 5-28
5-5 Delay CompositioDR and Heat Powders ................. . 5-29
5-5.1 Pyrotechn~c Delays .............................. . 5-29
5-5.1.1 Delay Elements ............................. . 5-29
5-5.1.1.1, Obturated Delay Elements ................ . 5-30
5-5.1.1.2 Vented Delay Elements ................... . 5-30
5-5.1.2 Delay 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 Performance ................ . 5-32
5-5.1.3.1 Composition ............................. . 5-33
ii-5.1.:l.2 External Pressure ............ . ......... . 5-34
5-ri.1.3.3 External Temperature .................... . 5-35
5-5.1.3.4 Terminal Charge, Anticipatory Effect ...... . 5-36
5-5.1.3.5 Particle Size ............................. . 5-36
5-5.l.::t5 Ignitiun Compositions .................. .. 5-37
5-5.1.3.7 Column Diacneter ........................ . 5-37
ri-5.1.3.8 I.Joading Preflsure ........................ . 5-38
fi-il.1.3.!) Housing Material ........................ . 5-39
5-5.LUa Acceleration '" ... . .... " ............ . 5-43
;'·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 ............ . ..................... . 5-45
fl-6.2 Characteristics of Idral Igniter, First Fire, and
Starter Co:npositions ........................... . 5-46

vi
AMCP 706-185

TABLE OF CONTENTS (cont'd)


Paragraph P(1,{}e
;}-6.3 Typical Compositions ............................. . 5-48
REFERENCEH ..................................... . 5-48

CHAFfER 6
PRODUCTION OF LIGHT

6-1 Historical Summary .................................. . 6·1


6-1.1 Consolidated Illuminants ......................... . 6.1
6-1.1.1 Flares and Signals ........................... . 6·1
6-1.1.2 'i'racers ..................................... . 6·2
6-1.2 Nuncollsolidated Illuminant:; ...................... . 6·5
6-1.2.1 Photoflash Devices ............................ . 6-5
l.i-1.2.1.1 Photoflash Bombs ......................... . 6-5
6-1.2.1.1.1 Composition Type .... . .............. . 6·5
6-1.2.1.1.2 Dust Type ........................... . 6-6
6-1.2.1.1.3 Segregated Oxidant Type ............. . 6-7
6-1.2.1.2 Photoflash Cartridges ..................... . 6..7
6-1.2.2 Spotting Charges ............................ . 6-8
6-2 Theory of Light and Color ............................ . 6·8
6-2J Behavior of Light ................................ . 6·8
6·2.2 Spectral Distribution ............................. . 6·9
6-2.2.1 Discrete Spectra ............................. . 6-9
6-2.2.1.1 Line Spectra ............................ . 6-9
6-2.2.1.2 Band Spectra ........................... . 6-10
6-2.2.2 Continuous Spectra ......................... ,. 6-11
6·2.3 Radiation Sources ................................ . 6·11
6-2.3.1 'rhermal Radiation Sources .............. , ..... . 6·11
6·2.:U.1 Blackbody ............................... . 6-11
6 .. 2.a.1.2 Graybody ............................... . 6·12
6-2.3.1.3 Incandescent Sources ..................... . 6-12
6-2.3.2 IJuminescel1ce ........................... . ... . 6-13
6-?.3.2.1 Chemiluminescence ....................... . 6-14
6-2.3.2.2 Pho!:!phoreseence and Fluorescence ......... . 6-14
0·2.3.3 F'lame Sources ............... , ............... . 6-14
6·2.4 Photometry ..... .................... . ......... , 6-14
6-2.4.1 Instrunwnts for Measuring Light Inteilsity ., ... . 6·15
6·2.1.2 Measurement of the Light Output of }<'!arel:l ..... . 6-15
6·2.4.3 Intensity .................................. . 6-16
6·2.4.4 Brightness ...................... , ......... , .. 6·16
6-2.4.5 Illumiilation ................................. . 6-16
6-2.4.6 Photornetrie lJ n its ............................ . G·16
6-2.5 Color ......................... , ................. . 0-17
6·2.5.1 Additive Color .............. , .... , ........... . 6-17

vii
1-------------------------------------------------------------

AMe? 706-135

TABLE OF CONTENTS (cont'd)


Paracraph Pag6
6·2.5.2 S:J.btractive Color ............................ . 6-18
6-2.5.3 Chromaticity C;)ord.i.nates ..................... . 6-18
6-2.5.4 Munsell Color System ........................ . 6-20
6-2.5.5 Color Value .................................. . 6-20
6-2.6 Atmospheric Effects .............................. . 6-20
6-a Consolidated Illuininaiing Devices ................. ..,. 6-21
5-:3.1 Jlluminating Flares .............................. . 6-21
6-3.1.1 Aircraft Fla.res .............................. . 6-21
6·3.1.2 Surfaee Flares ............................... . 6-23
6-a.2 TlluminatiolJ Signals . . . . . . . . . . . . . . .. . ............ . 6-23
()·a.2.1 Aireraft Illumination Si;;!1als ................. . 6-23
6·a.2.2 Ground Illumination Signals .................. . 6-24
6-3.3 Tracers ......................................... . 6-24
()·34 Typical Compositions ................. . .......... . 6-27
G-3.5 Faetors Affeeting Performance ..................... . 6-27
6·a.5.1 Heat of Reaction ................ _............ . 6-30
6-:l.5.2 Composition ................................. . 6-33
6-3.5.a Fmitters .................................... . 6-33
0-3.5,4 Color III trnsifit'rs ............................ . 6-37
1i·;~.5.5 Binders ..................................... . 6-38
(i·3.5.G Partiele Size ................................. . 6-39
(i·3.G.7 Consolidation ................................ . 6-41
(i-:l.5.8 F'larp Diamrtrr ............................ , .. 6,43
(i·:3.5.9 Case Materials and Coating ................... . 6-43
(i.:l.idO Temperature anci Pressure .................... . 6-45
6·:3,;;.11 Rotational Spin .............................. . 6-47
ti·:~.G.12 Moisture and Stability ....................... . 6-49
(j·4 ~()neollsolidatcd IlI11Illillant Charge~ ., ................. . 6-52
(i·4.1 Aerial Photo~raphie llhlluil\ants . , ................. . 6-53
1i.4.1.1 Photoflash Cllrtridgf:'s , .... , .. , , ............... . 6-54
(i·-4.1.2 Photoflash Bombs ............................ . 6-54
ti·4.1.;~ Othf'i' Photogrl'phie Illuminallt Systems ........ . 6-54
(i·4.2 Spotting Charges ........................ , ... , .... . 6-55
li·4.2.1 Small Arm Spotting Rounds .................. . 6-55
ti·4.2.:'. Trclcking ' .. , ................ , ............... . 6-55
li··L.? :s Indieation of ~'undioning ..... , ......... ' ..... . 6·58
li--l.3 Typical Compositions ., ........................... . 6-56
ti·-lA Li~ht Production ................ , ...... , .. ,.' ... . 6-56
(i--I·U Light Output ('haraett'risties ................ ,. 6·57
Ij .. u.~.l TiIllt' Intt'llsity ., ............. ,' .......... . 5-57
Ii 1.4.1.2 Spt...·traI Distribution .... ".,., ... ,. , .. ,., 6-58
li··l.4.2 ~!ltllrt· of tht' Phototh!.sh Burst .... " ....... ,.,. 6·58
(j··4.f) }I'act{)rs Affecting Perfor!llancr ...... ' ............. . 6-61
f ·4.5.1 Charge Wt·igh: ........ '., .. , .. " ........... . 6·61
h-4.5.2 Composition 6-62

VIII
AlfCP 736·185

TABLE OF CONTENT~ (cont'd)


Paragraph Page
6-4.5.3 Particle Size ..... , .......................... . 6-64
6-4.5.4 Cloud Shape .......... . .................... . 6-65
6-,t5.5 Bursters and Igniters ......................... . 6-66
6-4.5.6 Confinement ................................. . 6-67
6-4.5.7 Ambient Pressure ............................ . 6-69
REFERENCES ..................................... . 6-70

CHAPTER 7
PRODUCTION 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 Clouds ................... . 7-5
7-2.1.1 Optical Properties of Particulate Clouds ., ...... . 7-7
7-2.1.2 Properties of Particulate Clouds Affecting Their
Stability .................................. . 7-7
7-2.1.2.1 Motion of Smoke Particles ................ . 7-7
7-2.1.2.1.1 Sedimentation ....................... . 7-7
7-2.1.2.1.2 Diffusion .. '" ..................... '" 7-8
7-2.1.2.2 Evaporat.ion Hnd Condensation ............ . 7-8
7-2.1.2.3 Coagulation and Agglomeration ........... . 7-8
7-2.2 Travel and Persistence of Particulate Clouds ........ . 7-P
7-2.2.1 Meteorological Factors ........................ . 7.. 9
7-2.2.1.1 Wind Speed and Direction ................ . 7-9
7-2.2.1.2 Turbulence ............................. . 7-9
7-2.2.1.3 Thermal Gradient ....................... . 7-10
7-2.2.2 Stability of Aerosol Clouds Under Various
Meteorological Conditions ................... . 7-10
7-2.2.2.1 Stabh' Conditions ........................ . 7-10
7-2.2.2.2 Unstable Conditions ...................... . 7-11
'/-2.2.2.3 Estimation I)f Atmospheric Diffusion ....... . 7-11
7-2.3 Specific Properties of Militllry Smokes ............. . 7-12
7-2.:U Screening Smokes ............................ . 7-12
7-2.3.2 Signal Smokes .............. . ............... . 7-13
7 ·2.3.3 Tracking and Aequisition Smokes .............. . 7-13
7-2.3.4 Smokt' for Dissrmination of Agents ............. . 7-13
7-3 Dissemination Techniques ............................. . 7·14
7-3.1 Formation of t h· Dispt·rsed Phase .................. . 7-14.
7-3.1.1 Vapor Condt'llsatioll Processes ................. . 7-14

ix
AlICP 706-185

TABLE OF CONTENTS (cont'd)


Paragraph Page
7-~U.2 Dispersion Processes .......................... . 7·14
7-:3.1.3 Combined Processes .......................... . 7-15
7-3.2 Military Production of Smoke ..................... . 7-16
7-3.3 White Smokes .... . ............................. . 7-16
7 -3.3.1 Oil Sn10kc ................................... . 7·17
7-3.3.1.1 V~nturi Thermal Generators .............. . 7-17
7-:UU.1.1 Operation of Venturi Thermal Generators 7-17
7-3.3.1.1.2 F'uel Blocks ......................... . 7-18
7-:3.3.1.1.3 Typical V cntllri Tht'rmal Generators ... . 7-20
7 -:3.3.1.2 Other Methods for Producing Oil Smoke .... . 7-20
7 -~t3.2 Phosphorus Smokes .......................... . 7-~1
7-3.3.2.1 White Phosphorus ........................ . 7-21
7 ;).:3.2.2 Burnin~- Typ<' Mixtures Containing Red
Phosphorus ............................ . 7-22
7·8.3.'?'.:~ Metal Phosphide" ........................ . 7-22
7-:t:3.2.4 Other Rl'Rctions for Producing Smokes
Containing' Phosphorus ................. . 7-22
7-:1.3.2.5 'fypical DeVll'CS .......................... . 7-23
7-:3.3.:1 Metal Chlorid(' Smokes ............... . ...... . 7-23
7-:UUJ Litiuid Metal t 'hlilridef' ................... . 7-23
7-:U.3.1.1 }1'M Smokes ......................... . 7·23
7-:!.:U.l.2 Silicon Tetrachloride ................. . 7-24
7·:l.3.3.1.:l Stannie Chloride ..................... . 7-25
7·:J.:3.3.2 Solid Metal Chlorides .................... . 7-25
7·:i.:U.2.1 He Smokes ......................... . 7-25
7 -:J.:1.a.2.2 Chemist ry of 11 (' Smoke Mixtnres ...... . 7·25
7·a.3.3.8 Modified II (' Smokes ..................... . 7-27
7·:I.:i.:t4 ZillC' Ill'xaehlorobenZl'llP·Potassium Perchlorate
Systelll ................................ . 7-27
7 -:!.:I.:1.fi Typical Devices .......................... . 7-28
7 ·:3.3.4 Sulfuri(' A('id Smokes ........................ . 7-28
7·:3.:U.1 Sulful' 'frioxiue ......................... . 7-29
'l-a.:H.2 (lleuln .................................. . 7-29
7·a.a.4.:~ ('hlorosuifonit' Acid ...................... . 7-29
7 -:1.:1.4.4 Sulfuryl ('hloride ........................ . 7-30
7 ·:I.:l.4.fi }<'8 Smokt' " ............................. . 7·3C
7· :!.:I.fi SnlOkt'-Pr()dll('ill~ Rt'aetions Involving Ammonia
or A.lIin\'s ................................ . 7-30
7 ·:U. ;).1 AlIIlIlollimll alld Aillilll' Salts of Volatik Aeids 7-30
7·:l.:!.i>.2 :\1 t't al ('hlori(II'S HIlt! Ammonia " ...... . .. . 7-30
'/ ·:\:I.fi.2.1 llydrugl.·l. l ~hluridt' and Ammonia ..... . 7·30
7·:ta.;1.22 TitaniulIl Tt,trllt'hloridt' IIlllt Ammoniu 7-30
7·:U.fi.2.:\ ~.i1i(,ol1 Tl'trll('hloridl" A III llIon ill, aud
\\' IIlt'r ........................... . 7·31
Sulfur ('oltl}lollllds IIlld Amlll()nia .......... . 7-31
AJlCP 706-185

TABLE OF CONTENTS (cont'd)


Paragraph Page
7-3.3.5.31 ~ulfur Trioxidt' and Ammonia or Amines 7-31
7·3.3.5.3.2 Chlorosulfonic Add and Ammonia or
Amines ......................... _.. 7·31
7-3.3.5.3.3 Sulfuryl Chloride and Ammonia or Amines 7·31
7-3.3.6 Sl.lifllr Smokes ................................ 7-31
7-J.3.7 ()r~anic Metallie (~ompoullds .................. . 7·31
7-:1.3.8 Comparison of White Smokes .................. . 7·32
7-3.4 Colored Smokes .................................. . 7-33
7-3.4.1 Dyes ....................................... . 7·3S
7·:H.2 Fuels ....................................... . 7-39
7-:J.4.3 Oxidants .................................... . ,/-39
7-3.4.4 CooJin~ Agents .............................. . 7-40
7-3.4.5 Binders ..................................... . 7-40
7-:1.4.6 Evaluation of CoJorl'd Smokl's ................. . 7-40
7-:.lA.7 Sensitivity of ('olored Smoke Mixtures ......... . 7-40
7 -a. 4.8 'I'oxil'ity of l'olorpd ~lIIok(' Mixture ............ . 7-41
7-:t4.!l Typipal Dp"i('es .............................. . 7-41
7-;(4.10 nireet Volatilizatior. of Dye ................... , 7-41
7 ·:1.4.11 ('olorpd Hmokl' from Solution of Dyl's ........... . 7-43
7-:U.12 Black Smokt' ................................ . 7-44
7-:1.4.13 Explosive-TYf,(· ('olored Smokt' Bursts " ........ . 7-45
7-:!.4.13.1 Propl'llant Bursters ...................... . 7-46
,·:1.4.1:3.2 High Explosiw Bursters .................. . 7-46
7-a.4.14 Typh'al ~tixturl'S ............................ . 746
7-:U> Agent At'rosols .................................. . 7-46
RE}<~ERENCES ..................................... . 7-49

xi
AMCP 706·185

LIST OF ILLUSTRATIONS

Figur(1 No. T'itle Page


3-1 Compressibility !<'actors as a }<'ullction of Reduced Pressure ... . 3-3
:3-2 Cubic Lattices ... , ....................................... . 3-6
:J.:~ Effect of Tempt>raturp 011 Enthalpy (~hang,> for a Chemical
Hraction ................. , ............................. . 3-12
Enthalpy of Aluminum Oxidt' Vprslls 'femperaturr .... , ..... . 3-20
Euthalpy of Prodlld~ of l\1agl\(·silllll·Air Reaetion ........... . 3-21
Bnthalpy of PI·"t!lI<'1S of Magnesiulll·Sodium Nitrate }<'larp
(Rcaetion 1) ........................................... . 3-23
1~llthalpy of Products (If Mn!!'H'silllll.SotiiuIII Nit lte Flare
(Heaction 2) , .............. ,........... . ............ . 3-23
Enthalpy of IM·11 lrwt'IHlinry Mixture .................... ,' 3-26
:I.!I 'I'11t' Rf'b~iollship BetwC{'1J Hf'lIt of Heaetion Ilnd Heat of
Activation ................................. , ........... . 3-26
:I·lO Ignition Tirnp·T"lllpt'ratm',· Plots for 1\ Binary Pyrott'.~ilIlic
Mixtllr(' ... " ........................................... . 3-':'8
:1·11 Model for BI!millg' of Aluminum Pal·tiel!'s .................. . 3-29
Mod!'l for Stt'lldy ~tat(' Pr()~n'ssivp Burrlin~ , .... , ........... . 3·30
:1·1:! Difff'rt'ntial 'l'!wrrnlll Analysis T1H>rlllocouph~ (~ircuit ... . ..... . 3·31
3·14.1 Thermogravimetric Curw for the Ingredient Sodium Nitrate ... . 3-32
:!. l·l.~ TIH'rmogravilllt'tri(' ell rw fOI' t Ii" lngr!'Clit'nt Magnesium ...... . 3·32
:1·1·1.:1 Th,'rlllo~ra\'i!lll'tric (~llrVI' for t hI' ln~rl'di!'llt TJIlmilllle 4116 .... . 3-32
:I·li'i.l Diffrrt'ntilll TllPrllllll Allulysis (~lIr\'(' for th(, Ingor(·client Sodium
Nitrate ., .. , .. ' .. ' ................................. ' .... . 3·33
:1·1 fi.~ Di/f('rPlltia I Tlh'rlllal Analysis (~urvf' for thl' IlIgrt'd iPllt Magnesium 3-33
:1·1 fi.;{ Ditf!'rt'lltial 'l'hl'rlllul AlIIllysis ('lIrve for tlit' J.ngredient i..lllminac
J 116 ....... , .. , .. ' ..................... ,., .............. . 3·33
:l·16.1 Differential Tlwrmlll Analysis Curve for tht~ Magnesium-Sodium
'Jitratr Mixturf' (Curvp I) .. _ .. .. .. . .. .. . .. .. .. . .. .. .. . ... 3·34
:1· 1(j.~ Diifert'lltiul Tlll'rlllal Anal~'sis CllrV!' for til!' Sodium Nitrate·
Carbon Mixturt' ................... ,...................... 3·34
:1· Hi.:l Di/f('rf'lltial ThprlllHI AUuIYHi!l Curv(· for tIw Magu(,Hium·Sodillm
Nitrat .. Mixture (( 'Ilr\'!' II) ............................... 3·34
:1·lfi.4 I>i/f('rpntial TIIt'rn:al Anlllysis ('lIrV!' for tiw Rodium Nitrate·
TJIHninup ;\1 ixturl' .', .. , ...... ',.,. . .. , .............. ,.... 3-34
:1· Hi.;) Ditr,'rf'ntiai Thf'I'lIIul. Analysis ('"rve for' Hit' Magnt~sillIll.IJllmin8c
Mixturp ... , ...... ,., .. , ..... , ... , ..... ,................. 3·35
:1·17.1 l>itf"I'f'ntiul T!lt'rlllul Alllllysis ('II!'Vf' for thp MIl~l!esium·Sudium
Nitrutt,·Carboll ('ollipositi,," .. , .... , ....... " ......... ,.,.. :1·35
:1·17.'2 j)itrf'rf'lItial 'l'llI'r 111 II 1 Anlllysis ('111'\'1' for tht' MagneHiulll·SodiuID
Nitrlltp·J ,lIll1ill;(I' ('ompositiull 3·35

xii
AMCP 7()6..185

LIST OF ILLUSTRATIONS (cont'd)


Fi.gu.re No. Title Page
4-1 Thresholds of Brightnes.3-CNltrast for 80% Detectiou for Five
Angular Fields (Minutes of Arc) ......................... . 4-2
4-2 Apparent Contrast as a F'unction of Distance ................. . 4-2
4-3 Optical Slant Range Dift.gram for the Optical Standard Atmosphere 4-5
4-4 Brightness Requirement::; as a Fun oJion of Acuity and Contrast 4-6
4-5 Effect of Direction of Illuminati:m on the Luminance of II.
Smoke Column .......................................... . 4-9
4-6 Effect of Relative Direction of Sun and Smoke on Time of
Discovery ............................................... . 4-9
4-7 Visibility Nomograph ...................................... . 4-12
4-8 Visibility Nomograpt for Signal Lights ...................... . 4-14
4-9 Visibility Nomograph Showing Calculation .................. . 4-16
4-10 Visibility Nomograph for Signal Light!l Showing Calculation ... . 4-17
5-1 Constant Ignition Probability Regions About a Fuel Jet of
Gasoline or Kerosene .................................... . 5-14
5-2 Maximum Temp')rature, T, as a Function of Heat of Reaction and
.Average Specific Heat, C ................................. . 5-16
5-3 Cooling Time to 800 0 K as a Function of Temperature and H~at
Capacity, C ............................................ . 5-16
5-4 Cooliug Time to 800 0 K as a Function of Heat of Reaction and
Specific Heat, C ., ....................................... . 5-17
5-5 Ti..ne-Temperature Histories for IM-H, IM-23, and IM-I03 ..... . 5-18
5-6 Cooling Curves for Mixtures Containing Various Particle Sizes
and Shapes of Magnesium-Aluminum 50/50 Alloy ........... . 5-19
5-7 Typi.cal Caliber .50 Incendiary Bullet ....................... . 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 Ty pical 20 rum High Explosive Ir.cendia:ry Projectile ........ . 5-24
5-11 Four-Pound Magnesium Alloy Incendiary Bomb .............. . 5-23
5-12 Four-Pound Thermite Incendiary Bomb .............. < ••••••• 5-30
5-13 Typical Napalm Bomb .................................... . 5-31
5-14 Typi('al Incendiary Grenade ............................... . 5-32
5-15 Obturated De~ay Element .................................. . 5-32
5-16 Sealing of Vented Delay Element ........................... . 5-33
5-17 1'ime Delay Ring or Train, Vented ............ '" ........... . 5-38
5-18 Total Heat Evolved Vcrsus Burning Time of Binary Barium
Chromate-Bor,)n Compositions Loaded to a Height of 0.79 Inch in
M112 !<~uze Housing at 36,000 psi .......................... . 5-38
5·19 Burning Time of Ml1~ !<'uze Versus External Pressnre ....... . 5-39
5-20 Burning Time of M112 Fuze Uontair,ing 90% Barium Chromate-
10% Boron UompositiuIl Versus Logarithm of Absolute
Temperature , ........................................... . 5-43
6-1 Emission Spectrum and Energy Levels of Hydrogen Atom ..... . 6·10
6-2 Various Types of Spectra and Corresponding Electronic,
Vibrational and Iwtational Motion ............ < •••••••••••• 6-11

xiii
AMCP 706-185

LIST OF ILLUSTRATIONS (cont'd)


Figu'l'o No. Title Page
6-3 Planck's Law: Radiance as a Function of Wavelength for Va.rious
Temperatures ............................................ 6·12
6-4 Uadiant Energy in Different. Wavelcngth Band:o; as a Function
of Temperature ... ,...................................... 6·12
6·5 Isothennal Efficiencies: ,F!'aetion of Energy Emitted by an
Isothermal Radiator in Various Wavelength Bands as a Function
of T'JID,peraturc ........... , ............................ ". 6·13
6-6 " Optical" Temperatures of a Tungsten Filament ............. 6-13
6-7 Dimensions of the Psychological Color Solid .................. 6·18
6-8 Additive Mixture of Primary Colors ......................... 6-18
6-9 Tristimulus Values of the Spectrum Colors According to the
1931 I.C.I. Standard Observer ............................. 6-19
6-10 C.I.E. Chromaticity Diagram ............................... 6-19
6-11 Illumination Diagram for Parachute Suspended Flare ........ 6-23
6.12 Intensity Curves for Various Pa~achute Flare Heights ......... 6·24
6-13 Typical Aircraft Parachute Flare ........................... 6-25
6-14 Operation of Typical Aireraft Parachute Flare ............... 6-26
6-15 Typical Aircraft Tow Target Flare .......................... 1)·27
6·16 Typical Surface 'l'rip Flare ................. ............... 6·31
6-17 Typical Hand-Hcld Illuminating Signal ...................... 6-32
6-18 Small Arms Tracer .................. ...................... 6-32
6-19 Armor-Piercing Tracer ................ ,.................... 6-33
6·20 Artillery Tracer Element in Projectile ........................ 6-34
6·21 Artillery Tracer ................... ,....................... 6-35
6·22 Zones in Flame Propagation ............ ................... 6..39
6-23 Temperature Distribution in a Pyrotechnic Flame ............ 6-40
{:·24 Luminous Intensity as a }1'unction of Magnesium Content of
Binary Mixtures Containing Various Oxidizing Agents . .... 6-41
0-25 Burning Rate as a Function of Magnesium Content of Binary
Mixtu:,cs Containing Various Oxidizing Agents ............. 6-42
6·26 Chromaticity De.ta for Red, Yel!ow, and Green Flares ......... 6-44
6-27 Typical Spectra of Signal Flares ............................ 6-45
6-28 Spectral Energy Distribution of Green Flare ................. 6-48
6-29 Magnesium Content Versus Excitation Purity for a Yallow Flare 6-49
6-30 Effect of Polyvinylchloridc on the Candlepower of Mixtures
Containing Strontium Nitrate and Ground Mab'llesium, Grade.A. 6-49
6-31 Effect of Polyvinylchlorid\~ on the Color Value of Mixtures
Containing Strontium Nitrate and Ground Magnesium, Grade A. 6·50
6-32.1 Burning Rate vs Particle Size of Magnesium ................. 6-52
6-32.2 Candlepower vs Particle Size of Magnesium .......... '........ 6-52
6-33 Effect of Loading Pressure on Burning Rate of Pyrotechnic
Compositions ................. ,.......................... (j-53
6-34 Effect of Spin TJ pon Tracc Duration of Various Standard Tracer
Compositions When Loaded into Calibl'r .50 M1 .racket ...... 6-53
6-35 Diagram of Bomb Burst alld Trail Angle ..... , . . . . . . . . . . . . . . .. f)-6~
6-36 Typical Characteristics of Black and Whitc Negative Material ... 6·56

xh
AKCP 706-185

LIST OF ILLUSTRATIONS (eont'd)


F'igU,f'6 No. Title Pat(J8
6-37 Typical Photoflash Cartridge .. , .......... ' ................ . 6-58
6-38 Typical Photoflash Bomb .................................. . 6·61
6-39 'fypical 20 mm Spotting Round .................. , .......... . 6-63
6-40 Photoflash' , Daisy" Cartridge ............ , ................. . 6-63
6-41 Typical Flash Charge for" Indicathn of Functioning" ........ . 6-65
6-42 Typical 'rime-Intensity Curve ..... " ........................ . 6-6tl
6-43 Synchronization of Shutter .............................. " 6-67
6-44 Time-Intensity Curves for M120A1 Flash Powder and M':'22 Dust
Phototlash Bombs ....................................... . 6-67
6-45 Spectral Energy Distribution Curve of !l1120 Photoflash Bomb .. . 6·138
6-46 Effect of Particle Size of Potassium Perchlorate 011 Luminous
Efficiency of 60/40 Pota!!;sium Perchlorate-Aluminum
Compositions .. " ........................................ . 6-68
6-47 Size and Light Output of .Flash Cloud vs Time .. , ............ . 6-68
7-1 Approximat{' Size Range of Airborne Particles ............... . 7-5
7-2 Scattering by Sphericai Pa..·ticles With Indicated Refractive
Indexes ................................ , ..... '" ........ . 7-6
7-3 Typical Venturi Thermal Generator ......................... . 7-18
7-4 Typical Oil Smoke Pot (Floating) ......................... . 7-20
7-5 Typical Oil Smoke Pot (Training) .......................... . 7-20
7-6 Typical WP-Filled Device (M15 WP Smoke Haud Grenade) ... . 7-22
7-7 Typical Red PhoEphorus-Filled Device ...................... . 7-23
7-8 AN-M8 HC Smoke Hand Grenade .......................... . 7·28
7-9 M5 HC Floating Smoke Pot ............................... . 7-28
7-10 Differential 'rhermal Analysis and Thermogravimetric Analysis
Curve for 1,8-dihydroxyanthruquinone .................... . 7-36
7-11 Differential Thermal Analysis and Thermogravimetric Analysis
Curve for 1,4-di-p-tolnidinoanthraquinone ................. . 7-35
7-12 105 mm M84 Colored Smoke Projectile ...................... . 7-41
7 -13 MIS Colored. Smoke Hand Grenade ......................... . 7-43
7.14 4.2-in. Colored Marker Projectile, Colored Smoke, E75 ........ . 7-44
7-15 105 mm lvIl Colored Marker Projectile ...................... . 7-45

xv
AMCP 706-185

LIST OF TABLES

Table No. Title Page


2-1 Tabulation of Pyrotechnic Devices .......................... . 2-2
2-2 Comparison of Some :?:operties of Pyrotechnic Compositions
With Explosives ....................... , ................. , 2--5
3-1 Criteria of Spontanelty .................................•... 3·11
3-2 Thermodynamic Proper-ties of Solid Magnesium Oxide ......... . 3·14
3-a Thermodynamic Properties of Solid .Aluminum Oxide .......... . 3-15
3-4 Thermodynamic Properties of Solid Sodium Oxide ............ . 3-16
3-5 Thermodynamic Properties of Liquid Sodium Oxide ........... . 3-17
3-6 Thermodynamic Properties of Oxygen ....................... . 3-18
3-7 Example of Thermochemical Calculations: 'Lanthanum-
Potassium Perchlorate Reaction .......................... . 3-24
3-8 Example of Thermochemical Calculations: Zirconium·Oxygen
R.eactiou ............................................... .
4-1 Meteorological Range for Typical Weather Conditions ......... .
4-2 Reflectance Values (in percent) of Various Terraia Features
and Building Materials ................................. . 4-7
4-3 Maximum Angular Size of Light Source as a Function of
.Adaptation Brightness ................................... . 4-10
44 Visibility of Flashing Light Uompared to Steady Light ....... . 4-11
4-5 .Absorption of Sunlight by Atmosphere ..................... . 4-11
4-6 Sky Brightness ............................................ . 4-13 '
4-7 Sky-Ground Ratio ......................................... . 4·13
4-8 Increase in Illumination R.equired for Positivc Recognition .... . 4-15
5-1 Heats Evolved from Reactions of .Aluminum and Various
Oxidizing .Agents ....................................... . 5-6
5-2 Oxygen Coutent of VariJus Nitrates ......................... . 5-7
5-3 Oxygen Content of Various Perchlorates ..................... . 5·8
5-4 Oxygen Content of Variuus Oxides and Peroxides .......... ,. 5·8
5·5 Hellt of Reaction of Reducing Agents With Barium Peroxide ... . 5·9
5-6 Summary of Limits of ~~lammability of Various Gaseu and Vapors
in .Air and in Oxygen ................................... . 5·12
5-7 Typical Small Arms Incendiary Mixtures .. " ............... . 5·20
5-8 Heat of Reaction of 'rhcrJlite-'l'ype Mixtures Copt.aining
MagntJsium .............................................. . 5·25
5-9 Modified Thermite Uolllpositions ............................. . 5-25
5-10 Heats of Combustion and Hydrog(·r•. Carb'lu Ratios of
Selected Fuels ., ....................................... . .:i-26
5-11 Compositioc of 1M-Type 1ncpndiar-y Gels ..................... . 5·27
5-12 Composition of PT Incendiary Mixtures .................... . 5-28
5-13 Gasless Delay Compositions in Current Use ................. . 5-34

xvi
A](CP 706-185

LIST OF TABLES (cont'd)


Table No. Title Page
5-14 Burn;ng Rates of Gasless DeldY Compo5itions ................ . 5-35
5-15 Heats of Reaction of Inurganic Mixtures Considered for Delays .. 5-36
5-16 Effect of Percent Composition un Burning 'l'ime, Heat of
Re~ction, and Impact Values of the Barium Chromate-Boron
System ................................................. . 5-37
5-17 Ii]xtent 01' Anticipatory Effect as a }4'unction of Burni.ng Rate of
Variom: Barium Chromate-Boron Compositions ............. . 5-38
5-18 Extent of Anticipatory Effect as a Function of Column Length of
55/35/10 Tungsten-nat'ium Chromate-Potassium
Chromate Composi.tion ................................... . 5-39
5-19 Effect of Specific Surface o~ Burning Time of Tungsten Delay
Compositions ............................................ . 5-40
5-20 Ignition Powders for Gasless Delay Elements ................. . 5-40
5-21 Effect of Fuze Housing Material and Dimensions on Burning Time
of Barium Chromate-Boron Compo!:itions ................... . 5-11
5-22 Effect of Loading Pressure on Barium Chromate-Boron
Compodtions ........................................... . 5-42
5-23 Effect of Storage on F'uzes I.;oaded With Barium Chromate-Boron
Compos;.tiontl ............................................ . 5-44
5-24 Burning Times of Fuzes Loaded With 93/7 Barium Chromate-
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-Anywhere") Match Composition ............. . 5-47
5-28 Friction Primer Compositions .............................. . 5-48
5-29 Some I<'irst Fire, Starter, and Igniter Compositions ........... . 5-49
6-1 Conversion Faetors for Photometric Units .................... . 6-17
6-2 Candlepower IWquirements Versus Height of Illuminating Source 6-21
6-:3 Characteristics of Various Illuminating Flares ............... . 6-22
0-4 (A) Characteristics of Various Aircratt Signal Flares ............. . 6-28
6·4 (B) Characteristics of Various Ground Signal Flares .............. . 6-30
6-5 'fypical Illuminating, Signaling, and Tracer Compositions ..... . 6-36
6-6 Heats of 1V:action of Aluminum With Stoichiometric Quantities
of Various Oxidants ..................................... . 6-37
6-7 Heats of Reaction of Magnesium With Stoichiometric Quantities
of Various Oxidants ............................ , ........ . 6-38
6-8 (A) Physical Data and Burning Characteristics for Stoichiometric
Mixtures of Various Oxidants With Atomized Magr.tJRium ..... 6-48
6-8 (B) Characteristics of Binary Mixtures Containing Oxidizing
.~geuts and Atomized Magnesium, Grade A ................. . 6-46
6-9 Charaderistics of Pyrotechll;c Compositions Containing
Various Polyester lksin Hinders .......................... . 6-47
6-10 Effect of Particl~ Size Oil Burr,ing Hate and Ctmdlepower for
Mag-llcsium-Sodlum Nitrate-Polyvinylchloride-I.;aminac Mixture 6-49
6·11 Effects of Chung(· in Speciti<~ Surface of Magnesium Particle.s ... 6-50

xvii
AMCP 706-185

LIST OF TABLES (cont'd)


Table No, 'Pitle Page
6-12 Effect of Loading Pressure on Burning Charactflristics of
Magnesium-Sodium Nitrate Flares .............. . ..... _. .. 6-50
6-13 Effect of Simulated Altitude and Temperature on Illumination
Characteristics of Ypllow Signals .................... ..... 6·51
6-14 Effect of Simulated Altitude and Temperature on Illuminat.ion
Characteristics of Red Signals ............................. 6-51
6-15 Effect of Simulated Altitude and Temperature on Illumination
Characteristill>; of Gi'een Signals ... ,....................... 6-52
6-10 Designation and Description of Photoflash Cartridges .......... 6-55
6-17 Characteristics of Type III Photoflash Compositivn ............ 6-57
6-18 Designations and Descriptions of Flash Powder Photoflash Bombs 6-59
6-19 Characteristics of Dust Photoflash Bombs ..................... 6·60
6-20 Segregated Oxidant Photoflash Bombs ....................... 6·61
6-21 Typical Compositions for Photoflash and Spotting Charges ...... 6·62
6-22 lJUminosity Characteristics at Sea Level of Photoflash
Compositions Consisting of High-Energy Fuels in Stoichiometric
and Fuel-Rich Combinations With Potassium Perchlorate 6·64
6·23 Thermodynamic Data for Stoichiometl'ic Mixtures of
oxidizing Agents and Atomized Aluminum .... , ... ,........ 6.65
6-24 Luminosity Velues of Various Oxidants With Atomized
Aluminum and Atomized MagneslUm Tested in M112 Photoflash
Cartridge ............................................... 6-66
6-25 High Explosives Tried As Bursters in Flash Bombs ........... 6-68
6-26 IJuminosity Characteristics of Photoflash Compositions
Consisting of High-Energy Fuels in Stoichiometric Combination
With Potassium Perchlorate .......................... _. . .. 6-69
7··1 Terminal Velocities and Diffusion Corfficients of Rigid Spheres
of Unit Density in Air at 760 mm Hg Pressurp and 20°C. . . .. 7-8
7-2 Characteristics of Typical Oil Smoke Pots .................... 7-19
7-3 Characteristics of 'rypical Devices Using Phosphorus :B'illing .... 7 -24
7-4 Variation of Burning Timr of Type-C He Smoke Mixture Witt
Alulninum Content ....................................... 7-26
7-5 Characteristics of Typical Devices Using He Mixture. . . . . . . . .. 7-29
7-6 Total Obscuring Power of White Smokes .................... 7-32
7-7 Amount of Smoke Agrllts RPljuired To Produce 1,000 Cubic Feet
of Standard Smokr ....................................... 7-32
7-8 Amount of Smokt' Produced Per Ifnit Weight of Smoke Agent
at 75% Relative Humidit:r ................................ 7-33
7-!J Some Dyes Which Havp Been lTsed in Burning-Type Colored
Smoke Muuitions ........................................ 7-34
't-10 Some Dyes Which Have Bet'll llsrd ill Explosive-Type t~olored
Smoke Munitions ........................................ 7-35
7-11 Charactpristies of Typical Ejectioll-'rypr (~()lored Smoke
Devic:.es .................................................. 7-42
7-12 Basic Differences Betwet'lJ till' ('olored Marker and Bllie-
Ejection Smoke Projeetii's for 105 mm GUll. . . . . . . . . . . . . . . .• 7-45
7-13 Typical Smoke Compositions ................................ 7·47

xviii
AMCP 706·185

CHAPTER 1

HISTORY OF MILITARY PYROTECHNICS

1·1 INTRODUCTION in Europe mentions the lWman 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 framework& were fitted with
oxidizing agellt and a ftwl that produce an exo- ad,iustable parts and desiglled to set in motion
thermic self-sustaining reaetion when heated to various colored lights.
igIlition temperature. Man's earliest pyrotechnic A military use of pyrotechnies that began early
devices may have been the result of an accidental and llersisted for many centuries was the use of
mixing of saltpeter (KNU 3 ) with charcoal; or fire shipg 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 arc: as incendiaries; as show that thl' U~eeks used them against the Turks,
luminoilS sourees for missile tracking j as aecl's- the Crusvdl'rs used them at Acre, and the English,
sories in aircraft, missiles, and .lUelear devices; 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
arc also used for photography.4 Recent adaptations 1-2.1 GREEK FIRE
include devices designed for actuation by radio
OIlr of the earliest and most successful means of
signals directrd to a missile thcusands of miles
ehemieal warfare was the mixture known as Greek
from rarth.
fire, the us~ of which is first reported in the 7th
cel,tury, A.D. This mixtcre of sulfUr, resin, cam-
1·2 EARLY HISTORY1.~,~,r..n.7
phor, and ('thl'r unknown combustible substances,
(l\eclldiary and colored smoke mixtures were melted with saltpeter, was a powerful incendiary
lIspd for war, religious edebratiolls, and entertain- that also produeed suffocating fumes. It was Ui~ed
lI1('nt in Arabia, ('hina, Egypt, Oreecl', and India in many different ways. Sometimes woolen cords
ill \'Pry <ll\ell'llt tillH's. As early as 2000 lU '., tales werl' soakrd in the mixture, dried, and rolled into
of war in [ndia mention int'elldiaries, smoke balls. The balls were thl'u lighted and hurled by
SI'I'l'enS, awl noxious fUmes. Later, al!'aillst Alex- large rngines at l'nem,Y ships or tents. Defenders of
alldl'r the Ureat (:Hj;1-;~2;l g, C,), dl'fpuders of an citirs preparl'd it in liquid form; poured it into
Indian eity wert' rt'portl'd ablt' to •. shoot thunder jars; thl'll ignited til(' Iflixture and poured it upon
aBd Jig-htlling from tlit' walls. " 'l'o this day, natural those besirging t hf' city walls. III open battles,
deposits of saitpt'ter arr abundant in Illdia, and it wa.<; squirted by hand pumps and bl'ilows through
Ilrobabl.\' sel','t'd as a soure,' of this Illatt' rial for pipes into enf'my ranks, or against wooden barri-
t'llIpIOYIlll'lIt in tit!' "olllpositioIlS making- these dis- ('adrs. In 901 A.D. thp Raraerlll; wprr reported to
plllYs possiblt,. haw blow/l it from pipes lllolllltrd on HIP derks of
Knowlt·t!g-t· of JlYl'ott't·hlli{·s trll\,p\toll frolll the tht'ir ships. P;w t'Plltllril's lut!'r, in Emperor Ij('o's
East ttl EUl'opt> at tilt' 1Jt'~illllillg' of tht' Christiuli attal'k 011 t 'ollstuntilloph' in H5:J A.D., 2000 ellPlI1Y
PI'a Tht' parlit'st rl'l'ord of pyrotl't'hllit' l'xhibitions ships wert· I'!'purtl'd til'stroYl'd by its ust'.

1-1
AMCP 706·185

1·2.2 CHINESE PYROTECHNICS the use of I'ontaet or short raHge incend.iary de-
Recorus of Chinese pyrotechnic items go back vices.
to the 10th century. Rockets and Roman candles
are mentioned in 969 A.D. and, by the 13th cen- 1-2.4 MISCELLANEOUS USES
tury, colored smokes for signaling, incendiary-
The first r('corded use of sCi'eening smoke in
carrying firc arrows, and rocket-propelled arrows
more reeent times occurred in 1701, when Charles
were employed, The roci,et-propelled arrows, fired
in clusters from metal containers, were sometimes
xn f)f Sweden bUl'lled damp straw to produce a
smoke screen to cover a river crossing. Elsewhere
ritted with poisoned razor-sharp heads for attacks
ill Europe at this time pyrotechnic devices were
from ambush and the defense of defiles. Other
being developpd for their military value. The
('hinese weapons of this time included •. flying fire
J.'rench kings encouraged experiments and tests,
spears" equipped witt, tubes that thrt'w fire for-
saw that proper records were kept, of which many
ward for about ;;0 feet. Pyrotechllie devices were
are still available, and colle(~t('d information from
also used. in ,iefpuding eities-·thp Kin Tarters travelers returning from other countries. French
are known to havp used fire powders and other pri('sts retul'lling from China brought detailed
pyrotechniC' devi('es against a Mongol attack in knowleclgp of the state of the art in that country.9
12;j2 A.D.

1·3 18TH AND 19TH CENTURIES:!,:i,5,6


1·2.3 GUNPOWDER
Berthollet's discovcry of potassium chlorate in
Till' im'pntor of gunpowder is gpnerally be-
1788 began the modern erll in pyrotechnics. Po-
lit'ved to haw been the English philosopher, Friar
tassium ch\orute made color effects in pyrotechnic
Roger Bacon. In 1242 A.D. hp t'ewaled the ill-
fiames possible and the introduction of magnesium
gTl'llieuts for black powder in deff'llding himself
in 1865 and aiumiLulll in 1894 added greatly to the
against an accusation of witchcraft. Although
variety of effects attainable.
Bacoll knt'w of th!' explosive power of gunpowder,
In Em'ope there was also a great interest in
he apparently did not recognize the possibility of the use of rockets. ~evpral types were developed,
IIsing it for projection of missiles.
the most sUccpssful being the Congreve rocket,
The earliest reeorded use of firearms or of gun-
whieh was ao illl,hes lor.g, 3% inches in diameter,
[Jo\\der as a proppllaut is in the beginning of th(' and carried an incendiary eharge. 'Hie British
14th ('Putury. Itt'cords of thr Univprsity of Ghent llsed rock(,ts with pyrotpeimi(' compositions in a
ill Bt'lgiulIl indicate that the first gun was invented Humher of l'ampaiglls. A rocket corps was part
by Berthold ~I'hwarz il; 1:113, and 1'0mnWrcillJ of ~hp British Army during the Revolutionary War.
reeords illdil'ate that gun~ and powdpr were ex- u!ld again during the Wllr of 1812. 'l'he 1805 ex-
pOI·ted front Ghpllt to England ill thl' following p('(litioH of Sir ~i:llley Smith against Boulogne
year. (iuns alld gunpowdt>r may havl:' been used included boats fitted for salvo firing of rockets, and
ill t he English invasion ,)f Scotland in 1:127, but ro('kets were used sucl't'ssfully in the British attack
thl' l'arlit'st undisJluted record of the use of g'un- 011 Copf'llhagf'n and by V/('llillgtoll'S army.
powdt'r ill war is ill Fralll'P at tht' battle of Crecy In the United States at this time, a number of
ill 1:l-!6. (lunpowdl'r was also used as an l'xplosiv(' pyrotechnic devices wer(' items of genertll am-
to blast fortifil'atioll walls, thl' first rpported at· munition issue,. An 1849 Ordnance manual de·
tempts beillg at Pis'! in HO;j, and in land mines, scribes signals, lights, torches, tarred Jinks, pitched
,
whieh werl' dl'sl'rib"d ill 1405.
'Vhl'n g'lInpowdpr bpg!lll to bl' used a.~ a pro-
fascines, incendiary matehes, and ot)}er illumina-
tion devic{·s. 1'he mllnnsl also lists firestone,
ppllallt ill thl' 14th to 15th l'entllr)" tht' usefllirll'SS Valencielllll's "ompositioll, and firebails-incendi-
of tht' iW't'lllliaril's thl'll available deL'lillpd. Ht" aril's, WitI'll pro,ll't'lpd from mortars, designed to
('/',IISP of tilt' liSt' of gllllpowdl'r, armil's hl'gllll to Bl't fire to ellemy property. Bl'sides the Congreve
/'IIi!lIgt' t'!l(,h uthd' at stich t1istalll'(,s as to prohibit l'<ll'k,·t, whil'h calliI' itl 2 1/i' and 3'i4-inch sizes. The

1-2
AltICP 706·185

2%,-inch rocket bad a maximum range of 1760 screens with sucr:ess at the Battle of Jutland in
yards Itnd the 314-inch rocket had a somewhat 1916. As a r?sult of this success, the AllieD and
greater range. The rockets wel.·e made of sheet or the Germans dev('loped pyrotechnic screening smoke
cast iron and fired from tubes muunted on portable for nse on both Jand and see, during World War I.
stands or light. carriages. An 18t'1 Ordnance
manual lists most of the 1849 devices with more
1-4.1 WORLD WAR I
detail and some improvements. Two new items
During W orId War 1, opposing troops in
were also listed: an iucendiary projectile filling
trenches sepallted by short distances r('gularly
called rockfire, which burned s!owly and. was hard
employed pyrotechnic devi~es. Illuminating pro-
to extinguish. It was employed to set fire to build-
jectiles w?re USN! as protf(!tion 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 ,,'ooden box
stop artillery firo,; 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 numbl'r of guupowder improvement" were
The advent of the airplane overcame the diffi-
:nade in the U llited Stutes and Europe during the
culties of m~iug incendiaries against distant armies,
latter half of the 19th century. After General
I<'orerunners of to,lay's incen.diary bombs were
Thomas .J. Uodman, U.S. Army, disco,'ered the
first dropped on {,ondon in May 1915 from Ger-
principle of the progressive imrning of propellant
man Zeppelins, and 8 prototype of the portable
powder in 1860, powder grains were made in sizes
flamethrower was used by the Germans :l.gainst the
adapted t.o the caliber of gun, with larger and
French in April and June of that year, although
perforated grains used in larger weapons, The
with Iittlc success. l,ater in the war, bombs con-
Swedish inventor, ~obel, made many of his im-
taining white phosphorns, thermite, and thickened
portant discoveries at this time. In 1863 he first
liquid fupls were dropped from airplanes.
manufaeiured nitroglycerin commercially, and dur-
Before and during World War I most pyro-
ing the next twenty years invented dynamite, the
techul.c development and manufacturing in the
fulminatr hlasting eap, blasting gelatin, gelatin
United States was carried out by private contrac-
dynamite, and ballistite. Another improvement
tors to the AMny or Navy. The Star rifle light, the
eaml' in IH8(j whrll Vieille, It French chemist, dis-
\' ery pistol, position lights, and simple rvckets
('overed the means to colloid nitrocellulose and thus
were the main items used. As the war continued,
control the grain sizr of the propellant powder,
the armed services began to test and develop pyro-
technic devices for special purposes.
1-4 EARLY 20TH CENTURY :!.a.~.tl:l.k,O.10 'l'he me of chemical ul5ents during the war rr-
An illtportant pyrotechnic development early suited ill the <.>stablishment of a Chemical Warfare
in this century wus the tracer bullet. 'fraccl'S have Serviee iii HIl8, This organization b<lcame a
bl'en used ill hll types of projer.tiles, but their de- permaul'nt branch of the lJ .S. Army in 19?O,
wlupment has bel'll most desely connected with and in 1946 its Ilame was (·hanged to the U.S. A:rmy
IIlIIlllunition for !lutomati(' slllall arms. Tracers Chl'I:~ieal Corps. This technical service pursued
w('rt' the Ill'st [\t'vil't's for directing automatic small thl' dl'vf'lopmPJl, of im'l'IHliaries, scrl'l'lling and gig-
arms fire again::;t f:lst moving ground t!l.l'gets. In IIltliug Sll1okt·s. fiame throwers, and t{)X~i) eheroical
this l'oulltry, J"t'sl'a "['h and devt>lopment of small l'ompoillldN.
anJlS tral't'I'S was ['aITied out a+ }<'rtmkford Arsenal. Alwrdef'1l Proving UroUlHl in Maryland was
'fhl' U. S. Xav)' and Pil'atiIlIIY Arsenal also COIl- al'tivutt·tl in Octob,'r 1917, liud by I'l'cember of
lludt'd tral't'r dpVt'lopIlH'nt for :>.0 lIUl!, 40 mm, ap.d that yt'rll" was making Il('eept'llll'{' test.s of ammuni-
largt'r gUllS. tioll alld othl'r Ordnllllel' lIlatt'I'iel Abl'rdel'n rec-
The tlt'rllIlill Na,y l':'llllu('tl'd tlet't IlIIUH'UVt'rs ()!"t!s for l!nH liNt tests of illnminating paraeput!'
l1Sill!! dWlIlil'ally prodlll'l'd Sl'f{'Plling sllloke for tht' projl'l'tiit's for tht' 1!i;)lf!1I1 gun.
tirst till\\, ill l~HHi, alit! later Ilill'd slIe' smoke l<'rallkford ~\rs(,llul, l;uring the e1\rly days of

1-3
AMCP 706-185

the war, adapted foreign pYI'oteehni(, t'ompoilitiolls bPdl littl" scientific trsting \Jf pyrotechnic de-
to small arms ammunitioll, I.Jatm', it deve10ped vit,l's, th(' botly of data that l'xisted at Picatinny
traeer and igniter eompositiolls and started a well- ArsPlIal at the out;Jfl'ak of y.,rW JI was of COll-
illtegratrd program for standardization. 'l'hese !';itiPl'ahlp valllP in developing improved pyro-
early tracer compositions W(,1'1' madr by a s:llall tl't'hnie itt'TllS llrpdcd for the hig-hly mobile forces
batl'h proeess, Wl't mixed, dried, and ground to of that war.
produl'e a stablp, uniform eompositioll. These early Aberdeen Proving Ground added development
('om positions Wl're only Illocieratply :o;atisfactory in tl'sting to its proof testing in the 1920 's, In 1921
that thl' ralonlPl used as a flam!' brightl'n!'[' pro- development test.<; werl' reported on green, yellow,
ducN] >:l'ason {'racking' ill bras.;, and also limited and white s\l1okes, and two years later trsts of long
thp life of the composition. burning white parachute signals were conducted.
During thr war til(' ~av:.. dcwloprd and used Abollt 19:33, Frankford Arsenal refined the
:3-, 4-, 5-, and 6-ineh illnmillati!l~ pro.it'etiles with proct'ss of making tracer eompm,itio[)s so that only
a projection rang{' up to 7 miles, a major a<ivantll.ge tilt' ('aleillm resillate hJII.! the hygroscopic strontium
bel'ilnst> thp Ntar rifle light \\as projeett'd to a maxi- pproxide wprp wpt mixpd, Hin('{' then, streamlining
mum range of only SOD yards, Thc ~avy also de- of th<; proprss has eontinu('d and nOw all ingredi-
wloped watf'r marker!' for lISl' from submarines, as puts in the trae('r mix arp purchased in the required
well as for dropping from aircraft, These markers granl[latioll, bl~lldptl dry, and charged into bUllet
l'onsisted of 'lurfacp burning- smoke and flame-pro- ('avitips Ilnder high preSSllI'eS, In 1936 Frankford
{hwing itrms, l'olored aerial star~, and :mrfacr bpgan developing drlay action and dim igniters,
marking dyes. some of whieh are now standard compositions. Just
bp1'ol'p the United Statl's entered 'World Wal" n,
I:<'rankford gol'{'atly improved incrndiary mixture
1-4.2 BETWEEN THE WARS
bU-l1. This standard illcl'ndillry Jllixturl', which
-:Juring the period between World War I WIIS originally de\'('!opt>d by Picatinny Arsenal,
and World 'Val' II, arsellals, such as Picatiuny wall quickly adoptpd by the British and was used
and Frankford, HUrl t 11(> Army Chemical ('orps hy Allwrican fO!'t'PS ill all small arIns incendiary
(~arried Oil limited resl'ar('h on military ilpplieatioll~
blllh·ts tIming World War II.
of pyrolr,'hlli('"l, l'j')[lle llliiwl'sities also af>sisted 1'1)(' Navy pyrotl'l'hnie tiewloplIlt."nt between the
i II this work. wars was ('('ntered at till' U.S. Navy Yard in
PichtinllY Arseual, which had been established \YashingtoIJ, D. (', Productioll was l'arried out at
hy tllP OrtiIlIlIlC,' Corps i[1 1879 as a snnll powder tl1l' :\"<[\'al OrdnClnct' Plaut at Baldwin, ~ew York.
d<'J)Ot to mallufadur" awl load lIlunitions, begall }·'or Ii tim!' its ontO produei W/IS illuminating pro-
loading' propl'lIallt ('harA'('s il! IH!lti, projl'l'till's ill .it,(,till·s, bllt ill 1n:W prodlldion of aircraft para·
1902, HIl(1 prop,'!Iallt mallllf'al'tlll'p in 1907. III l'llllt!· tlart's was also addpd. A Iso, by 19:3:{ thr
1!11 !l, it begall to dt'vt'lop and mal!ufadur(' pyro- l~xpt'rillH'lllal .\m!llllllitio[) Unit of tht' Naval (i1111
h'(,hllil' sig'lIllls, and <'Olltilllled tIl!' pyrot<,('hlli(~ Par'tory had d(·\'t,lopp(} a IIl1mbpr of PYl'ot('ehni{'
['(';;par('h allt! dl,\, .. loPIIH'llt !'frol't ill I hI' period hl'-
it ('Ills i [It' Ilid i Ilg' ('ll1prg('[I(''v idt'll tificil t iOIl signals,
t\\'('1'1I tIl(' lI'a:·s. lJuriHg' this tilll(" it mud(' ('011- II i r''I'aft signa I ('art ridr~('s, alld am [[Ill IIi t iOIl t ra(·l·rs.
sidt'rablp pr'og['PSS ill d(,\,l'lopill~~ I1t'W Slllok(', flllr!',
trw'l'[', lilld d,·la,v ('omposit iOllS, and begall to lil'-
('lIl1lllllltl' ('\'idl'l1l'(' rt'g'ardillg' lIlt' llt'l'('ssit,v for 1-4,3 WORLD WAR II
PIII't'[' ilJg'rt'tiit'llts, IIIOI't· /',1 "t'flll ('olltrol of plI[,tiel!' I II 1940, alld latt·t' with thl' (,Iltl',\' of th., 1:nitt'ri
"iZt', IIlId iIllPI'OI't't! pl'nt'!';;sillg' 11I<'!lwds. (lthl'!' il!- Ntalt's iJlt(; World \Var II, pyrotl'l'hlli(' itl'llls such
\·t'st igat lOllS pl'Od IIt'l'd t('('1t II iq lIt'S to 1IleaSHr.. lll- as fllll't·S, illuminating' projt't,tilt's, s/llOkt, sl~llals,
Illillosit,\' alld t'olo[' of PYl'ot"t'hIJi(' flall1l's, [t'('/lllil'al spott i JIg' ('}lIIl'g('S, IIlUIl,\' t,\'lw;; of ground aIHI air-
l't'qUil'l'/Il"llts for spt,,·ifyi/W illf!rt'dit'uts, '1I1t! r"('og'- t'raft Sig'IIHls, lind in('t'[Hiiarir;,; were needed in
Hitiou til' tht' ilJlpn[ ta/ltT Ill' I\\'nidi[lg !lIoistllrt' ill .'Il"!'IIlOIlS '1lllllltiti!'s
pyrot""/tui(' ('ollJpositilJlI"i. ,\ ItliolJg'h tllt·!'t, Jiad Plar!'s w('rt' wid(']), wwd to illuminutl' landing

1-4
- - - ---------------------------- ------------------------ ----- - --- - - -

AMCP 706-185

fields at night, in rain, and ill fog. They were tracers, amI troop warning dt'vic('s wpre de\'eloprd
dropped from aircraft to illuminate enemy terri- to m~t't th£' Ilt'W tactieal requirements. New in-
tory; to silhouette ships for observation; and to gredients sueh as atomized magnesium, resins, color
Iucate targets for bombing. Photoflash bombs il- intensifiers, and others werp tested and adopted;
Illlnjnatrd large areas for night photography. improvpd techniques to measure luminosity and
Smoke s~n'l'm; were used by land and sea forces ('olor, sueh as thf' barripr-layer cell photometer,
for a variety of purposes: aircraft and smoke boats \\'('re introduced.
scrpened ships during air attacks and amphibiow; The Ballisti(· Research Laboratories had been
landing'S, cOII{'!'al!'d underwater demolition teams established in 19:38 to ('entralize research activities
awl tactical JIl,lJlPuvers of ground troops. at Aberdeen Proving Ground and to undertake re-
By tIll' pnd vf tIlt' war pyrutpchllics provided search in fUIHlamPlltal Ordnanee problems. With
visual eummllllil'dtion h(It}. day and nil!ht be~·.veen (·omplption of d new l'lboratory in 1941, ba!>ic
plalh>s and tanks, t auks and artillery, infantry studies \\'(>rl' bt'g'un in areas pHtinent to pyrotech-
and airl:raft, and ships and the shore. nil'S sUl'h as flame propagation, burning rates, sen-
Inct>IHliary builds, b()mbs, projt>dilps, and sitivity of pyrotechni(' eompouuds, and the physical
grpnad~>s WPft' widely lIsed ill Europf'. Allied tac- ('hemistl'Y of gases.
li('S ill bumbing" (it'fman citit's PJIlployed equal ~aval pyrctechllics development during World
lIualltitips of ilh'PIHiiarirs and high ,'xplosivrs. On War II was et'ntered at the Naval Ordnancp
a wpi~ht basis, t!l(> ineendiary bombs caused five LaborutOl'Y, thpn located at the Naval Gun Factory,
limps more daJJlag(' than high pxpiosive bombs. The \V ashington, D. ('., and production was l'entered
(·pniral parts of 11,01'(' than ;')0 of Gf'l'many's largest at t!tp ~aval Amlllunition Dppot, ('rane, Indiana.
"iti"s werr> Ipvpled oy firp. Beforp 1l1Iclt>ar wee-pons 'I'hl' ~a\'y improVt'd existing itplIls for greater re-
Irprp wwd fifty pl'r('ent of 70 .Japanpse cities had liability awl stG!'ag!' !'ilaracteristics, and developed
bl't'll bllmpc\. l'lol'!' than !19 lwr('('nt of the total s'_ll'h it('llIs as dlPllli~al dpluy powde:os, self.releas-
bomb load droPPf'd Oil ,Japanps!' ('ities WIiS iu. in.!.!' buoyant submarillP signals, rt'seue flares, depth
,·,·tuliary, with I('s,~ than 1 IWr('f'ut high explosive. t' ha,.ge markt,!,s, aireraft sir,nal cartridges. and
Durillg' til" war, huncll'('ds of ll~ilJi()IlS of incendiary paral'hutt' flares.
hombs, projf·,t iles, and grt'lIadrs w('rl' provided by
Ill,· ('lil'lIlical Warfun' ~(,,'\'ie('--over 48 millioll
1-5 POST WORLD WAR II PERIOD4.1~
ill"('lItiiHI'Y bombs alOlw W('fl' sdppli{'d to the U.s.
Army Ail' J1'orc~. J<'ulJds for res\'ereh and devplopment of pyro-
Flalll!' thrOWN!';, whi,·1! lllul hl'I'1l d('vploped t('(·hllil· itt'lIlS wI'r!' limited ill the period following
during \Vorld War I, were improved and used with "'orld \\'a,. II; howI'v!>r, signifi"llut adVllllN'S wert'
SlH't'PSS ill HlP ('ampaigns in the Pacifie areas during C\(·[·omplish.>d w"ieh madt' l\vuilllhle impreved pyro-
Wodd War !I. tt'eltllil' devi('l's, sigllals, sllIokes, iU('t'll(liaries, and
I'i('atillu), Al'sl'lHtl dt'I't'lo!wd lIlallY impl'Il\'('cJ battlt'ti"ld iIJlllllillllllts \\'hl'l1 tit,> Kurt'an Conftiet
JlYroh ... ·hlli,· itt'llts to 111('('1 lhl' military dllUlgt' dt'\'t'lop"cl ill til(> early 1!HjO's.
1'/'(1/11 tl'l'lh'll Warfh!">, whidl had t'Xlst('c\ ill \Vol'ld Most }lyrort'('l!ni(' r,'st'al'('h lllIil d!'vt'lopltlt'nt to-
\\'Il!' !. to !ht' hiv.h1y sjI<'('jaliz!'d lllOlJilt· foret'S day is (·ani.·11 Ollt I,." tlH' (}owrlll!lt'nt at Pi('atiuny
or \\",,!'ld W'll' I; 1':;I'O\t'('lilli(' 1I1111JlllIlitioli fUl' Ars('llal, Ahl'l'dl't'\l Pro\'ing' Urouud, F,'allkfonl
lIliiila/'y lIIallPUVI'rs alld Hwans for prGviding visual ;\ l's"nal, t hI' ,\ rilly ('h('llli('nl HOlD Lahoratorit's,
(·"HlIll\lIl.il'utioll awolIlX I h,' various t'lt'lllt'llts ill- tht' :-:u\'al I )rdllall('t' Laboratory, tl\(' NUlla) Ord-
".Il\'(,!l w,·),,· (·s.~f'!itial. :\lof't· I'tli('lPlIt flar,'''' tlash !l 1\ 11<',' 'I\'st Stlltioll, tilt· :\IIVld AlIllJJllIlitioll Depot,

dllll'I':t':!, and II vllI·it·!.\, (If spottill,.;' phargt·s, siglluls, IIlId h\' (lo\,prlllll\'JlI-spOllSOrt,d 1Ij!!' IJ I' it's.

1-5
AMCP 706·185

REFERENCES
1. a. T. L. Davis, "Early Pyrotechnics. I. Fire Dictionary of Applied Chemistry, VoL X, p.
for the W am of China; II. Evolution of the 781, Logmans Green, London, 1950.
Gun; III. Chemical Warfare in Ancient R. History of Research and Development of the
China," Ordnance 33, 52, 180, 396 (1948-49). Chemical Warfare Service in W arId War II,
b. L. Katz, ,. Pyrotechnics ill Missile Design," published for The Chemical Corps Association
.
Washlllgtoll, D. C., Reinhold, N. Y., 1948.
'
Ordnance 44, 334 (1959).
c. H. Ellern, "Military Pyrotechnics," Ord- 9. L. P. Brophy, D. M. Syndam, R. C. ('...ockrane,
nance 44, 662 (1960). The Chemical Warfare Service from Labora-
2. T. L. Davis, Chemistry of Powder and Ex- tory to Pield, Office of the Chief of Military
plosives, John Wiley & Sons, Inc., New York, Jlistor: , Department of the Army, Washing-
tOil, D. C., 1959.
1943.
:1. H. B. .b'abcr, Vol. 1,1 .. History and Develop- 10. C. H. Custard, G. Frll.llcis, W. Schnackenberg,
Small Arm~ Incendiary A.mmunition, A Re-
ment of Military Pyrotechnics, U. S. Govern-
l'icw of the History and Development, Frank-
ment Printing Ofi1ce, Washington, D. C., 1919.
4. S. Sag!' and H. W. Evans, "Pyrotechnic. Re- ford Arsenal Report R-1407-3, December 1956.
11. L. Finkelstein, A. E. Gaul, Incendiaries, Vol.
search COIl1t's of Age," Ordnance 48, 262
18, H~'story of Research and Developn ':nt of
(1964) .
ChemtCal lVat'fare Service in World War II
G. AlaI! Ht. II. Broek, A History of :"'ireworks,
publishrd for The ('hemical Corps Association'
George C. Hanap awl Co., Ltd., Tjondon.
Washington, D. C., Reinhold, N. Y., 1948. '
fl. A. M. PrPlltiss, Chcmicals in WIZr, McGraw-
I:!. D. 1Iart, R('.~llIrch and J)evelopment of Milt:-
Hill Book Co., Npw York, 1!l37. tary Pyrotf~('hnics, Piratinny Arsenal, DO'ler
7 . K . f' .'S awypr, . , .:wreenlllg
co ' ...,
"mo k es," Thorpe's
N. J., 1955. '

1-6
AMCP 706·185

CHAPTER 2

INTRODUCTION TO MILITARY PYROTECHNICS

2-1 IN1'RODUCTION With the advent of the space age, pyrotechnic


~lodern military pyrotechnics as an outgrowth devices have becoTl1l' increasingly important. They
of "Greek }<'ire" alld the "art of making fire- are used extensively for spotting and tracking
works" has progressed to the extt'nt where pyro- rockl'ts and missilt's, for r!'covery operations, and
tpcilnic devices alld systt>ms ill both offensive and for speeial purpOSl' l'ountl'rmeasures, To meet the
defpllsivl' military oIwratiollS have be{~ome indis- rcquirelllt'nts for these applieations, it has been
peJ:sablt', It has dpwloped into a science requir- IH'Cl'ssary to inV\", ig-ate pyrotechnie reacti('l1s un-
ing l'xtf'llsiVl' and intt'llsiw hasic alld applied re- der eOlltiitiollS of It)W pressure, low temperature,
search to 1Hf't't new l'ollvputionul aud unique mili- greatly reduced qualltiti!'s of atmospheric oxygen,
tary and space rt'ljuirenwnts, varied degrees of eOllfillemrnt, and with different
'fh!' t'arty llIotit'st state of progress was ehanged types of initiating systenw.
eOllsidl'rllhly, hOWl'Vt'r, wlll'1l military operations Basic studies have been ulldrrtakl'1l to attain
bl'callll' IIH'('hanizl'ti with the developmcnt of th!'
a fundauwlltal Ilnderstanding of the preignition,
ignition, and st'lf-propllgative real'tions of pyro-
tank, tilt' bomhing plaUt'. lilt' submarine, long-range
techllie ingrt'tlients. Theories haVl' been developed
a!'t illcr)" tilt' airera ft t'arrier, other vehicles, anti
whil'h 111'1' Ilsl,d as a gllidl' for formulating flame
Wt'apollo,;; alld th\' illtroductioll of t'ombined opera-
,'ompositiolls burninA' tigarettc-fashion, with spe-
tiolls, To l'ool'dinatt' all thl'St' forces and to pro-
(·ifie burnillg !'atp requirelllents, Theoretical and
\ ide 1'01' risual l'Utl'lIllillil'utiol1s betwt','n plane and
t'lllpiril'al rplationships haw bpen developed ti>
tank, tank awl art illt,!,y, infantry and air force,
prpdil,t tilt' I'ates of propagative burning of slow-
both da~' aud Hight, till' dt'\,t'loJllllt'llt of pyrotpehnie
hnruiug' pyroh'l'hnies as /I function of particll' size
allllHlIliit iOIl for t h.,s(' plll'pOst's WIIS absolutely anti t'olllposition, InstrUIIlt'utation has been tit'-
('sst'lltiai. !Ill'l','ased liSt' of air-('ruft for' bOlllbill~ I't'lopl,tl to ,,\'II)ualt- lUluinolls intt"lsity and colors
and "lIlWI'\'lItiull )llll'IHlst'S rl-quirt'd tilt' liSt' of flint's of PYl'llft-t'hllit, tilllllt'S, luminous inh'llsity and dura-
aud phototiash bOlllbs whidl ('ould lw l't'l~-ast'd fr-om
t ion of tlaslws, t'olo!' of SI\lOkl' clouds, and improvl'd
rilpidly IIw\'illg' plall"s to illuminatI' t'llt'IIlY tPHi-
OlltPIII of P,\'I'otpl'hlli(' tiart's, Laboratory studirs
tory for lli~llt photography lind obseryatioll and to
illl'llIdt' lI~" of I ht'rlllal aliltiytil'al teehniques, spec-
iOl'lIt(, target»; for bombing,
t!'opitotolllt'trit' /llld t'hrollllltographic analyses,
.\ "lIrid,)' of "lIJokt' siglllll ... , spottillg' ('har'gt's,
To "lIlltill1Jt' to 1II(,I't lit'\\' l,hallt'Ilg'I'S, principles
h"'Hhul'dlllt'lit fll1rt's, illllJllillatillg sht'lIs, g'rolllltl alld
IIl1d t IIporit's of t'ngilH'l'ring' IlIHi Sl'il'll('l' lIltlst be ex-
lIir-l'l'lIft si"mllb had tll ht' dt'\'t'lopt·d to slItisfy Ill'\\'
pillitt'd IIlId pllt tll pral'tit'p, Only wht'll thi" is done
till'! i,'1I1 l't'lllli/'l'lIlt'llts :\t'\\' dt'lIIl1ll1h; for Sig'lllllill~
will it ht' possihlt' to "/twit/atp !,padioll 1Ilt'l'!IIU1islIIs,
l'apllbility rt''1l1in'd tlit' dt'\,plo!lult'llt of illlp!'o\'t-d
Pt'!'fUrIIlHIl"" of PYI'n!t'('hlli!' til'\'il'PS /llid to tIp-
"Ollll'I'd sllInkt's IIlld sigllals.
\'('Iop SI!JIt'I'illl' ('OlllpositiollS IIlId itellls.l,~,:l,4,~,H
1"01" SlIbllllll"ilt(, itit'lititi.'atil"l /llld air-st'a rt',WIl('

"p"I'litiolts, ",'a WlIlt'l' Iwti\'lItl' i, lmttt'ry-olwl'lItt'd.


flolltillg' !lIlIr-killg' sigllals \1'1"'" d"\,,,!tl\wt/ \\'itli g'ood 2-1.1 PYROTECHNIC DEVICES
lit'" 1111.1 "tability, .\1 Il II ,I' tYPl'S of silllullltol'S for AND USES 1,~',6.1,U, III
IUlld /llid S,'/I trtJ()]l t!'lIi'lillg' \\"'/'1' IIlso d"\'"l"p,,d TIll' t('l'Il1illlll t,tft,(,t of militllry Jlyrot.'('hnie
alld h"l'Hlllt' 1111 illdlSllt'lISlIhll' aid ill tll"St' np!'!'II' it,·III.S sHeh Wi lig'lll, IIl'lIt, Sl1\llkt' or ~(]IIJltl rt'!iult..'i
t iOIlS, frolll /til "xutllt'l'lllit, lIxidlltioll-··rt,,!tll't't! ('hemica)

2-1
AMCP 706-185

TABLE 2-1
TABULATION OF PYROTECHNIC DEVICES
»
1. Jilares
11. Reconnaisslln('t'
b. Observation
e. Bombardment
d. Dpplsning and emplalling" of tJ·oops and materit'l
e. Prevention of enemy infiltratioll or rp(~Ollllais~:all('('
f. Target ideutificHtion
g. Battiefirtd illllmination
h. Marking targets and blllllU I'pleusp lint's
1. EnH'rg'!'ney airstrip location aud id~~lItifieation
j. De(~oys
k. Missih' tru(·king
;J. Sigllals
a. Betwe('u various 1'l<'U1pnts of g'rolllHi troops
h. Between ground troops and plallp~. 01' vit'(' v('rsa
e. Betwcpll plalH's in thp air
d. Hearch lind r(,'>(,IIt' opt'l'ations (lo('atl' slll'vi VOI'S)
e. SubmurilH' to Slll'flll~<' 01' ail'
f. Prl'(~isioll I<w:ltioll of point OJ' tilllP in SPIW(' 1'01' /lSS('SSHlellt of missile
funetioll
g. EstablislllJ Wilt of points 011 II trajpl'fory

.'J. Colorcd a,nd Whitf Smokcs


a. 1<'01' daytimp sigllalillg'
h. }<'or screelling
e. !<'or spotting
d. 1<'01' Ularkillg' tat'gets
e. Thermal attplll!utillg' S('r('pII
f. Disselllination of ('helllil'lll ag,'lIts
g. 'frll.eking' allf! He<juisit 1011
h. Rescue
4. '/' raeet's
u. '1'0 t.l'lwe traj('l'Iol'ips of projpetill's or roekPts
h. For self-dpstc'uctioll of ammunition I1ft!'r It definite time interval
.J. Incendiaries
a. !<'or ust' against A'roulld lur~,'ts
b. For liSt' againi'lt air('I'aft t/ll'f~t'tS
e. !<'or emergency dr<:IlIlt'lI: alld ,'ql1ipmt'l!t 'il'struetion
6. Pyr(ltechnic Delatys
Tim!' (1('111), for t'xplosivf' IrlllllS
7. Photoflash Bombs and Car~~i!~{//'s
Aprial Ili~ht photegraphy
H 8p~ttill{/ and 1'racklny
All(CP 7()6.185

TABLE 2·1 (cOD.t~d)

9. Atmosphere (1,114 Space Studies


10. Simulated A.mmunition for Troop Training
11. Rocket Igniters
12. Fuel Igniters for Ramjet Engine~ and Guided Miss-iles
13. Aircraft Engine Igniters
14. Water Mark~rs
15. Heat Sources
16. SpeC'/4l Devices

reaction within a mixture of a fuel and an oxidant. luminous intensity through an appropriate colored
Additives or modifiers may be included to produce filter to the total luminous intensity.
more saturated colored flames, 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 val'iety of munitions that classification is weight or volume of compositions; for illuminating
difficult. These devices are, however, tabulated, or signaling it is expreRsed as candle/seconds per
with their principal uses, in Table 2-1. gram or pcr milliliter; for smoke-producing devices
efficiency is considered to be the per<!ent of chern ..
2-1.2 CHARACTERISTICS OF PYROTECHNIC ical vaporized hased eIther on the weight of chem-
COMPOSITIONSl,2,4,6,7 ical originally contained or 011 the total weight of
The applicability of a specific pyrotechnin . 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 of smoke. Compared to
not only to the terminal effectiveness I\nd output standard charts or by observers' ability to det.ect
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 (TOP).
actrristics. Predse and analytical determination 2-1.2.2 Processing a'nd Sensitivity !Characteristics
of the various parameters involved requires con-
Information on the processing·, st.orag~, ship-
tinued resrarch to jevelop improved evaluative
ping, and sensitivity characteristics of pyrotechnic
methods.
compositions can be found in ,Part Two of this
The more important characteristics of pyro-
series, AMCP 706-186.
trchnic compositions used for wilitary purposes
may be statrd as follows: 2-1.2.3 General Functioning Characteristics
a. Ignitibility. The ease ,nth which a pyro-
2-1.2.1 Performance Characteristics technic 'lomposition ignites, determined by standard
a. Heat of reaction. cal/gm or cal/ce. May bf' time-to-ignition tests described in Part Two of this
used as a basie criterion for seh'ction of fuel-oxi- series, AMCP 706-186.
dizer combinations. b. Hygroscopicity. The ease with which n com-
b. Burning ratf'. inches/seconr1 inches per pf1l':ition picks up moisturo:l at a preselected tem-
minute, seconds/ineh. Applied to consolidate!'! mix- pe~'ature and relative humidity.
bin's and rnrasured as a linear rate. c. Reaction characteri"tics. Puns:lamentally im-
('. TJuminous illtensity. eandela or eandlepower. portant are the heat of rfjact'on and rate of reacti:m
Visihlr output or illumination in eanlf'la. of a pyrotechnic composition. To make a consoli-
(1. Color value. The color quality of a eolorerl datt>d composition burn pNpagatively, sufficient
pyrotedmi(' flame taken ru; the ratio of the apparent llt'at must be evolved and the rate of reaction Dlust

2-3
AMCP 706·185

bt' of sufficit'nt magnitudl' to morf' than cfJmpen- 2·1.3 Constituents in Pyrotechnic


satt' for heat losses. CompositioDS1,2,4,e,'1
In addition to the heat of reaction and. the rate The ,)onstituents upon which the performance
of reaction, display \~haracteristics are influenced of pyrotechnic compositions and devices is depen-
by many othl'r fa(~tors. ROlliI' of thl' morl' impor- dent include a basic fuel and oxidizer combination
tant include: with other ingredients. These may consist of
dyes, color intensifiers, retardants, binding agents,
1. Granulation or particle sizl' of ingredients
water-proofing agents, and substances to create a
2. Composition of ingredients
specific effect,
3. Purity of ingredients
Typical ingredientfl in each of these categories
4. Burning surface art'a
are:
5. Heat transfer characteristics
6. Flare ease matt'rial and eOllfignration 1. Oxidizing Agents. Nitrates, perchlorates, per-
7. Loading pressure oxides, oxides, chromates and chlorates. These are
8. Prps('llee of moisturt' all substaners in which oxygen is available at the
9. Degret' of confinement high temperatures of the chemical reaction in-
10. Ambil'nt tempprature and pressure voh'ed. [n addition, fluorinating agents such as
11. Method of ignition Teflon and Kel-F arr finding use as oxidizing
agents.
12. Lengtll-to-diametp,r ratio
2, Fuel!'!. .Metal powders, metal hydrides, red
1a. Method and pnergy of dissl'mination
phosphorus, sulfur, charcoal, boron, silicon, sili-
14. Bomb burster geometry
cides. When these substances are finely powdered,
Ii). Y ploeity, acceleration and aerodynamics of
they readily undergo an exothermal oxidation with
dl'vicf'
the formation of eorresponding oxides and the evo-
lution of heat and radiant energy.
'rhe importance of a particular influential fac-
3. Color Intensifiers. Highly chlorinated or-
tor may vary eOllsidel'ably with the applicati()n.
ganic compounds, such as hexachloroethane
l<'adors snch as the average partiele diameter, Spl'-
( ('~CIII)' hexltchlorobenzene (CaCl n ), polyviuyl-
cifi!' snrfa('e, shape, and distribution will affect the
chloride, and dechloranp (ClOCIl~)' These com-
buminA' rate of consolidated pyrotechnic mixtures.
pounds are uti;ized to produce specific spectral
Changes in thp gp:wral charactpristics of the flare
pmitters in pyroteehllic flames.
casp and the area of the burning surface combine
4. Retardants. Inorganic salts, plhstics, resins,
to infiuencp thp output of flame produeillg items
waxes, oils. These are used to slow down the reac-
With pyrotp('hl\ie delay compositions, the burning tionr. between the oxidizing agent and t.he powdered
\'att' iR of prilllary signifil'allce al,d may be varied metal to produce the dpsired burnin,.. rate. Some
by ('hang'ps in till' pf'r('('ntagps and particle size of behave merply as inert dilucnts while others par-
the ingrt'(Ii('nts in the ('omposition, incorporating ticipat(· ill thp reaetioa at It much slower rate than
adrlitives, varying the l'ompaction, and by other t hc main constituents.
means. ~OJIcolls()lidated pyrote!'hnie photoflash i). Binding A?:ents. F.ins, .. dXPS, plastics, oils.
mixtures used ill fiash items are influf'nCNI by the Thr5le art addrd .. , prev,'nt segregation and to ob-
method of ignition, ratio of length to diameter, tain more uniformly blended cum positions. In ad-
hursh-r g'l'OnH'tI'Y, and dl'g'rt'!' of eonfint'nH'nt. rlitiol]. thpy sprw to mll.kr finely-divided particlas
III addition, thprp arp lllany otlH'r faetors PI'- adherp to (·ach oth('r whl'n compressed into pyro-
I'nljar to tilP s\w('ifi(' item lllldPr consideration that te('hllie itt'llls and help to obtain maximum density
llIay !'X(,l't varying il\:illelH'eS on pt'rformanee. In alld bnrning t'ffi('ien('~r. Binders also frequently
til(' dt'"igll alii I d('\'(,lopnwlIt ,)f !H'W pyrutpchll~(' des(,ltsiti7.!' llIixtllrl'S which arf' otlwrwisr sensitive
1ll11llitiuw;, a' fresh appl'lHH'h should always bp eon- to illlpad, friction and static ph·et.ricity.
sid('rt'd, usillg tht' data uvaiJahlf' 011 ('xisting' de- G. 'Vaterproofilll! Ag<'nts. Hesins, waxes, plas-
"il'PS ollly as II glli<lplilll'. t i(·s. nils. di('hrolllatillg' soilltiolls. These are used

2-4
AMCP 706·185

TABLE 2·2
COMPARISON OF SOME PROPERTIES OF PYROTECHNIC
COMPOSITIONS WI'JH EXPLOSIVES

Impact

••
•• •
<.
~ S
Composi tion r.QQ ll< .S

PYROTECHNIC:
Delay
Barium chromatp 90
Boron 10 480 18 o 650 12
DeLay
Barium chromate 60
Zirconium-nickel alloy 26
Potassium perchlorate 14 4H7 12 o G6 23

fi'larc
Sodium nitrate 38
M&.gnesium 50
T.Jaminac ;) 14;)() ti40 60 19

Smoke
Zinc 69
Potassium perchlorate 19
Hexachlorobenzenc 12 (lIB 475 23 15
Photoflash
Barium nitrate ;{O
Aluminum 40
Potassium perchlvrate :{O 2147 15 7 700 100 26

HIGH EXPLOSIVE:
TNT 10(j0 ]000 4H 475 100 14
RDX 1240 (j00 (j() 260 18

BLACK POWDER 684 272 288 32 16

• 3'sl'('ond value .. Bureau of Mine.s u* PicatimlY Arsenal

a~ proll'l'ti\'t' (·()(ttinl!s on lIH'tal;; slwh as lIIaglH'siulll. than OIlP function, thus simplifying the composition
aluminulIl aud zirconium-nickel alloys to reduce of some pyrotechnie mixtures.
t hpir read iOIl to atlllOsphpri(' lIloistul'P.
i. Dy('s for ~llIok('s. Azo alld allthraq\lillolH~ 2-1.4 Comparison of Pyrotechnic Mixtures
dy('s. Th('st' (iy!';; providt' t hI' ('0101' for smokef; IlSl'd and Explosives1.:!,6,lO
1'01' sil!llalilJl!. lllarking. and sWltting. Pyrotrrohnic mixtures can be devised to produce
MallY of the' aboV{' substances pprform more as litt 1(' as 200 (~alori('s Jwr ~ram o{ mixture or ill

2.5
AMCP 706·185

~xc('ss of 2000 calories per gram. ReactiOI: tern· f'xplosives.


perature~] exceed ::WOooK in some cases. A comparison of some of the more important
Such amounts of energy and the high tempera- properties of pyrote<,hnic compositions and ex-
turfS attainpd can be extremely dangerous. In gen- plosives is given in Table 2-2. As indicated in this
eral, b~cause the quantity of gas produced is less, table, pyrotechnic comoositions, ill general, are not
and the release of energy is '\t a lower ra.te, the as sensitive to heat as explosives. Impact values
terminal effects produced by pyrotechnic composi- Hsted indicate that some pyrotechnic compos.itions
tiol1' are less severe than those producsd by high are at least as sensitive to shock as explosives.

REFERENCES
1. G. Weingarten, Chemistry of Pyrotechnics, f). L. Katz, "Pyrotechnics in Missile Design, I,
oral presentation at Picatinny Arsenal, Dover, Ordnance 44, 334 (l9f19).
N. J., 1955. 6. TM 9-] 910, JlJilitary Explosives.
'J D. Hart, Research and Development of Mili- 7. TM 9·1370-200, Military Pyrotechnics.
tary Pyrotechnics, Pieatinny Arsenal, Dover, H. H. Ellern, "Military Pyrote(jhnics," Ord-
N. J., 1955. nance 44, 662 (1960).
:3. So Sage and R. W. Evans, "Pyn'teehnic Re- 9. T. C. O'Hart, Elcments 0.' Ammunition, John
search Comes of Age," Ordnance 48, 262 Wiley & Sons, N. Y., 1946.
(1964). 10. 1'. I... Davis, Ohcmist1·y of Powder and Ex-
4. H. ElIem, .1lodcl'n Pyrotechnics, Chemical plosil'CS, .John Wiley & Sons., N. Y., 1943.
Puhlishing Co., 1961.

2-6
AMCP 706-185

CHAPTER 3

PHYSICAL-CHEMICAL RELATIONSHIPS

The output characteristics of a pyrotechnic Similar ('xpressions can be written with T and p 'is
munition are determined, to a large extent, by the the dt'pendent variable. If a system has n com-
tempp-ratures to which the reaction products are ponents, 11-1 (·omposition variablrs mnst br speci-
heated as a rt'sult of the chemical rf'action between fied.
the fuel and oxidizer. Thf' maximum temperature
of the reaction products depends on: (1) the state 3-1.1 THE GASEOUS STATE
of the products at thp r!'action temperature, (2) 'fhe gaseous state is characterized by changes
the heat !'volved by tIl{' I'xuthermal chmical reac- ill volume with ('hanges ill temperature and pres-
tion, and (:3) the r3te of heat production and heat sure. Gases normally have no bounding surface
loss. Physical-r!hemical relatiollships allow the aud, therefore, tend to completely fill any avail-
state d the products, the energy rel!'ased, and the able spacp. A knowledge of thl' behavior of gases
maximum r!'adion tt'lllperatnre to be calculated. with changl's in t!'mperature and prl'ssur!' is es-
The rate of heat production and hfat loss, which sential becansp of the importanc!' of tht' gaseous
are iniiuenct'd by the ambient temperature and state at the high tt'mpt'raiUl'!'s involved in pyrn-
pressure, (·o!lfinenwnt. and many other inter-re- chemical reactions.
lated faetors, eall also be calculat!'d for certain Gaseous products formed in the combustion of
sim pie (·ases. However, for 1ll0S i rt'actions, these
many pyrotechnic mixtures may range from es-
qU8ntitips must bp det('rmined expprimentally.
sentially zero, for most thermites and some types
The physieal-rhemical relationships which are
of delay mixtures, to 15 to 20 percent for light-
applicabl!' to pyrot!'chnics aI'!' summarized in this
producing compositions, to 50 percent for some
chapter, and p!'rtilH'nt examples ar!' given to il-
smokp-produciug mixtures. At the high tempera-
lustrat!' th!'ir application.
tures produced by the burning of pyrotechnic
compositions, many substances not usually con-
3-1 STATE OF A SYSTEM sidered gaseous will exist in the gaseous state.
The slate of any system (gas, liquid, or solid) The formation of gas, both as a pei,'manent product
can hl' dl'sr:ribed by specifying a sufficirnt number and as an intermediate product which exists only
of it." properties such as mass, volume, tpmperature, during the reaction, is indicated in light-produc-
aud pressurt'. l'hl'sl' properties are elassified as: ing mixtures by the presence of a flame. Gaseou:;
( 1) exit'usiVl' propertit's which depend on the size combustion products are necessary in smoke-pro-
of the system, and (2) intensivt' properties which ducing' mixtures to aid in the formation of dis-
are indepeudent of tht' size of thr system. It is persed, particulate matter and to earry this matter
unIlecn;sary to specify all the properties of a sys- into dIP atmosphere.
trIll iu order to ehuraeterize its statr; two indepen-
dent variables, eOInmollly til(' intensive variablrs of 3-1.1.1 Ideal Gases
pressure and tpmperature, are sllffi(~ipnt for a given Th!' behavior of gases at low pressures and
amount 'of pure substalH·p. A mathematical expres- high t('mp('ratures is often approximated by an
sion for this rt'latiollship is an !'({uation of statr rq uation of statr known as the ideal gas law:
whieh, for Ollt' mole of a pure substance with vol-
ume as th dt'pendent variable, has thp form: lV
pv=nRT=M RT (3-2)
V=f(T,p) ( 3-1) wh!'r!' p is th!' pressure, l' is the volume, n is the

3-1
AKCP 706·185

number of moles, R is the universal gas comltant, be given in weight units of a particular gas in-
T is the absolute temperature, tV is the weight of stead of in moles. In this case:
gas, and Jl is the molecular weight of the gas, us-
ing any s~t of consistent units. The density d of R '-~
-M (3-5 )
an idea) gas at variOlls temppratures and pressures
is: wherl.' Jf is the molecular weight of the gas, and R
is the univprsal gas constant.
d= ~_= pM ( 3-3)
v RT
3·l.1.3 Rcal Gases
The ideal gas law applies, strictly, to a hypo-
thdieal gas, which is composed of mass points be- In a real gas, the forc!:'s acting between the
twecll which 110 forces are acting. At the high moll'tules as well as the volume of the molecules
temppratures and relatiy('Iy low prpssures pro- ('ausp deviations from ideal bphavior. Several equa-
ducpd by burning ulIconfhH'd pyrotechnic mm- tions of state have bt'!:'1l proposed to more closely
p08itiolls, thp idpa! gas law is fairly accuratp. At approximatp thl' behavior of real gases. Rome of
the higher prpssures which lIIay be produced when thrsc p<lllations of stat!:' include:
a confined pYfotcehnit, composition is burned, the Van !fa lVaal's Equation:
behayior may flt'viatp appreeiably from that of an
ideal gas. ( p + ~~-) (I' -Ill,) = nRT (3-6)

3-1.1.2 The Un"versal Gas Constant and Standard whprl' a is H corrretion for the forces between mole-
Conditions (·ulrs of a real gas, and b, termpd the co-volume,
I t has been determined that one mole of ,an is a corrpdioll for the volulIH' of the molecule.
dl'al gas /)(~cupips 22.41-1 liters at 273.HioK and The units llsl!d for a alld b must hI' consistpnt with
()lIP atlllospherp. Tlwll, from Equation a-2: thmw ns(·t1 for tht, ot}wr yariahll's.
A bl'l 's Eqllation:
R = pv = (1) (22Al-!l = () .(lH')()'" !iter-atm
01'\. moll' = nRT
7' ('>7" 1l!)
. - .). 1>
_.J (p) (1' - nb) (3-7)
(:l-4 ) where b is the correction for the vtJ1ume of the
Thl' Itni\'('rsal g·as l'OllstHnt R has tIlt' units of lIlolp('IlIf's. This equation, which is a modificatioll
PIll'r)!y lH'r dt'l.(TPI'-ppr molt,. It lIIay hI' ('aleulatC'd of Vall ([('1' lVaaZ's Equation, applicahle where the
fl'Olll gquatioll :J--l for OIH' llIoll' of gas at standard pressurp is high, has been quite widely used for
('ouditiolls. 1'11(' \'alllP of R lllllst 1)(' ('ollsistC'nt with ('alculatiolls involving' explosives and propellants.
th" ullits or 1)J'I's:-H\rl', tl'IllIWratUI'I" and voluJIle I'iriql Equation:
IIst'd ill thl' idl'al ::as law. ROJllP vailH's of R in-
dudl' : pI' = IIRT ( 1
('
+ -B,1 + ~. + --- )
1'-
(3-8)

l' allll' l' /I its


when' thp coefficipnts R, C, etc., vary with tern-
litpr atmospht'res
pt'ratlll'l' aut! art' l'alled tllt' sc('ond, third, ete.,
~rHIll 111011' d('~I'(,(, Kt'IviJl vi rial coefficiPllts. This particular f'quation is a
psia ('nbi(' f('l't wry g'!:'lwral ('quatioll of state for real gases. By
]lolll)!l lIloll' drgl';:p--Hanki;l-p- using (mough tprms, thl' values calculated from
('alori('s the aboy!' ('qllation ('an he madp to agree with ex-
1.!IH7 .---
::r'am llIolr drgTI'P /{phin Iwrimt'lltlll data as (·Iosely as desired,
BTU
1.!IH7 (,'omprcssilllTity Factot·
pOIlI;J~~l('/!I'('l'l~all~
Till' dpyil(tioll of a ga.s fl'otH i(\l'aI brhavior t:1l1l also
III ~Olll(, rt'f('rPIH'E'S, inl'luding many of thOR!:' deal- Iw ('xPl't'sSl'd by tlil' IISi' of II ('omprt'ssibility fal'tor
ing with roeket propulsioll, a gas constant R' may K whert':

:~-2
AMCP 706·185

7
1.!

1.0 U
.liI
... 0.9 a.o
Au u

f: 0.6

G.4
2.8

2.4

1.2

2.0

o.a U

Q.J 1.8

1.4

1.!

12 14 16
• 28

Figure 3-1, Compressibility Factors as a Function of Reduced Pressure

Ii- = -----
JlI' allows a valtlt· for allY Ollt· of tll{' thn'(' variahll's
liNT 1', I', alld T to Iw (~aleltlatt'd ill ft'I'IllS (If thp other
(II', III t('\'J\I~ of l'l'(hlt'l'd variablps: \'al'iahl!'s with a fail' dt'grp(' of a.'('ura.')', Tht- l'OIll-
pl' .. ssihilit~, fadOl' ('Ill I Ilt' dt'tl'l'lllilwd p~peri­
,-
i= (' Ollstallt) (PrJ'/')
-r;--, IIlt·l\ lall .l' or by ('al('lIlatioll usillg' a suitablp P'l"ll-
tioll of stat,·,
III whil'h a J'('.hlt'l'd val'iablt- is th., variabll' dividl-d
by its vall\.' at titl' .'I'ili('al pOilll, i,.',:
3-1.1.4 Gas Mixtures
/1, ,=- (jlp,I,T, :=c (TIT"I,alld l-,_, 1'/1'" (:!-11)
Oas lIIixt Ul'.'s art' lIol'mally II'pat('r] L.v l>altoll's
TIt(· l'I'iti.'al poillt is d(·filll'd whl'1I till' propp 1'- Law, i,l'"
ti,'s of a liquid alld g'as pitast' whi(,1t al'l' ill (.qlli-
lihl'iulIl b.·"OIlI,· idl'lIti('al. Tltt' p. ,', alld T tjUlIlI- /1,«,,,/-, /1 1 + II~ -+ ---- ::cc- ~" p, (:~-12 )
tilil's, asstJt'iatl't\ with tltis ('riti('al point, al'l' r]t'- '=1
fillt·d as II" /'" alit! T" TIt("'l'foJ'(', as I'\,(·dit'!(·d by Wltt'I't' till' pari ial IH'PSSIlI'P PI of each of thl' eClD-
tli .. Jawor .'()\,('(·spolldiilg stat,·,s, if II is plllttt'd POIH'llts is d .. fill,·d as tilt' !In'ssul'(' whieh wo~dd be
iI/wi list /1, at it gi\, II 1',. d sill~d(' ('III'\'(' will I'!'sult (·xl'I'I,·tl if it ()('I'IIJlit'd IIII' total \'"lUIIII' at til,' saml'
fill' all ~!a".·s as sll<l\\'\1 ill Fil!'III'" ;l-I, Til" .'0111- t"1I1P"I'i1t 1\1"', (:as Illixllll'l'S "all aho h.· In'all'd by
pl'l'ssibility fa"',,\, "~t illlat,·t! fl'olll tIlt'S(' ('IlI'\'('S lit,' ;\Illdgat additiy,· \Olllllli' la\\'
AMCP 706-185

n
application of both of these laws to real gas mix-
Vtota! = VI + + ----=
V:! ~ Vi (3-13 )
tures is sonH'what more difficult. l
<=1
where the volumes of the individual components
3-1.1.5 Sample CalculatioDs
etc., art' the volume each would occupy at
VI. V:!,
E:rarnpll! Olle: Analysis of the product gases
the (total) pressure and temperature of the mix-
ture. For ideal gas mixtures, the r{'snlts obtained producE'd by a burning fuel block composition,
containing ammonium nitrate and charcoal, indi-
with this equation will be the same as those ob-
cates thbt the reaction taking place could be repre-
tained by use of the additive pressurE' law. 'l'he
sented by the overall reaction:

(a) The volume of gas produced per gram of mix-


ture hurned at standard tcmperatnr(' and pressure
can be calculated from the above reactiOlI and the
ideal gas law. 'I'he reaction produ('f's 22 moles of
product gases from 6 moles (If NH 4N0 3 (480 Example Two: A cylinder having a volume of
grams) plus 4 molC's of cha reoal (4H grams) or a
Oil('liter is prt'ssurizeli to 200 atmospheres with
total of 528 grams of fuel block.
('arbon dioxide at a temperature of 4ooC. The
Moles of gas per gram of fuel blo('k hurned:
amount of carbon dioxide can be calculated by:
22 (a) Assuming carbon dioxide bphaves as an idt'al
--- = 0.041 moles per gram
528 gas:

Volume of gas produ<~ed (RTP) per gTlun of __ puM _ (200)2) (44-) = 34:3 'rams
fuel blo(~k bu;.-ned is: ' v- R'1' - (O'(JH2) (31:~) g

nRT (O'()41) (0.082) (273) (f)) A::.;suming that carbon dioxidr behaves as a
V = --p- :=:: '-1----
Van der Waal 's ga::.;:
= 0.Hl8 liters per gram
(h) Siu('(' the aetna! tpmpprlcJtnrp of the product
gas('s is 10000C, tlw ealeulated yolnmp at thif': tem-
pl'raturp and (lIlt' atmosphere would b(' ronsid('rably
[ RT

greater: .I'or
L' ":!, a =,.~ .oJ,
('" -q \iters~ atm molc-~; b= 0.0427
liter Illcle-' 1
127'~
VIOOOo C = 2'1~~
(c) 'rlIP partial
produets may hr
(O.9IR) = 4.2H lit('rs per gram

preSSllrp of 011(' of thp gaseous


found by using tilt' idel:! gas law
(4¥):! (a.5!))]
[ 20() + -----(1)2 ---
[ 1-~ (4~-) (0.0427)
,
1
aud moll'S of ttlp COmpOTIPnt dl'sired and the total
volume for nand V. Thp partial !ll'l'SSUrt' of car bOll
dioxidp would be l'l\leulatpd 1\:; follows:
~oll'illg' ('ubiI' p(Juatioll in w: W = 625 grams
1Ico~H'l' (:I/fi~l'i) (O.OI'i~) (:>7:1) (') \ :sP of tll(' g'('lwraliz{,d compl'pssibility ehart,
p co • =, ------ - - - O.9J!'I-----
• V'o,al l<'igul'(' :~-1 :
= (),14 atlllOsphel'P (·ritil'allH·t~SSUl't· ('arbon dioxi<lt' :c:: 72.!1 atl1losphert's
('ritil'ul tt'IIlPI'l'lItllrt' ('lll'bUIl dioxidt' = :104.2°K
Hill(,l' the partial prt'ssul'(' is proportiulJal to the
mole fradion of c'll('h gaseous COlllpOllt'llt, a ~iIllpll'r
pr = 200 = 2.7!)
method woul(; be: 72.9

il-4
AJ4CP 706-185

T,.
;na
= :J04.2 = 1.03
, I
ogp =
- 0.0522::J (540,000)
2373
+ 14.22
log p = 2.32
!<'rom Figure 3-1, K = 0.42 p ~-= 210 mm mercury
pvM (200) (1) (44) The vapor pressure of small droplets, such as
w = . KRT = (0.42) (0.082) (~13) =: 608 grams
mist droplets, is higher than the bulk: vapor pres-
sure. If Po is the bulk vapor pressure of the liquid,
The experimentally determined value is 835 grams.
the vapor pressure. of a droplet p is given by:

3-1.2 THE LIQUID STATE p ( 21M)


= po 1 + rd RT (3-15 )
A liquid, like a gas, has no definite shape alid,
where y is the surface tension, M is the molecular
hence, t.akes t.he shape of t.he vessel in which it is
weight, d is the density of the liquid, r is the radius
})laced. The surface of a liquid, ill the absence of
of the dI'OP, R is the universal gas constant, and
other forces, will tend to ('ontrad to a minimum
area and is responsible for many of its characteris-
T is the abs.)lute temperature.
tic properties. The m')lecule8 of a liquid are less
mobile than those in !!;ases but more mobile than 3-1.2.2 BOiling Point
those in solids. The temperature at which the equilibrium
III pyrotechnic reactions, liquids are formed vapor pressure of a liquid equals the ambient pres-
by the melting of solids and condensation of vapors. sure on the surfaloe of the liquid is known as the
I.Jiq uid fuels must h(' vaporized before sllstained boiling point. If the ambient pressure is one at-
eombustion will take Jllact'. The burning of many mosphere, the temperature at which the liquid boilij
solid fuels, induding l!lo:-;t of tht' metal fuels, in- is termed the normal boilihg point. }i'or many
volves the formatioll and vaporization of a liqnid liquids, the normal boiling point is approximately
phase as a step in the combustion process. two-thirds of the eritical temperature. According
to 'rroutoll's Rule, the number of calories required
to vaporize one mole of many liquids, including
3-1.2.1 VapGr Pressure sonlt' of t.he metals, is about twenty-oue times its
'fhe pressure exerted by a vapor, ill equilibrium normal boilillg telllpe"'aturf' (degrc('!; Kl'lvin). By
with a liquid, is the vapor pressure ,)f the liquid. ust> of 'I'1'LlUtOll'S Hule, the heat of vaporization of
The vapor pressure increases wit.h temperature sonw of Ih!' IIlt·tal fuels egn be approximated if the
until the eriti('al tempI'raturt.' is reached above boiling- tel!lpel'litul'l' is known. a
which till' liquid eallllot exist. 'rill' vapor pressure Lithium hasll boiling point of la:noC (If.04°K)
at the eriti('al tpJIlperaturl' is termed till' eriti(~a.l allll its l'I'IHll'tf'd heat of vaporization if: 32,190
prpssltrr. The illl'r.~ase in vapol' pl'e~~ur(' with tf'ro- ('idol'ies pt'\' mole. Applying 'l't'outon 's Rul~:
perature ('all bl' 'tpproximatrd by tilt' empirical 6.fJ,.ap = 1604 (21) ~= :~:J, 700 ealories per mole
('qllatioll ::!
3-1.3 THE SOLID STATE
i'l.,lids lUlv/> II iix!'d shup" and volu1I11l with the
individulll units (at/)m~, molN'ules or ions) so
wiH'r!' fJ is th!' vapOI' preSSUI'(' ill ltlilimdl'l'S uf Jllf'r- firmly boulld tog!'!ll(·!' that. t.iwrf' i~i littl~ frt'(>dorn
('ury, T is tilt' absdutl' telllIH'ratur(' OK, 1Inll a and for tl'lll!"latiollal IIl01HJll, ('l'ystaEint· solids e,h~bjt
Ii art' t'lllpiri('ai!y determined l'Onstllllts for eaeh (lrd!'rly interllal aITalll~('IJlCllts IUld I.'xhihit tl sharp
liquid. For /'xIIlIlpl(" alulIlillulJI oxidl' ill tilt' jl'Ill- 1I11'lt ill l! \loint. Cryslals whos!' propl'rtit~1-~ life lif-
I,t'ratul'(' rallg'!' lK-l!J°(' In ~~2()OO(' has ('()Jls!allts of fl'rt'lLt aloll~ ditT!'I'!'lIt ax('s of dl" I'rystal are ealled
:,·li),()OO and le~~ for (f atll! 1>, l·t'Spt·di\,P!y. At !lnisotl'Opi('; if the properties an' tht, Sllme, they
~lOO')(', tht' vapor Pl"'SSIII',' of tht' liqnid would hI': 1Il't' nill!'d iso! I·opi(·. A llIurphous solids (sueh as

8-5
AMCP 706-185

glass) m().y be fegardt'd as super-cooled liquids of


high viscosity" They hcwe indefinite melting points
and und(:fined internal arrangements.
The properties of solids art' important to the
study of pyrocht'wical reactions, which involve
solid ingredients re:lctillg to produce mainly solid
(I) ~2) (3)
products. Intermediete steps in the reaction in-
volve litlUid aad gaseous phases; however, some Simple Face-centered Body-centered
pyrochemieal reactions Iliay proceed by a solid- cubic cubic lattice cubic lattice
solid reaetiOll medwnism. lattice
There are 230 possible crystal forms whi(~h can
Figure 3·2. Cubic tllHices
be grouped into :12 classes w hidl, ill turn, ('lill hI'
I'eferrt'd to Ollt' of the following six ('I"ystal systems: ;{. BtJJy-eentered cubic lattice. One unit at
('ach corner of ·;-,he cube and one unit in the
1. Cubic. Three ax!'s of equa I length inter-
s('cting each othl'r at rig-ht lin gIl's. ('pnter of the cubt'.
2. Tetragonal. Thret' axl'S int<'rsl'cting each X-rayt; may IJP used to determine the internal
other at right angll's with ollly two of the structure of crystallinl mat.erials, which ('an ht'
axf'S !'qual ill It'ugth. ('alclllat('tl by Bragg's 1,aw :
:\. llexagolllll. 'l'hn'(' axf'S of f'qual length in II (3-16 )
sing!t' plaue intf'I'sl'ding- at 60° angles, and
wht'rl' n is th(' ordl'r of I'!':it'ctioll, ), is the wave·
a fourth a.'(is of (li/f"I'ellt 1(,lIgth and lwr-
1t'l\t~th of till' X-rays, d is tht' distaJlee between two
pl'lldi('ular to til(> plane of Tlw oth!'r threE'.
4. Hhop.lbi('. Threl' axes of ullequal length in·
planes, and e
is the auglt' oj refleetion.
X-ray tt'ehniqut's are employrd to identify
ters<~ctillg at right angles.
lIIany solid prodlJ('t,; of ('Ombllstioll from pyro-
5. l\lolloclinil'. Thr,,1' axes of unequal length,
tt'('}lIli(~ J'('adiolls. 4 'rhis is t'spl'eially llsdul whell
two of whit'll illtl't'bect at. ri~{ht angles,
allalysis of a pal'ti('ular prod\wt'to; mixture would
0. Tricliili('. Thrpp axes of u/ll'qual length,
I]ot bl' prlwti('al hy w('t, dh'llli(~al methods and
/lOllt' of whieh illters('d at. right angles.
wht'r(' rdt'lltioll of th(, samp\t' is dl'Rirpd.
'I'll!' ma('nls('ol,ie symlHPtl'Y of ('I'ystals is dllt' &lli<ls ('all he divided into three classes based
to tilt' rt'g'llIarity of tht' arl'llllg-t'ltH'llts of tht' {·Ip- IIpon tlwir tlH'rmal and dectrical conductivities:
IIlt'ldal pal,ti"I,'s (atoll1s, iOIlS, 01" moll'I'III('s) ill a 1. ('ont!l\d,w., or metals which have high COIl-
latti,'("" I·ollsistillg· of a thr('t'-dilllt'llsiollal r"pt'titioll liudivilips which dcer,'asl' with an increas(~
of SOlJ\t' st nl\'tural IllIit ()f fbu'd dim"lIsiolls. 'l'llt' ill ll'lIlIH'rature.
IIl1it ('('1/ is thl' SI)lllll('.,1 'mit of t iiI' ,'I"y,:t a1 latti('!' .) I !\sn!alUl's whidl ha\"(' low ('OIhlll<,tivitit's.
whi"11 rt'~aills all tl)(' SYIllIII!'tl'y of tlit' III(Wl'os('opil' ::. St'1I1i-\'olltlut'lors whi(·1t Ira\'!' illtel'meciilltl'
1·!"y"taL III g"t'IIt'l"l\I, tltt'!"!' art' sl'\,('l'al t)(,ssibll' Ill'- "(dltiwti\'itit's whi(,1t iJl<'I"'IIS(' with rising
ra II gl'llI I' lit S of ('I,'lIIt'lItal'Y 11IIrti(·lt'." ",hil'h will I ('Ill (It'ra t 111'(,. IIsually :IS (' .1/'1' W lI!'r(' A IS
ha,'I' th,· sYllJllldry a""lI'iatt'd with II gin'lI (·rystal a t"Ollstallt a1\d 'T is tltt· absollltt' t,'llIlwratun'.
syst('IIl. slidl as thl' ('I!lli(, systt'lIl.
Tit!' tlwrllJaj IIlld 1'1t,(·tri{'al ('()lIt\ul'1 j\'ity of pyro-
TIII'n' a/"I' thrl'I' possi},I" aITallg"I'llll'llt;; of spal'('
I !'..JI IIi,'illl.!"l"I'dil'llh !Hay hI' "tllltl'ibntillg fadors
lalli,·!'.' for tilt' ('lIhil' s.\"SII'III. ,\ ... 1Iluslrat,"d III
J.'iglln' :l-~ tiJI"Y al"t": atl""l"!ilt:! tit" pprt'onllillll't' of a Pill'ti"lIlar item.
Tllt, tli,'rrllal ""lldlWti\'il~', whidl is of gT,'att'1'
I. ~ill'pll' 1·III>it· latti,·". I hi,' .sll'lIt'fliral ullit "i)!l:iti(";tIIt·". ird!III'II""s thl' l'Olldlwti\·I' h,'at t I'III1S-
at ,'a../I ("(11'111'1" of thl' '·lIb,', fel" ,·lIarad"'rist I("~. Th"s,' prol'l'!'t it'S hl'('olllt' ,"t·ry
'j Fa'"'"-I"·llt"I"1'd "\lbi" lat t i, ". ()JI" Hllil at i:llportHII\ ill t!",·j,·"s tll'pI'lltklll Oil a fUlldiollal
I'ad, ,·')1"111'1" of fitl' 1'111i., ailt! 0111' IIlIil ill tht" I f"iIIlSf('1 tlf llt'al .~II..}I a" il .. pyro-liwitl'il." SIIt"h
",'111,'1' "t' ,'a'·'1 fil'·" ot' tit" '·lill". d,",i,·,'s IIla.l" btl Illll'lIJally I'!os('d or lIoJ"lJlally opell

:l-(j
AMCP '106·185

and will either be conducting or nonconducting fol- discussed showing' their fj,pplieation in the field of
lowing the pYJ:'otechnic reaction. pyrott'chnics. Relected calculations, induding those
The propertit's of solids arr markedly affected for fldiabati(' flame temperatures, whi('h are im-
by defects 5 in crystal structure. Small amounts of Th)rtant to the oVl'rali analysis of ('hrmical reac-
impurities in an insulating material may make the tions, arr also prt'!'ented.
material a semi-conductor. Such doped materials
may also exhibit enhanced chemical activities. De- 3-2.1 THERMODYNAMIC RELATIONSHIPS
parture of a crystalline compopnd from chemical Thrrmod.v; i:-lI11i('s is based Oil three laws and the
stoichiometry, due to incorporation of extra atom~ implipatiolls \i~'ri\'('d from thest' laws. 'I'he applica-
into the crystal at interstitial sites or to vacancies tion of (,prtain t hermodynami(' rt'lationships de-
eaused by the abser\('t' of atoms i\'om normal sites, rived from th(' thr!'!' laws i!'; a useful tool for use
also rt'sults ill semi-eonductivity. ill pr!'dieting' the performan('p and out com!' of
Point defeds, inclUding those ill which an ion lIlallY pliysi('iH·hpmi(·al systt'ms.
mov('s from its lattiCl' site to an interstitial posi-
tion (Fr!'nkt'l dt'ft'l't), or t host' in which a pair of
3-2.1.1 First Law of Thermodynamics
ions of oppositp ('harge art' mi,;sing from their lat-
The first law of th!'; JIlociynami('s is a statement
ti!'p sitr (S{'hottky dt'frct), do Hot altt'r the t'xact
stoidliolllPtry of the sl)lirl but do provide a means of tIl(' law of eOllsPl'vatioll of ellPrgy, i.t'., that
PlIt'!')!Y {'an bt' ])('ith!'r <:rpatptl lIor dt'stroyed,
by which atollls can lllOW in thr solid phast'. I~inpar
dt'f,'ds. disl<)('atiolls. provide a 1\1 '1' Ilwans for
'I'h., first law of thprmodYllamies ('an h,c> ex-
\.1 ('ss(>d matlwlllati('ally:
atoms to movp with rpslwct to t'u('h ( ' I ' in tht' solid
pllast'. 'rJwse tlt'fpi'ts pl'o\'idt' mt'('hanislllS for mallY tlE =: (i --- II' (3 17)
of HlP pro('t'ss('S whit'h Ol'enr in th" solid stab'.
",h('I'(' (I is the' t'llt'I'gy ill tir!' forrll of hcat, trans-
TlH'Y provid" sitl's at whidl \'ht'mieaJ reaetions
f,'rrt'd illtn or 011t of tilt' sy~tPlll; W is til(' rllergy,
alld physieaJ (·han!res ('an take pia!'!' l'radily. '1'111'
;ll tht, fOl'llI of work t!'ansft'rr('d to or from til('
point of P!llt'rg-i'IH'(' of it dislo(·atioJl at th{' surface
is a sit!' of in(,I'PIIst'd dlt'miea] rel1l'tivity. systt'Tll; alit! j,E is tlIp l'han!rl' ill intt'rnal elll'rgy.
'1'11(, P:'PSt'IH't' of ('rystal dl'fpds ill p,vl'ot{'C'hnie If til(' syStt'lIl ab~orbs ht,tlt, If has a positive valne;
inl!rt,(lit'lltS ('11ll haYt' a mal'kt'd illfllll'llCI' on tl;t' if tlIl' systt'lIl dot's work. w hilS a lJositivt' valut'.
('OIlI'l>;t' of tht' rpadioll lind, th('I'pfo!'p, illflllt'I!!'(' tilt' TIlt' val1lt' of 1lJ..' dqwJlds only 011 tht' initial and
fIllal statt' 0 1' tht' systt'lll. 'I'h!' qualltitit,s fJ and w
('hal'lIt"tt'I'isti(' 1}{'llayior (imilldiJl)! stability and out-
Pllt) o~' P,\'l'ot ('('hlli(' (·olllj)ositioIlS. d"\H'lIt! 011 t h(' path tak"ll fro\ll tilt' initial til tht'
/illal stat!'. }.'!)I' <l ('YI,li(' pro('!'ss, i.t'., a. pnw.ess
'.Vhidl Itas the sam!' initial and final stage, ilE = ()
3-2 THERMODYNAMICS
";0 tllat (I == 'U'.
'l'h("'III(HiYllilllli('s is th,· study 1)1' t ht' quulltita-
t i ':t' J't'lai lOllS hips hd \\'('('11 h('at and ot Iwl' forms of
3·2.1.1.1 Heat Effects at Constant Volume and
t'lIt'n!y, i!l all ('as('s. ('llI'IX)' ('all ht' p;;pr'l'ss('d as
Constant Pressure
tilt, pl'odlld of t\\'/I fal'!ol's. all int('nsity t'a('/ol' (i.t",
Th,' h"al !'t,!t'a>i('d b~' II pyrot('I'llIIit' rpal'1 ion t'llll
t"llIlkl'atllJ'(' ditl't'r"IIt't'), alld a (·illllll·ity fador (i.t'.,
I'aist' III,' l<'lIIpt'ratlll't' of th(' !'l'udioll pr()(lut,ts,
llt'llt ('a/lilt·it." I. III th,· 1'1,'lwti,H\ of a l'Yl'o!I'\'hlli('
('a liS" plraSt' .·hl11I~'·S, alld ('allSt' otlI .. !' ('hpllIi(,1l1 re-
(,OlllP(ISititlll, th,· (,II,'mi('1l1 "ll"I')!,\' is ('OIl\'P!'t,'d illto
avl iOll," (;IIt'\1 as diss(wiat inll) to takt' pial"', If a
Ilth,,1' 1'1l['1I.\" of t'lll'J'g-y. pl'illlilrtly It,'at 1!lltl work.
dit'llli"HI l'<'lwliUII or ph::si"111 dian!!,' tukt's plan' at
'I'll" pl'<,dlH'\:i hI' "OllllillstiOl. aI'" IIt'id"t! to tli(, I','al"
('()IISlalll \,ollllllt', alld ollly prt·ssllrt'.\,olulllt' work
tioll I ('llIJH'ratlll'l', aJl(l, if 11Ill'ollfillrd, \\'ork l'all b('
i" ('oll"iti,'r,'(L llit' IIl1illllllt of wlIrk d01l1' is z\'ru IIlld
dOlI<' :t!!lIillst I lit· at lIlo"ph,·r,'.
tilt' II,'a I .. Il'"v' iU't'Olll pllll!, illg- tilt' rt'ad iOIl is t'q Hill
III t\I(' f(/lI(}wi/l~ Plll':I:.'I'<lI'II,;, ,,'rtHill La"i(' laws
tll 1ht· ,'''itlll!(' ill illl"I'lI1ti .'!It'I·),!,\'.
of t 1i('J'IIIIlt\y Jlilllli··.... t \)/'l'dIOdit'llIist I'y, ,·h,·lllil'll!
"'1llilihl'illlll, 1\1t' ('Oll("'i'i Ill' 1'1'"., "IItT~y, t'!('" arl'
,------------------------------------ ----- ----

AMCP 706·185

Chemical reactions, including many pyrotechnie 3·2.1.1.2 Heat Capacity


rea;~tions,
and pbysical changes may also take place The heat eapacity of a system is defined as the
at constant pressure where only prt'~sure-vo:.ume quantity of heat required to raise the temperature
work is considered and tbe heat effect L, equal to 1°(; or, eXJlrrsf~d mathematically:
the internal energy change plus the work done in
expansion, dq
c= dT (3-24)
qp= 6.E + pAv (3-19 )
Under conditions of constant volume, dq = dE,
In this case, it is convenient to use another thermo- Equation 8-18, and the heat capacity at constant
dynamic property, the enthalpy II, defined by: volume is equal to tht' change in internal energy
with trmperaturr, or:
H=E+pl' (3.20)
(3-25 )
Then, for a chemical rt'action or phase change oc·
curring :1t constant prt'~sure, when only pressure- While thr intrrnal energy E is a function of the
volume work is considered; thrl'e yariables 1', P, and 1J; only two are required
to defillt' the systrm, A derivative, therefore, with
Ml = 6.E + pAt' (:3.21 )
respt'ct to only 0111' variable T is expressed as a par-
and t}1(' heat l'fi't'l't at constant pn'ssurr is equal to tial df'rivatiw (~~),' with the subscript v denoting
thl' l'hallgt' ill enthalpy:
tht' \'ariabll' to be held constant.
lJp = 6.H (3.22 ) At constant pressure, the heSot capd-city includes
both Ule heat ahsorbed to illerease the internal
If gaSt'nus products are assumed to bt'have i(leally : I'Ilt'rgy pIllS th(' heat l'qui\'alent of the work term
pill'. Hinet', under thest' l'onditions, dq = dH,
6.1I = dE + AnRT (3 ..23 )
Equation :~-22, tht' heat l'apacity at constant pres-
wherl' 6.n = ~11 (produds) -- ~n (rl'aetants) for snrl' is t·qllal tll the ehange in enthalpy with tem-
the gaseous matt'rials involvt'd ill tilt' rt'actioll, perature, or:
Thl'rt'iort', (lyrot('chllil' l't'aetions ill\'olving solid
j'pal'tants aliI! till' formation of ga~t'l)llS products
whert' Iwat is t'volvpd «('xothermil') will have a
hig}wr heat of rl'lIdioll at COllstallt YOIUIIIl', 6.E(l/v), 'I'hl' ht'lii {'/lplIl'ity lit \'Onstllllt prrssurt' ('an hI'
thull I1t l'OllstUllt preSSllrt', 6.1J (1/,,). III the latter 1'i\Il'lIll1tt,tI by t'qllatillH of tiH' form (l'itill'r OIl!'):
('aSt', I/p is rl'tiul'.l'll by till' ht'at t'ljllivlIlt'llt of thr {'p = (t + hT + c1'~
i/H'f('llst'd /-fIlSI'OUS produds, AnN?'. 'l'ht'sl' 1'I'll1tio11- {,'p =.:: a + b7 -t- (''/'
1
.'1 (:1-27 )
ships l'/lII bl' IIst'd to obtaiu ,,/lilli'S ('tllli\'ull'llt to tht'
wht'rt' II, h, HIllI (' art' ('Ollstllll!S. This tY!lI' l'qua-
standard hl'at of rt'al'! ion from homb l'alorillH'tril'
tioH IlJlJllit'S onr 1\ 11101'1' or It'SS limitt'd rallge of
llIl'lIS11rt'IIIt'lItl'o IIllldt' at ('Ollstllnt \'ohlln,'.
tl'IllJlt'l'lltlll"t'S 1I1It! for IIIlllly thl'rmoehl'lIlil'lIl I'al-
I'yrott'l'hui(' l't'lIt'liol1s takl' pla('t' IIl1dt'r ('Olltli-
1'lIiatiollS it is lIlort' l'ollvl'lli!'lIt t,) IIS{' 1111 {lVI'rag'I'
t iOlls of pitil,'r ('oust alit \'01111111', "ollstallt prl'ssurt',
ht'lit t'nplll'ity dl'till.'tl by:
or ('olllbillatiolls of both. COllstallt \'0 111 lilt' l'oudi-
tiolls O('I'UI' for til'lay systl'JIlS tlillt <In' obturatl'll,
allti ('Ollstllilt pft'SSUn' systt'lIIS t/l'('UI' for flart's, sig-.
1I1l1x, SBlokl's, awl thl' likt'. III photoflash itt'llIs, SUl'l1 (' (:J.2A)
liS ('artridgt's or' bombs, thl' ('oldill,·t! l'Olllpositillll
1'(11'
'/'., 1'1
fll II 1'1 inlls l!lId('I' ('OllstUllt \'Ollllllt' ('ollditiolls whell \\'ht'll lIt'I't'SSiI,..\". (', cUll Ill' uhtuilll'd hy sllbtrlldillg'
iuitiatt'tI alld it thl'lI ('olltillUt'S to l't'lIt't at t'Ol/stallt Ii \ t ht' IIlliVITSlI1 ~IIS l'(lllstallt) frol11 tIlt' \,Illllt' for
pn'sslIr •. , wht'll disl"'rst't! as till' l'aSt' rllptllrl's. ('p.

;J-H
AMCP 706-185

Heat capacity values are l'ssential for many capacities of solids at higher temperatures. s Where
thermochemical calculations involving pyrotech- thest' values are not available, the room tempera-
nics. 1'he temperature attained by the p~oduets of ture value may be used in conjunction with a value
a pyrotechnic reaction will drpend, in part, on the of 7.25 calories per gram-atom per degree-Kelvin
hea.t capacity of these products. Calculations of for the next transition point, assnming a linear in-
the heat balance for a given system utilize the creasf' of Cp with temperature.
heat capacity to obtain tht' t'uthalpy t·hange in 'fhe lwat capacities of molten inarganic sub-
going from ont' tt'mpt'rature and/or state to an- stances do not differ greatly from those of solid
other. The latest tablt's, however, provide enthalpy materials. When handbook values are unavailable,
ehallges directly, making it UllIWt'essary to calcu- Kopp's Rule may also bt' applied to compounds by
late heat eapal'itit's illdepl'ndt'lltly. assigning' thp following values of atomic heat
l'apacities to thl' atoms of the liquid: C, 2,8; H,
3-2.1.1.2.1 Heat Capacity of Gases -t.,3; 13, 4.7: Si, 5.8; 0, 6.0: F, 7.0; P, 7.4; S, 7.4,
awl to most oth!'r elements a value of 8.0.
Aecorciillg' to the kineti(' th('ory of gases, the
()t.IWI' Illl'thods for I'stimating heat capacities
heat capll('ity of ili('al gast's, Hll(i of mOllotomic real
of liquids and solids are Ilvailable. 6 In most cases,
gases sUl'h as h('Iium and argou, to relatively high
"aieIlJatil)lls are UIlJlt.'cessar~', as tht' -"alues have
tl'mpera~ures is:
bN'1I <'xpt'rillH'Iltally detcnnilwd and may be ob-
Ct , = 3/2 R = 3 caljgmole OK (3-29) tainl'd from handbook tabulatiolls,
The ht'at l'apaeity of liquids and solids decreases
(\' = C" +R= [) cal/gnwle OK ( 3-30)
('()Il,;idt'rably with II deerl'asp in temperature and
Diatolllil' 1'l'1I1 gases, iU('luding gast's such as oxygen is zt'ro at IIbsolllt.(· zero. For tt'IllIwratures below
and nitrogPll, and lint'ill' polytOllli(' 1ll0Il'l'lIlt's tave ;iOOK, tllP ])pbyt' gqllation applies and:
two dl'grl'('s of rotatiollal frl't'tIolll ill addition to
(' _ -tr-t :- . 'I n. ('a I OrIt'
.
tlt(' thl'l't' d('gn'('s of fl'('('doIll ass(wiatt'd with trans-
latiollal lIlotion. At lIol'mal Il'mpl'l'lIll1rt's the heat
, ..- ) •• J es de~rce-Kelvin gram-atom
(3-33)
('apa('itit's of tht's(' gaSt'S aI'!' IIppl'oxilllatt'ly:
WII!'I"> 'J' is tlit' absollltt· tplllpt'rature in dt'grt'es-
Cu ::::: 5/2 R = [) cal/gmole OK (a-:u)
I\.t'lvill, allll ~ is tl'rlllPd th!' l'harat~t('ristie tempel'a-
Cp == V" + R = 7 cal/gmoh' OK ( 3-32) IIII'!' and is dt'tillt'd by:

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


AI'I'OI'dilJ~ tu Iht' Illw of Dulong aJl(I Pl'lit, the
\\' hl'l'l' " is tilt' I'IUlll'k (·ollst.ant, k is till' Boltzmanll
molar hl'/ll ('aJlltl'it it'S of solid t'l('lIIt'llls (t'sJll'l'ially
Iht' J\ll't/lls) (', and ('p IIrt' IIpproxilllatt·ly li calories "OllstUllt IIlld v'" is tht' lIIaximuJlI vibration fre-
P('!' gl'allJ-atulIl 1ll'1' ,!t'I!l't,p-I\l'I\,ill. This is ill agret'-
qllt'llt'y. 'I'll ('St' \'/lltH'S Illll)' ht, found ill a suitable
II it'll I willi Iht, "/lllIt's of :IH, i.t' .. :i.!Jt.i (·a)oril·s per
hUlldbuok.
g'!'IlIll-ilIOIIl pl'l' dl'g'I"'t,-Kt'I\'ill, sug~t'stt'd Ly kineti('
11I1'01'Y· 3-2,1.2 Second Law of Thermodynamics
Thl' /lIolal' Ii I'll I t'apill'itit's of solid ('olllJlounds 'I'ht' S(>('Olld III\\' of tilt'rmodynamj('s llIay be ex-
,'all /)(' t'stilllall'o/ by lIsillg' l\o/lP 's Hull' ",hii'll slatt's PI'I'SSt't\ ill liluny WIl)'S. A \'t'f,\' Rt'llt ral litat.t'rnent
that tht' ht'at ('/lllIlt'ity of a solid ('Olllj)(llllld is ap- i~ Illat 1I1l,\' spolllallt'OliS t'hallg-t' will rt'lldt'r H sys-
JlI'UXilllllldy ,'qlllli to tht' SlIlIl of th,· ht'ilt ('/lJlllt'itit,S It'llI IIfld its Slll'rol"ldin,,~ ('Iost'r to lUI ultimate state
tlf tht· t'()Il"titll"llt I'lt'IIIt·lIts. III w,illg' Ihis I'll It·, tht' ()t' t'1jllilihrilllll 1'1'0111 whil'h 110 further (,hllllgt> can
followilW IIIOllli\' ht'al t'/lil/It·it it,S ar.' IIss!g'Ilt'd to spollta 1ll'()llsly Ot't'llr. '1'lwt i... , lilly isolatt'll system
llit' t''''IlIt'llls: C, l.s; 11, :!:!; H, :!.7; ~i, :l.s; 0, Itoft llllilllt'lldt,d will dllllll{t· tcwlll't1 a ('ollditiun of
·1.0; }<', ;,.0; 1', '-,.-1; ~, ;-1.·1; IIlld 1111 otht'l's, Ii.:!. 1I111xilJllllJI probabililY. III ortit'r to oblliill Ii (IUlill-
(lth.'r Illt'lhods art' IIllIilablt' ful' ('stillwtilJ~ !it'lit litlllir,' IIlt'a;';llrt' of tli,' prllbahility or rHlldollllll'!\S

3-9
_Ud,GP 706,185

of a system, the concept of elltropy has been estab- (3-39)


lished,
}<'or pyrotechllie r(~actiolls, ma.ny of which proceed
The absolntp entropy 8 of a substance in It par-
at ('Ollstant prf'SSlIre and temperature, the Gibbs
ticular statt'-ullder specificd conditions of tem-
free PllPrg'Y }I' is a mori~ useful function, The driv-
pcrature, volulIlP and pr('ssurp and in It known state
illg' fOt'cr or dlallg'e ill frc!' energy is important ilnd
of aggregation; solid, liquid, 01' gas-is propor-
is ('X pressed by:
tional to thl' )ogl"'itJ.m of the probability of finding
tlw substlUwe ill that statt~, ap = a[[- Ta/3 (3-40)

J /l this ('ase, till' ('riterion of spontaneity is:


1-: = k III 1fT ( 3-35)
( 3-41)
wher~~ It is B()lt~Ill'lIln 's ('Ollst<lnt, and W is the
Jlmbabilit.y, As Ii ('O/lS('qupllce of Equations a-:3S and a-40, addi-
Entropy, I:k(' internal t'nl'rgy, d('IH'II(),' ulII," 011 h;JIIal stat(,lI:ellts lIlay he made reg'arding the spon-
tht' init.ial ilnd tillal stal('~ of :! S,Ystt'1I1 and, for an t all('ity of ehplllil'al reactions, 'rlH'se art> summa-
iltiillit('silll<l I I'('\'('rsihl(~ pl'()(~eSS, is ddin('d by the l'ilWd in 'rabl!' :1-1,
f'q uHtion : At ordinary temperatures, eptropy effects are
slllall so tlwy haY\' little I'ffect un the direction of a
dq (f(~\')
d8 = --'--'-:::-- ( :l-:JG) ('hl'llIi('al rl'actioll IInless the ditrerellC(~ in energy
'I'
DB or all betweell real'tauts and products is rela-
where dll ( !'('v) is t h(' ht'at absorlwd frolll t111~ Sl\l'- ti\'ely slIIall. At higher temperatures, such as those
l'OlllHlillgs ill a /'('\'(,I'sibl(' pl'oeess, i.('" tL J)l'Q('CSS I'('sult.ing' frolll pYl'oteelllli(~ reaetions, tlw relative
('alTi('d out in s!lt'll a IIHlnl\(~I' that It eould hp 1'('- illlporta/l(~l' of till' ('hang'1' ill l'lItropy inerrascs until

\'(,I's('d h~' all illtillitl'sillllil ('hallg'(' ill ('xt(,I'llai ('011- il IH'('OIlH':, a (loll1inl'Lllt fa('tor, Hrlll'(', all chemical'
diti()n,~, J';lltI'OPY has tht' SI111I(' lIllils as heat cu- I'padiolls wili('h illvo)w an illl'reas" ill entropy will
JJ:~I'ity, i,I' .. ('alol'it's IH'I' g'nlllHttolll !lP!' degl'('('·KI'I- (I('('Ul' spontulIl'ollsly if tltt' tcmperaturp is high
VIII. t'/lollg'h, A dis('IISsioll of free l'llcrgy and the equi-
By lIsiJlg ('nlroJlY, th(' S('('oIHI law ('1111 IH' ('x- libriulII (~()llstHI'I is JH'('S(mtl~d ill Paragraph 3-2,3,
11I'('s~;l'dIllal h(,llIati(~ally :
3-2.1.3 Third Law of Thermodynamics
A('('ol'tiillg' 10 tIl(' third law of thcrmodYIU!mics,
g\,(,I',\' spolllalll'ollS dl1l I!i!t' ill a S,\'sj('III, 1I1I'I'('fol'!', I hI' (,lltl'f)P} oj' it IWl'fl'et. (~rysta\liIH' sllbstance at
IS III a dil't'l'l i"ll slwh 111'.1 ils ('III I'Opy, pillS that of OOK is ZPl'O, AltI\lIu~dl it is impossible theoretieally
its SIII'I'Ollllllillg's, illt'l'paSl's, lIo\\'I'\'t'I', if thl' sys- to attai,!, absolut(' 7('1'0, tlH' validity of ~lle third law
1t'lIl alOlll' i~ ('ollsidl'l'l'd, SpOil 1alH'i I y of ('Ii('mica I hw.; h"('1l t,h('('k('d hy ('Xllel'illl('ntatioll. It ran also
l't'al'1ioll" lIIay ht' 11'('alt'<I hy tal,ill~ lwo (It'ivillg' h(, slil)\\'ll thai till' "'1tl'opil's of all pm'(' ehelllical
1'01'l'('S illio ;\('('011111; a tl'lld"II"Y to adopt tl\(, lo\\'('sl ('olllllllllllds ill tili'il' st.ablt, stlltt'S at ()'"l( art' zero
"lIt'I':!,\' alit! a 1('lIdl'II(',Y to :Idopt. IIt(' Ili).rh("'t, (,II- !J('('lII1SI' ~ ht'i,' j"Jl'lllatioll 1'1'0111 th(, dt'IIH'lIts is:
I I'Opy, I r I h" hl'o ('ltall).!'t's <11'1' Oppos('d, tilt' syst('1II ~''''II· 0, 'l'his law stat!';; iha t absolut!' l'Jltropips
will PI'O('('I,d ill tIll' din'('jillil ,d' ,h(, lal'g('I' ('hallg'I', 01' ~o-l'idlt'd thil'd law ('Iltl'ol,h ,; t'lt11 bl' dl'terrllim'd
If Iht, I\\'() 1!llillltiti('s al'l' t':-;;!I'II,\' t'qual, 110 ('hallg'I' t'I'OJlI Itl'ltt t'apl11'it,v data ('xt 1':l}Jolal('rl to 0° K whidl
will (w,'111' alld tIll' "y:-;II'1I1 is said to !)f' al ('qlli- "illl lit, lISl'il ill ('l!lIilihl'iulll (~al,~lIlati()lIs:
lilll'illlll, Tit" 111'1 dl'iyillg' 1'01'('" is t('~IIII'd IiiI' \Vnl'k
1"llllt'lilHI 01' 11"lltdll!ll;t, 1'1'('(' t'lIt'I':!,\' .1, alld al ('011-
~;t;1II1 1"lIlp, .. ,,,III/'(' :1:"Jt;
8 ~':: or
L. ( , r
'/'f)
!.:!~- )
'I' ( ,II,/, --t ( :1-42)

(:1·:11-1 i
I tI'l'
----
(
I' l' tlrl' 111('I'I'a"I' III I'II/rupy, is ob-
"'01' ;( "jllllllalll't111s (l1""'",;s at ,'oll:-;tallt \',l1ll1l1t' alld
""llst<lI:1 1,'lllp,'I'all/l"" .1.1 Is alwllYs III'galiYI': 1'(1

:1- 1()
AMCP 706·185

TABLE 3·1
CRITERIA OF SPONTANEITY

Condition.~ '1'y '~ of Reaction Criteria

General , Reversible 6,8 (t0tal) = 0


SpontaneIJU8 6,S (tctal) > 0
E, v constant Reversible D.S lisolated sYRtem) = 0
Hpontaneol1s r\S (isolated system) >0
'1', v constant Reversible D.A = 0
Spontaneous D.A < 0
7', P ('onstant Rpversible D.F = 0
Spontaneous D.F < 0
8, v consi;ant Rpver<:~ble D.E =0
Spontanpom', AS < 0
S, P (·onstant P'versible il.1I = r
~pontaneous D.H <: 0

talurd for each phase by graphical integration and 4. Whether or not the re lction is at constant
~pc, the entropy increase due to a phase change,
volume or COl stant pressure.
The specific influence of these conditions j'J de-
is determined for each of the phase changes. The
scrih£>d in the para~raphs which follow.
Debye Equati0n (Paragraph 3-2.1.1.2.2) is used
for the temperature range OOK to approximately
0
50 K as experimental data a.;.-e difficult to obtain 3-2.2.1 Heats of Reaction
in this temperat'lre lange. Absolute entropies can The heat effect associated with a pyrotechnic
also be caleulated by the method of statistical or other chemical reaction is the heat of ~·eadion.
IlIpehanics. r. 'l:'he heat of format·.vn is the heat of the reaction
associated with the formution of a compound from
3·2,2 THERMOCHEMISTRY its elements. 'l'he heat of combustion is the heat of
'l'hermoeht'm:stry is the study of tiI<, heat effects the reaetion associated with the complete com·
at'companying ('}lPmical reactionR, the formation of bustion of a substance in oxygen. The heat of ex-
solutions, and (~hangt's in state such as fusion and plosion is the heat vf reaction associated wH;h the
v.lporizatiou. Since tl:e amo.Hlt of hrat librraten rapid explosiVt' decomposition of a material in an
from a pyrotecnni(' reac·tion stl'ongly int\uPIlces the inert atmosphere.
~haracteristi(' output, I'n un(ierstanding of the For pyrotechnic reactIOns at constant pressure,
principks and applieation of thermm'hemistry is if only pressure-volume work is considered, the
of vital importance. heat effeci. qp can be obtained from the enthalpy
Thf' heat ~>volvrd (vr absorbl'd) ill a ehrmical l'hangp for the reaetion as follows:
r!'Retion depf'udfl upon:
qp = D.H (reaction) = 'f.H (products)
1. 'rill'propl>rtif's of thl' products and reac- - 'f.H (reactants) (3-40)
tants, and the amount of thest' substatH'es in-
volved. Tf tlw readion is u standard st.ate reaction,
2. The physi('al stat!' of the substaacl>s ill- whl'f(' th<' rC'aC'iallts in their standard states react
volwd. to giv<' the products in their s+andard states and
;~. Thp t\'mperatutt' and prt'ssnrt' at whid} the the fltuTJilard lleats of formation D.H 7'0 (f) of the
rt'action takps plllt·f'. plemt'llts is assullw!l 10 bp zero at any given tern-

3-11
AMCP 706-185

)liP

Figure 3-3.l3ff8(;t of Temperature on EntflallJY Change for Chemical Reaction

perature, then the standard heat of reaction i1HT o 3-2.2.2 Effect of Temperature OD the Heat of
(reaction) is: Reactil)D
As illustrated schematically in Figure 3-3, the
AHrD (reaction) = AH(f)To (products) heat of reaction at ar'v temperature T and constant
- MI(fh o (reactants) (3-41) pressure is :

AHT~ = + ~ (f~:dT + AlIpc) (reactantR)


The actual choice of standard states is somewhat a
arbitrary. Normally, the standard state is the most Allr R

stable state at one atmosphere pressure and at the T


given temperature. (Most tabular data are given
at OaK or 298°K.) T
Most thermochemical ealculations are hased on + ~ (fCpdT + AlIpl') (products) (3-47)
tabulated standard heats uf iormation. 'l'he heat Tn
"ffect .. t constant pressure (qfi) can be calculated where AH TO is the heat of reaction at temperature
by: T, AN°TR is the heat of reaction at a reference tem-

\ reaction) = AlIT (reaction) ::::::::


( q,,) '1'
All 'f' ° (reaetion) (3-45) perature TIl, ~ ( 'fTRGpdT + Allpe )(reactants) is

Unless the actual pressu:..·,: is high, no appredable T


error is introdu(~ed. thp heat evolved or absorbed in cooling or heating
~imilarly, the heat e/feet itt eonsuwt vol'Jme the reactants from T to 'I'll, including that evolved
(qv) can be obtained by: or absorbed 8,8 It result of phase changes AlIpe.

~
(q"h (reaction) =: AE (reaction)
A.Ti} r ° (reaction) :-:::: I:.AE (f h 0 (prt,ducts)
Rimilarly, (f TCpdT + AliI"') (products) is the
-- 'f,AE(f)rO (reactants) (3-46) TIl

3-12
AIICP 700-18..')

heat absorbed or evolved in heating or cooling TheL:e tabl!'s clln also he us('a for calculations
the products from T/I to 1'. According to Equation of free ('Ilrrgy (~hanges for chemical reactions. This
3.47, if th(' heat rvolved by eooling the reartants is shown in Paragraph :1-2.3.5
from the higher to the lower temperature is gl'eater
than the amount absorbed in heating the products 3·2.2.4 Bond Energies 1
from the lower to the higher temperature, the heat Bond energy (B.E.) is defined as the average
of reaction at the higher 1emperatllre will be great. mnl)unt of energy per mole required to break a
PI" than that at the lower temperature. particular type G1' bond in a molecule. Bond eneI'·
In cases where reactiolls begin and rnd at the gies may be calm:.ln.tcd when heat of combustion
same tempcrature and where no changes in ph lise data are available. However, of l:,'Teater utility is
are involved, the standard iwat of '"eaction at the estimation of the heat of reactivn from bond
temperatllrr T is defined by: l~nergy data for compounds for which no enthalpy
data are available. In this casc:
(:3-48 ) ~H = B.E. (bonds broken) - RE. (bonds forn;.ed)
(3-51)
Til
where ~Cp = ~Op (products) -- ~Cp (reactants), Bond streugths or hond dissociation energies may
and H T o R is the standard heat of reaction at the differ from mean boud energies derived solely
reference temperature T1/. 'fhis is known as Kirch. from thermochemieal data on Illoleculeb and atoms.
hcjf's Equation aJJd, for small temperature
ranges, heat wtpacities may be treated as constant 3-2.3 FREE ENERGY AND EQUILIBRIUM
and the equati(Jll r~duces to: A state of chemical equilibrium exists in any
~]{TO = J.Il T o II + ~Cp(T-TR) (3-49) chemically reacting system when no further change
in compusition with hmc can be detected provided
For othrr eases, experimental heat capacity data
the temperature and pressure are not altered. The
expressed in the form shown in Paragraph 3-2.1.1.2
(~riterioll of equilibrium is that the change in free
must be Ilsed; however, if enthalpy tables are avail-
energy of any possible reaction !lnder these condi-
able, heat eapal.~ity data need not be considered as
t ions shall be zero.
such.
Wher(~ data are l'equired at temperatures above (~Fkp=O (3.52)
~hofle listed, it mel)' be ucce£:>ary to e:l!.:trapolate the
111 ordrr to estimate maximum flame temperatureE
data to the desired temperatllrr.
from pyrotechni(' reactions, a knowledge of the
3·2.2.3 Enthalpy Tables e'lllilibrium concentrations of the combustion prod-
ucts is required ill additIOn to information on the
Calculatiollf> of heat of reactiull at differ('nt
heat released. If a state 01 equilibrium exist.s among
temperaturl's art' simplified if tabular enthalpy data
the JH'oduct species, the equilibrium c(lmposition
are available. Tables 3-2 for solid magnesium ox·
for the combustion products is fixed at a given
idc, :l-:l for solid aluminum oxide, :3-4 alai ~-5 fIJI'
temperature and pressure (or volume) when t,he
solid and liquid sodium I)xidr, and :3-6 for ga.seow'
atomic composition is specified.
oxygen, (!ontain these data. In these tables, stan-
Pyrotechnic reactions often illvolvc the oxida-
dard hpats of forma.tion ~Jlfo, at different tcmpera-
tion of a metal to form a refractory oxide. This
tures, are tabulated. In other tables only values
reaction limits the ma."dmum temperature attain-
for tht' puthalpy ilUwtioIl, HO - II T /I 0, along with
able to the vaporization temperature of the metal
the heat of fOJ'mation at S(l!ll(~ referenel' tempera-
oxide whpther this oxidl' decomposes on vaporiza.
turl', usually O°I( or 29B.9:3°K are tabulated. The
tion, 01' not. Th~ mptals commonly used as fuels
heat of r('aet ion at any temperature becomes:
ilL pyrotechnit·s deeompos(' Oil vapo:oization. In
fill T
O
cc::: ~/lTR ° + ~(HO --1I"'1I 0) (products) mo;;;t cases, thl' metal dc::!omposrs to yield metal
- '2:,(H" - HTR 0) (reaetallts) (8-50) atoms; how('\'t'r, a few metal oxides, such as alum-

3-13
AMCP 706··185

TABLE 3·2
TB'ERMODYNAMIC PROPERTIES OF SOLID MAGNESIUM OXIDE
Magnesium Oxide (MgO) (SoUd) Mol. Wt 28.32 =
,_.. _ . ____.__.___ ~al. mole- l deg.-' _ _ _ _ ~ ~_ _ _-_--kcal. roole- I _____- - - - - . .
T, OK. C~ SO -(Fo-}lo",)/T }1°_Hom ,6.Ho 1 6Fo, LogKp
0 .000 .000 INFINITE - 1.235 -142.702 -142.702 INI<'INITE
100 1.865 .608 12.488 - 1.188 -143.156 -140.918 307.961
200 6.380 3.369 7.184 - .763 -·143.559 -138.501 151.340
298 B.9Otl 6.4:19 6 439 .000 -·143.700 -13u.981 99.672
300 a.g39 6.494 3.439 .017 -143.701 -135.933 99.022
400 10.148 9.252 6.807 .978 -143.705 -133.310 72.850
500 10.854 11.598 1.537 2.031 -143.654 -130.755 57.150
600 11.323 13.621 8.386 3.141 -143.583 -128.181 46.688
7GO 11 .656 15.393 9.263 4.291 -143.513 -125.619 39.218
800 11.905 16.966 10.130 5.489 -143,457 -123.067 33.619
900 12.098 18.3~ 10.969 6.670 -143,4?.5 -120.521 29.265
1000 12.251 19.663 ll.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 -145567 -109.478 18.404
1400 12.638 23.854 14.658 12.874 -176.04'/ -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.a51 - 81.574. 9.383
2000 12.915 28.415 18.139 20.551 -174.008 - 76.699 8.381
2100 12.945 29.046 18.644 21.844 --173.665 - 71.84.4 7.477
2200 12.il71 29.M8 19.130 2:j .140 -173.321 - 67.004 6.656
2300 12.994 30.225 19.600 U.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 - 52.572 4.596
2600 13.052 31.822 20.920 28.346 -171.955 - 47.790 4.017
2700 13.068 32.315 21.333 29.652 -171.616 - 43.018 3.482
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 - 33.518 0.526
3000 13.107 33.6!H 22.501 33.578 -170.613 - 28.785 2.097

(JANAF Thermodynamic T ..bl.... Interim Tablel.. ued D_mber 31.1960)

inullI oxide, deeomposp to yield a llIixtm'p of other chemical reaction is directly proportional to the
oxide molecuh's. 'l'ypical of the decomposition re- "active ma1'ses" of the reacting materials. For
a(,tion is the following general reaction: 8 any ehemical reaction:
MxOv (1) ~ xM(g) + y/2 Oz(g) (3-53 ) aA + bB + ... ;= gG + Hk ...
where M represents a metal t'lpllIrnt. Since the where the capital letter indicates a chemical species
reactions are reversible, the degree of decomposi- and the smaH letter indicates the number of moles
tioh will depend on the oxygen partial pressure as of each species.
well as the temperature. At the high temperatures An equilibrium constant for this reaction, desig-
produced by pyrotechnic reactions, many other natl'd K, can be written in terms of conce.ltrations:
equilibria, such as the dissociations of gaseous
products, relatively unimportant at lower tempera· K_ .J!Jil. _. [Gjll (HI h
( 3-54)
tures, must be considered. - k(r) -- [AJa [B]b

3·2.3.1 Chemical Equilibrium where the open brackets r 1 indicate a concentra.-


Aecordiug to thl' law ~)f mass action as stated tion term, k (n is the specific rate constant for the
by C. M. Guldberg and P. Waage,D the rate of a forward reaction. k (r) is the specific rate constant

3·14
AMCP 706·18.5

TABLE 3·3
THERMODYNAM.IC PROPERTIES OF SOLID ALUMINUM OXIDE
Aluminum Oxide (alpha AI2 0 a) (Crystal) Mol. Wt. = 101.960

'-----------ca. mole-I deg.-l _ _ _ _ ~ ~-_ _ -_,-kC81. moI6-1______ ~


C~ -(F -W,08)/T HO-Ho... L:l.Hor Ll.For
O
T, oK. So Log Kp
0 .000 .000 INFINITE ,- 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 -385.3~ 421.047
298 If/.889 12.174 12.174 .000 -400.400 -378.078 Zl7.125
300 18.979 12.291 12.174 .035 -400.406 ·-377 .940 275.316
400 22.986 18.339 12.972 2.147 -400.555 -370.418 202.378
1,00 25.345 2::!.752 14.598 'L577 -400.475 -362.89J 158.612
600 26.889 28.517 16.529 7.193 -400.304 -365.389 129.444
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 :n.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 11.681
1600 31.920 57.5S9 34.321 37.181 -402.119 -Zl8.334 38.017
1700 32.220 59.SOa 35.745 40.388 -401.635 -ZlO.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 29.3·59
2000 33.000 64.803 39,716 SO.175 -400.075 -247.619 27 .057
2100 33.220 66.419 40.949 53.486 -3')9.521 -240.011 24.Sn
2200 33.450 67.969 41..142 56.819 -398.\J56 -232.427 23.088
2300 33.670 69.461 43.298 60.175 -398.374 -224.872 2L367
---~.-- - - - -- - -- - - - - - - - - - - - - - - . - - - - -- - - - - - _.- - - - - ~- - - --
2400 33.880 70,898 44.418 63.553 -397.779 -217.339 19.790
2500 34.100 72.286 45.S05 66.952 -397.172 -209.834 18.343
2600 34.310 73.62i 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 -S35.307 -171.598 12.931
3000 35.140 78.596 SO.S08 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 3&.720 81.973 53.217 94.894 -530.908 -121.718 8,06l
3400 35,9C3 83.042 54.078 98.476 -529.777 -109.338 7.028
3500 3lL095 'Yf.085 54.\)21 102.07!i -528,634 - 96.992 6.056

(JANAF Thermodynamic Tables, Interim T.ble ' .. ued March 31, 1964)

for the revel'S(' rt'aetioll, and K is th(' equilibrium stant. The expression in terms of p3rtial pressures
(·onstant. Tht' ('oll(~('ntration ean bp expressed as for the f'<juilibrium eO!lstant, therefore, will in-
a partial pr~'SSIHp or as a mole fraetion ill addition ('Iude only terms for tIlt' gaseous materials.
to the mort' ('olllmon eOI)(~t'ntratioll units. Por aetual The Pljuilibrium between phasps is an important
syst('rr1S, aetivities or fugaeities f..t)(H1ld 1)(' used in- tyP(' of heterogeneous (,quilibrium. Th(' free ener-
~tead of (·O/welltrations. 5 ,11 gies of til(' vapor and liquid phases are the same
WIH'll more than Ollf' phase is pr!'sP/lt, as is true whieh l,'ads to tilt' derivatiou of the important
for most pyrott'ehllie rpaetions, the (·quilibrium is ('In: lsins-Chqll'yron Equation: u
het{·rogell('(Jlls. ~ine!' tIlt' partial prf'&<;lIres of the
glls phas!'s ill t'qllilibriulll with the solid phases are (a-55)
('Ollstllnt at a giV(,ll telllperatur!', tlH'Y ('all be a~­
SUlIIt'd to h!' ill('orporated into tli,· "<juilihrium (,Oll- In this pqt!atiol!, p is til<' vapor pressure in milli-

3·15
AMCP 706-185

TABLE 3-4
THERMODYNAMIC PROPERTIES OF SOLID SODIUM OXIDE
Sodium Oxide (Na 2 0) (Crystal) Mol. Wt. 61.982 =
_ _ _ _ _ cal. mole-I deg.- I_________ kcal. mole-I _ _ _ ~
T, oK. C~ So -(PO-HOm)/T H o_H 0 . . . .6Hof .GFo, LogK,.
0
100
200
298 17.436 17.H90 17.990 .000 - 99.400 -9Cl.125 66.060
300 17.454 18.09B 17.990 .032 - 99.398 -90,007 65.610
400 18.442 23.254 18.687 1.827 -100.647 -86.862 47.457
500 19.430 27 .475 20.034 3.720 -100.601 -83.417 36.460
600 20.418 31.105 21.584 5.713 -100.428 -79.995 29.137
700 21.400 34.327 23.178 7.804 -100.138 -76.612 23.918
800 22.394 37.249 24.757 9.994 - 99.737 -73.277 20.017
900 23.382 39.944 26.297 12.283 - 99.235 --69.998 16.9'.17
1000 24.370 42.459 27 .788 14.670 - 98.641 -66.780 14.594
1100 25.358 44.828 29.231 17.157 - 97.966 ~3.629 12.641
1200 26.346 47.077 30.625 19.742 -143.685 -59.625 10.859
1300 27 .334 49.224 31.974 22.426 -142.423 -52.670 8.854
1400 28.322 51.286 33.280 25.209 -141.067 -45.~17 7.152
1500 29.310 53.274 34.547 28.090 -139.615 -39.004 5.691
1600 30.298 55.197 35.778 31.071 -138.067 -32.409 4.427
1700 31.286 57.064 36.975 34.150 -136.420 -25.854 3.324
1800 32.274 58.880 38.142 37.328 -134.681 . -19.40l 2.356
1900 33.262 60.651 39.280 40.605 -132.846 -13.044 l.500
2000 34.250 62.382 40.392 43.980 -130.916 --6.791 .742

(JANAF Thermodynamic Tables, Interim Tablel8llUod June 30.1962)

meters of mE'rcury, T is thE' absolutp temperature, 3-2.3.2 The LeChate1ier Principle


R is the universal gas constant, and 6.1I is the heat The LeChatelier principle states that if a stress
of vaporization in calol'ies per gram-mole. If 6.II is brought to bear on It system in equilibrium the
(~an be considered constani OVE'l' thE' temperature system will adjust itself to diminish thA applied
range of interest, then: stress. l"or exampll', in the decomposition of a
metal oxide in a confined system, the partial pres-
log P = (-;.~~) (- ~ ) + ('on stant (3-56 ) surE'S will increase and the reaction shifts to thl::
ldt. A high!'l' temperature is required to decom-
This equation is of the same form a:,; the empirical pose th!' oxide.
eq uation given ill paragraph 3-1.2.1 relating change WIWIl heat is absorbed by a clll~mical reaction,
ill vapor prE'SSUl'e and temperatul'f'. All ('!lua.tion an ilwrpase in temperature favors the reaction; on
(If similar form relates th~ sublimation pressure the otht'r hand, if heat is evolved by thE' reaction,
and temperature. an increase in temperature will favor the reverse
The heterogt'tleolls metal oxidt· de(~omposition rp!t('tion.
equilibrium iilustrated by Equation :3-fia is im-
portant to the study of pyrotechni(' reactions. The 3-2.3.3 Free Energy and the Equilibrium Constant
expansion for the eq uilibriulII {~()Ilstal\t for this l<~()r any (~h('fl1ical reaction the change in free
reaction ill terms of partial preSSllri'S Kp can be Plwrg-y is g-i vell hy
wnttRn:

(:3-57 ) 6.,,' = RT In ~ (3-58 )

wh?re Po:! is the partial pressnrp of the oxygen and whpre K is tlw ('(tuilibriUln constant. () is a ('on-
PM is tht' partial pressure of tIll' mptal vapor. tinllOw; flll1ctio/l similar in form to K (Equation

3-16
AlIICP 7()6..1B5

TABLE 3·5
THERMODYNAMIC PROPERTIES OF LIQUID SODIUM OXIDE
Sodium Oxide (Na 2 0) (Liquid) Mol. Wt. = 61.982

cal. mole· 1 deg.· t kcal. mole· l


T, OK. c~ So -(FO-HOm)!T HO-Ho", Ll.Ho r 6For LogK.,
0
100
200
298 Zl.OOO 17.889 17.889 .000 - 93.996 -84.691 62.077
300 Zl.OOO 18.056 17.890 .050 - 93.977 -84.632 61.652
400 Zl.OOO 25.823 18.949 2.750 - 94.320 -81.562 44.561
500 Zl.OOO 31.848 20.948 5.450 .. 93.468 -78.470 34.298
600 Zl.OOO 36.771 23.188 8.150 - 92.587 -75.553 Zl.519
700 27.000 40.933 25.433 10.850 - 91.688 -72.787 22.724
800 Zl.OOO 44.538 27.601 13.550 - 90.777 -70.148 19.163
900 27.000 47.719 29.663 16.250 - 89.864 ~7.624 16.421
1000 Zl.OOO 50.563 31.613 18.950 - 88.958 --65.201 14.249
1100 27.000 53.137 33.455 21.650 - 88.069 ~2.872 12.491
- - - - -- - - - - - - - - - . - -- - - -- - - -- - _. - - - -- - - -- - - - --' - - - - - - - - - - -
1200 27 .000 55.486 35.194 24.350 -133.673 -59.704 10.873
1300 Zl.OOO 57.647 36.839 27.050 -132.396 -53.592 9.009
1400 Zl.OOO 59.648 38.398 29.750 -131.122 -47.579 7.427
1500 Zl.OOO 61.511 39.878 32.450 -129.851 -41.655 6.069
1600 27.000 63.253 41.285 35.150 -128.584 -35.816 4.892
1700 27.000 64.890 42.626 37.850 -127.317 -30.056 3.864
1800 27.000 66.433 43.906 40.550 -126.055 -24.371 2.959
1900 27.000 67.893 45.130 43.250 -124.797 -18.755 2.157
2000 Zl.OOO 69.Zl8 46.303 45.950 -123.543 -13.209 1.443
2100 27 .000 70.596 47.429 48.650 -122.289 - 7.725 .804
2200 27 .000 71.852 48.511 51.350 --121.041 - 2.297 .228
2300 Zl.OOO 73.052 49.552 54.050 -119.795 3.070 - .292
2400 27.000 74.201 50.555 56.750 -118.554 8.390 - .764
2500 27.000 75.303 51.523 59.450 -117.316 13.649 - 1.193
2600 27.000 76.362 52.458 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 55.080 70.250 -112.421 34.234 - 2.580
3000 Zl.OOO 80.226 55.909 72.950 -111.213 39.269 - 2.861

(JANAF Thermodynamic Tabl€!!, Interim Table Issued June 30,1962)

3-54) but which applies to the "eoncelltrations" partial prf'SSllres. For example, thc equilibrium
or partial pressures of the products aml reactants cOllstant for the decomposition of a metal oxide,
at allY tinw during a partieular reaction. For real Elplation 3·57 is related to the standard free energy
gases and other substanccs, the K and Q should be c1langt' for the reaetiol1, Equation :i-fl9, as followtl:
terms of activities or fugaeities. If tlir f('action is
a standard stat(· reaction, til(' hypothrtical reac-
!::.po = _ RT In Kp = - RT In (Po 2(U) )1I/2(PM(O)'"
( 3-61)
tion in which thl' rt'actallts ill tlleir stalldard states
at OIW atmosplwrt' read to give j>rotiud.s in their where P02 is the partial pressure of the oxygen and
stalJ(lard ;;taU's at olle atlllosphpre, Q bt'comes unity P.II is the part ial pressure of the metal vapor.

and H('IH'r, Hw stability of th(~ oxide can be ealeulattd


!!..J;W = -- R'l' In R ( 8-59) from frequency data,
I<'dr a gasrolls rcal'tion involving gases which can
be ('ollsidl'1'ed idral:
!::.p o .= _
RT In Kp (:i·60) 3·2,3.4 Free Energy Calculdions
whef(' Kp is the equilibrium constalltin terms of Standard fl'e(~ energy ehanges for chemical reac-

3-17
AMCP 706·185

TABLE 3·6
THERMODYNAMIC PROPERTIES OF OXYGI<:N
Oxygen, Diatomic (0 2 ) (Reference Stat~Idea1 Gas) Mol. Wt. = 32.00

~ ______ cal. mole" deg-"___.. _~ kcal. mo16·'_ _. _ .. _.~


T, OK. C; So -(FC-HO",)/T W-Ho2U ~Hol Ll.F o I LogKp
0 .000 .000 INFINITE - 2.075 .000 .000 .000
- _. - __ - ___ - - - - - - __ - __ - - - - - - - - - - - - - _. ~ - ._0 _ _ _ .. _ _ _ _ _ _ ._ _ - - - -
100 6.741 41.52:2 55.142 - 1.362 .000 .000 .000
2f,() 6.871 46.233 49.641 - .682 .000 .000 .000
298 7.020 49.004 4~.004 .000 .000 .000 .000
300 7.023 49.047 49.004 .013 .000 .000 .000
400 7.196 51.091 49.28.2 .724 .000 .000 .000
500 7.431 52.722 49.812 1.455 .000 .000 000
600 7.670 M.09S 50.414 2.210 .000 .000 .000
700 7.883 55.297 51.028 2.988 .000 .000 .000
SOO 8.063 t;ij.361 51.629 3.786 .000 .000 .000
900 8.212 S7.320 52.209 4.600 .000 .000 .000
1000 8.336 58.192 52.765 5.427 .000 .000 .000
1100 8.439 58.991 53.295 6.266 .000 .000 .000
1200 8.527 59.'/29 53.801 7.114 .000 .000 .000
1300 8.604 60.415 54.283 7.971 .000 .000 .000
1400 8.674 61.055 54.744 8.835 .000 .000 .000
1500 8.738 61.656 55. 18!> !l.706 .000 .000 .000
1600 8.800 62.222 55.008 10.583 .000 .000 .000
1700 8.858 62.757 56.013 11.465 .000 .000 .000
1800 8.916 63.265 56.401 12.354 .000 .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 57.483 15.054 .000 .000 .000
2200 9.139 65.076 57.819 15.966 .000 .000 .000
2300 9.194 65.483 58.143 16.882 .000 .000 .000
2400 9.248 65.876 58.457 17.804 .000 .000 .000
2500 9.301 66.254 58.762 18.732 .000 .000 .000
2000 9.354 66.620 59.057 19.664 .900 .000 .000
~1700 9.405 66.974 59.344 20.602 .000 .000 .000
2800 9.455 67.317 59.622 21.545 .000 .000 .000
2900 9.503 67.650 59.893 22.493 .000 .000 .000
3000 9.551 67.973 60.157 23.446 .000 .000 .000
3100 9.596 68.287 60.415 24.403 .000 .000 .OOG
32()1) 9.640 68.592 60.665 25.365 .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
3500 9.762 69.461 61.383 28.276 .000 .000 .000
3600 9.799 69.737 61.611 29.254 .000 .000 .000
3700 9.835 70.006 61.834 30.236 .000 .000 .000
3800 9.869 70.269 62.053 31.221 .000 .000 .000
3900 9.901 70.525 62.'JKJ7 32.2O!l .000 .000 .000
4000 9.932 70.776 62..176 33.201 .000 .000 .000
4100 9.961 71.022 62.682 34 .196 .000 .000 .000
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 7J .728 63.275 37.196 .000 .000 .000
4500 10.062 71.954 63.4(;5 38.201 .000 .000 .000
4600 10.084 72.176 63.652 39.208 .000 .000 .000
4700 10.1(14 72.393 63.836 40.218 .000 .000 .000
4800 10.12.1 72.606 64.016 41.229 .000 .000 .000
4900 10.140 72.814 64 .194 42.212 .000 .000 .000
5000 10.156 73.019 64.368 43.2.57 .000 .000 .000
5100 10.172 73.221 64.540 44.274 .000 .000 .000
5200 10.187 73.418 64.708 45.292 .000 .000 .000
5300 10.200 73.613 64.875 'l6.311 .000 .000 .000
5400 10.213 73.803 611.038 47.332 .000 .000 .000
5500 10.225 73.001 65.199 48.353 .000 .000 .000
li600 10237 74.175 6.'>.358 49.377 .000 .000 .000
5700 lO.t47 74.356 65.514 50.401 .000 .000 .000
5800 10.258 74.535 65.668 51.4'JKJ .000 .000 .000
5900 10.267 14.710 65.820 52.452 .000 .000 .000
6000 10.276 74.88.1 65.970 s:; .479 .000 .000 .000

(JAN}}' 'l'hormodflWllic "'"bL", Jolerim Table Iaulld M... cb 31.1961)

3·18
Aliep 706·185

tions AJ!'To can be calculated from the standard the equilibrium constant with temperature is more
free energies of form~tion, t;.F'1'0 (f) : complicated.
flli' 'E 0 ="i:,AF'T ° (f) prod uets = };aFTO (f) reactants
( 3-62)
3-2.3.5 Tabulated Free Energy Values
Standard free energy of formation of the elements 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 fo1' the standard free energy of for-
The stand[l.rd free energy change and the associ- mation at variou:> temperatures. Tables 3-2, 3-3,
ated equilibrium constant (Equation ;j-fi8) are 3-4, 3-5, and 3-6 contain this information in ad-
functions of temperature. The change in free ditioll to the information on standard enthalpies of
energy, the enthalpy change flH, 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 compoupd
which, for a standard state reaction, is: from the elements in their standard states, along
with the equilibrium constant for the formation
-- dilF'° _ d(ET l~ K 1 ( 3-63) reaetion, are tabulated for various temperatures.
dT - dT
In other tabulations the free energy functioI!
If illP can be considered ('Olls:ant l'ver the range
of temperature, or is an average valti.;·: FT o - FTI'
T is tabulated for various temperatures
ilFO ilH o
R'l' = - log Kp = + 2.3RT -+ Constant (3-64) along with the standard free enf\rgies of formati(\ll
at sume reference temperature, whcre T is the reac-
If ilHo cannot be treated as a COllstant over the
tion temperatnre and Tn is the reference tempera-
temperature rangt', the ealeulation vf the change in
ture.
Then:
ilF'T" = };ilF7 ,O 11 (f) products - };ilFTR ° (f) reactants (3-65 )

+ "'T
,;., ----r--
( Pro --- FTR ) pro(I uets - ,;.,T
"" (FTO -T FTll
--- ) reactants

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

t1F298 ° = };f}.H~ U) products - };~H~ (f) reactan~"! (8-66)


F~!}Mo --1I~) "_,! H~)
+ ..,29R
" (
- - 298 products -- _ .. J8
(P29S0 ----
,--298 reactants

3-2.4 ADIABATIC FLAME TEMPERATURE ealeulations assume adiabatic conditions, i.e., no


The heat producl'd by all exotllerrnic reaction heat is lost to or gained from thr surroundings,
raises thr tf'mperatnre of the prod~.lets formed to and all the heat relea.<wd is utilized ill raising the
the reaetion temperature. 'rhis maximum tpmpera- tt'mperaturp of the produets and un reacted reac-
ture ellll bf' ealeulatl'd froUl a knowlef1ge of tIl{> tants til tht' HanlP temperaturr. At c:.mstant pres-
equilibrium composition of tIlt' ('ombustion produets Stir!', whrl"P the hrat eiTt'et assoeiated with a given

and of the energy I"eleasl'd by th(' reaction. The rpat'tion is ('qual to it.<; fllthalpy change:

( 3-67)

3-19
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -- - - - - - - - - - - - - - -- - - -

AMCP 706··185

composition of the combustion products allowing


for all elements and equilibrium relationships.lO
600 1 The calculation of the adiabatic flame temperature
is an iterative process for which use of a high
"0 ~ speed computer is recommended.
]'01' simpler cases, where the number of product

>00 ~ 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 rtlleased
..·1 by the chemical reaction will be absorbed.
400
The calculation of the adiabatic temperature
for some chemicall'eactions, including those involv-
»0
ing the oxidation of metals, can be simplified by
preparing an enthalpy or heat-content graph. This
,.
-'
0
graph consists of a plot of the beat content (above
.
"-
..J

"
>00

the selected reference temperature for the reaction


" products) as a function of temperature, using
~
.., 200

i
:::>
0
0
tabulated values for Hro - HTR 0; H T o - HO ,,0r
[ heat capacity; heat o~ fusion; heat of vaporization;
!
",£, .~ and heat of dissociation. The heat of reaction is
,'0
located on the ordinate of the plot and the hori-
zontal line is drawn from this value nntil it inter-

J -----
____ - - - - - BOILING
sects the heat content curve.l1 The adiabatic flame
- \
___ POINT
'00

\
AOIAeATIC fLAM( tpmpl'rature is read from the abseissa.
'1EWPER,ITUfiE'
')113- K
______ WUTING
'0

------
.----- POINT
3-2,5 SAMPLE THERM:ODYN AMIC
CALCULATIONS
The following sample caicubtioD3 have been
TEMPEFIATURE, ·K
selected to illustrate the application of thermo-
dynamics to pyrotechnic reactions.
F;gu'e 3-.-1. Enthalpy of Aluminum Oxide Versus
Example 1. The adiabatic flame temperature
/'emperature for aluminum burning in a stoil~hiometric amount
of (lxygen can be calculated as follows. Th~ overall
where 6.H r 11 0 is the enthalpy change for the reac- stoichiometric reactian is.
tion at a refereJ1(~e temperature Til; "i:,6.H (diss) is
the summation of the enthalpy ('hanges associated
2AI (R) + 1.502 (g) ~ AhOs (8)

with t hI> dissociatioll of gaseous pro(lucts and with The heat of reaction at 298°K is the same os the
iOllizati~\1l if tht' flam!' tt'mperatures art' suffieirntly heat of formation of Al 2 0 3 (s) ,..." 400 kilocalories
high: ;'':'6.1/,)(. is the summation of t.he enthalpy per mole. (See paragraph 3-2.2.) The heat con-
change!> af..soeiatcd with phase ('hanKes in the rear- tent plot for this reaction is given in Figu~e 3·4
wh!'l'e the reference temperature is taken as 298°K.
T 7' Approximately 400 kilocalories are released in
tioJl pr()liu('ts; alld ~
f
Til
(lp (products) dT is the
the formation of solid aluminum oxide at the
rt'ft'rt'Jwr tt'mperaturr of 298°K. As shown in
<-mOlln1 of heat necessary to raise the reaction I"iguJ'{' 3-4, approximately 140 kiJocalorit'A of this
products to the flam,> tt>mperature. l'lIf'rgy are rcquirt'd to raist' one moll> of aluminum
Befort' eaiculating th!.' enthalpy change for the oxid(' to its boiling' point. The diiferen('e (400 to
reaction, f'quations must be obtained for the molar 140 kiloealorit's) is ('onsllm('(l in vaporization of the

3-20
AMCP 706·185

Example ,g. The adiabatic flame temperature


/'
/' foJ' magnesium burning in air (20% oxygen, 80%
nitrogen) can be calculated in a similar manner.
110 _. The rep,ction, in this case is:

,.0 4 ..... ,...-144 ICCAL


The heat of reaction at the reference temperature
of 298°K is the heat of formation of MgO (s), or
144 kilocalories per mole_ Figure 3-5 is a heat con-
120 tent plot for the products of this reaction where
it is assumed that magnesium oxide vaporizes by
dissociation into atoms. It must be noted that the
;00
nitrogeu in the air ~ust be heated to the flame
..J temperature. The adiabatic flame temperature is
3
limited to the boiling point of magnesium oxide,
..."

~1
'">-::>
0
about 3400oK. II the magnesium were burned in
c
i pure oxygen, the calculated adiabatic flame tem-
!!: perature would still be limited to about 3400°K.
/
%;= Example 3. Compositions contaiIling magne-
I
X sium Mid sodium nitrate are used in many illu-
40
mi ... "tiag flares. There are several possible ways
fc, l' this reartion to proceed which, in turn, deter-
mine relative amounts of magnesium and sodium
20 nitrate required for the stoiehiometrio:! (balanced)
.O .....TlC fL ..... E
T(Mptll' ..TUIIt£:
140Q" Ie
chemit'al rea(ltion. Two of the possible stoichio-
I metric reacti.ms are:
+------~----r---~----_.--~I~I----,--
'000 '000 ZOO<> ""'" ..ao 4000
1. 5Mg(s) + 2NaNOa (s) ~ 5MgO(s)
+ Na20(S) + N (g-) 2

and:
Figure 3-5. Enthalpy :>f Product.. of Magnesium-Air
Reaction 2. 6.Mg(s) + 2NaN0 (s) ~ 6MgO(s)
3
+ 2Na(s) + N (g) 2
liquid aluminu!Il oxide. The v[lporizatio:l of
For tht' first rea{~tioJJ, the ratio of the weight of
A1 2 03 (1) at approximately 3800 0 K may take place
sodiuHl nitratt' required to weight of magnesium is:
as follows:
AI 2 1):J(1) ~ 2AlO(g) + O(g)~ 2(85)
--.-.-.-- 140
>-

5(24.3) - .
{<'or this reaction, t/IP standard enthalpy change is:
and for the seeond I'eadian is:
H021lS0K == 436 kilocaiorit's pcr moJe
As the!'£' i:-: lIot enough £'Ilergy available to vaporize 2(85) 116'-'
all tht' almnilluJll ()xitit" tht· maximum temppratllre 6(24.3) - = . "
is limitt·d to the boiling' poiut (If alllwiIllHll oxidt·, OJ'
TIll' ht·at of J't'aetioJl fOl' Ow first reaetioll at 29RoR
approximately 3800°K.
is:
~lf0298:::-: [5( ---143.8) -+ - 99.4] [;'l(O) + :2( - llfi.O) 1= . fi8~.4 kil()('aJorit's
and for the :ll'eonti reaction is:
fli(O) + ~( ---- 115.0) 1= --- fi:i:U' kiloealorit's

3-21
AMCP 706·185

From the heat content plots for the two reactions, in the hot (over 2500°1{) portions of the flame
Figures 3-6 and 3-7, the tidiabatic flame tempera- plume can b(' selected from thermodynamic con-
tnr(' is nearly the same for both reactions: approxi- siderations in the following manner.
mately 3280 0 K for the first reaction, and 3400 0 K At 2500 0 K, the free energy change associated
(the boiling point of magnesium oxide) for the sec- with th£> reaction:
ond reaction.
'fhe reaction equation which bf'st represents
Na zO(I) ~ 2Na(g) + .50 2 (g)

the reaction to produce the produe~s which exist is given by Equation 3-62 (Paragraph 3-2.3.4).

~}i'°2500oK = [2(0) + .5(0)] - [1( + 13.649)] = - 13.649 kilocalories


and by Equation 3-64 (Paragraph 3-2.3.4)
However, the first reaction better represents the
-13649 _ - (2) (2.3) (2500) log Kp overall reaction to form the products which are
. - 1000 stable at room temperature since similar calcula-
Kp = 15.4 tions indicate that Na20 (s) is the more stable
sodium-eontaining species at room temperature.
Also: Kp = (P,,'.):! . (P02) "" = (4p()2r~ . (P 02 ) "" Example ·1. IM-ll is a widely used incendiary
mixture. It consists of 50 prrcent magnesium-
aud: ( P0 2) = .746 atm
aluminum alloy (50/50) and 50 p(~rcent barium
Sincp the calculated ( P0 2) is greater than the nitrate by weight. Thill mixturp is fuel rich and
partial pressur(' of oxygen in th£> air, 0.2 atmo- if all thr fuel is to burn, extra oxygen must be
spher(', tIl(' eompound Na20 (1) is not thermo- obtained from the ail'. If it is assuIDrd that suffi-
dynamieally stable at 2500 0 K. Therefore, thes(' ei('nt oxygen is availablr to oxidize the metal fuels,
('al('ulations indi<'ate that th(' s('cond r('action better a balan('ed reaction can br written.
I'Pprl's('nts tl](' stoiehioru('try of th(' ov('rall reac- On It basis of 200 ~rams of IM-H, the molrs of
tion it'ading to til!' formation of the product species Plteh ('ollsti! IIcnt arr: Ba (NO a ) 2, 100/261.4 0.38; =
pr('s('nt at a tiam(' t(,lIIppratnre of 2;;000K. lUg, iiO /2-!.:l:.~ = ?06; AI, 50/26.97 = 1.86. Ac-
('ordingIy, the reaction is :

2.0tH\Ig + l.H6AI + .;38Ba(N()a)~ + l.-!HO~ + ;;.!12N~ - .:!HHaO + 6.:10N +2 2.06MgO + .!)aAl~Oa

TIlt' h('at of reaction at 29WK is;

illf0 29H = [.38( - 133.5) + 6.3(0) + 2.06( -143.7) + .9J( - 400.4)]


-- [2.06(0) + 1.86(0) + .:J8( - 237.06) +UH(O) + iUI2(O) I = 62H.1i kilocalories
'rht> ht'lit ('ontpllt diagraJll for this syslt'1ll is showlI
tiOIl, to bt' blll'lIl'd at low Il-llitud('s where (lxygt'll
ill 1<'igurt' :~-l'. As indil'ated 011 this diagram, thl'
is IIvllilllbll' from till' atmosphprt', can be estimated
adillbati(· fialllP 1t'lIIperatul'l' IS approximately
by assuming' that tlie amount of magnesium in
a400°K.
('X('PSS of til!' stoil~hiolllet ril' alIlount whidl ('lUi be
L('ss ht'at is l'volvt'd if it is assulllt'd that oXYI!t'1J
\'aporizl'll by t ht' stoil'hiolllt>tril' read ion, blL<;ed 011
frolll llit' lIil' is Hot availablp for thp T't'lldioll.
th .. 1I1llOlilit of sodium lIitrat!', ('11II burll ill tilt' air.
E.fI1/t1}JI:· :~. 'rllt, optimulIl ('ollljlosilioll for a
1<'or t iiI' ma~III'Sillll1-sotliulJl lIitrat!' systl'lIl the
lIlaglH'si IIIll-sodi lUll nil I'll tt' III UIlI i IJIl t i ng ('0111 Jlosi-
stoidliolllt'tril' rl'lIl'!ioll is (st't' EXHlllplt' :1) :

for wlii"1! til,· ht'at of r,'adioll ;).// o~UH is 1i:32.H kilo- whil·1! "oldd bl' \'aporil'A'd by this umount of !'IJt'r~.,r)r
'·lIloril's. 'I'll!' IlIIlllht'r of lI1olt's of ruag-llt'siUIll 11 IS:

:!-22
AMCP 706-185

"

./
./ ./
./

1000

900 9OO-
/"
..-

.00
-
700 -
700

600

tu
:>
• 00

400
."...
";;;
...
":>
-
400
Q
0
a:
"0
a:
~ ~

l· :z:
!
.00 t '00
I
Z i

'00 too

100

l
'00

,I

--
~

:...:;:.'----'T"~-~.
-'>-- - ~.~ m _ •• ~---. t----41
.-- t
0

'000 ''''0 '000


Tf~PE'RATlJRE, -.:

Figure 3-6. Enthalpy of .products of Magnesium-Sodium Figure 3-7. Enthalpy of Products of Magnesium-Sodium
Nitrate Flare (Reaction 1) Nitrate Flare (Reaction 2)

tHI0 21l8
n = -------------- -------------,------- ____ 6a2._~
40.75 -
__ 11: 1:<) 11101('."
~
.:llIll\1l{(\")l;l~IOOK --l\Ig(s)29H"KJ i).<J...

so that th!' wt'i!{ht Pt'f('l'utagl' of lIla~IIl'sium for


thl' optimum l'llllJposit iUIl WOU}(} l)t':
(Ii t /I) \]1 U' :\1 g)

wht'I't' JI W stalltis for till' molt'l'ullll' Wt'ig-ht_


('lllatiollS (Ill tht'St' Shl't'ts Itrt' fol' a rt'fer!'lll't' t!'m-
!,t'I'UIl! rt' :!!lH.l GO K 1I1lt! Ollt' Iltmospilt'rt, pressure,
3-2.6 SUMMARY OF THERMOCHEMICAL
CALCULATIONS 3-3 CHEMICAL KINETICS
H~'s\llts of tllt'rllllJl'l!t'lllit'l,t1 ('a!t-lIlatioll" slIell liS ('iI"mi"1I1 kilwtil's is ('OIH,t'l'Ilt'd with tilt' veloc·
thO~t' illllstrllt,'d ill til" f()i't'~oillg- t"OIIll p It'!'., 1'1111 lw ity of 1'('I\dioIlS /llId til\' illtt'rmt'diat(' stpPH (meeh-
slIlIllllllrizt'd IlS shown ill 'l'ab"'s ;{·7 /llld :-I-H. All cal· 1:llislII~ \ by whit'h tht' rt'lll'tllllts lire ultimately

3-23
AMCP 706·185

TABLE 3-7
EXAMPLE OF THERMOCHEMICAL CALCULATIONS:
LANTHANUM·POTASSIUM PERCHLORATE REACTION
THERMOCH:EH\l.ICAI..J CALCULA'T'IONS'"

% Mol Wt 6.Hf Density, g/ml


REAC'l'AN1.'S
l,anthanum (8) 72.6 138.92 O. 6.15
Potassium Percltlorat(' (s) 27.4 138.5f) 103.6 2.52
PRODUCTS
Lanthanum Oxide(s,\ 85.1i :J25.84 45H 6.51
Potassium Chloride (s) 14.5 74.5(i 104.2 1.99
REACT.lON CALCULATIONS
8La + 3KelO, ~ 4La 2 03 + 3KCI
Stoichiomctric: 8 (138.92) + :3 (138.6) ~ 4(325.84) + 3( 74.56)
Thermal: 8(0) + 3(103.6) ~ 4(458) + 3(104.2)
Wt Reactants, g 1521.2
Theoretical Density (calc.), g/ml 4.41
Heat of Reaction (calc.), Kcal 1834
cal/g 1205
cal/ml 5:330
Adiabatic Temp (calc.), OK App. 4750
Gas Volume (calc.), liters ()
EQUIl' ALENTS
1.0 g La 0.445 g KCI0 4 = 1742 cal
1.0 g KeIO, = 2.650 g I,a = 4400 cal
THEORETICAL OPTIlUTlM (!OMPOSITION
Ll!nthan~m, % 85
Potassium P('fchlorate, % 15

* All caJtouh!iollS refer to :!!l1I.15°K.

l'OlJver\!'d illto tlw prodw·ts. As most pyrotec,mic 3·3.1 MOLECULARITY OF REACTIONS


rt'ul'tio/llo; iIlVo\vl' hl'terogl'lIl'ous syst!'IIlS, the rela-· The simpl!', intermediate reactions by which
tiVl'ly simpl!' killl'tie I'q llatiollN dl'vl;'loped for tIll' reactants I!rl' ultimatel~' convertt'll into products
hOll1of!l'nl'ous Syst!'IlIN arp useful but 1I0t adeq uate. l'UIl hl' dassifh,d as:
TIH'sl' I'I(Uatioml do, howeVl'r. provide backhPJ"ound
fOI' IllldeNtandillg of' tht' l'helIlil'al killl'tics involwd 1. iTnilllol(,l'ular. A rl'll<'tion ill which only one
ill II heterogt'l\t'olls reaeti!'II. It is to bl' noted that "lOll'(~uJ{' r('uds to yield the product l s).

tIw rat(' of a pyrotl'ehnie 1'\ adion, which is affl'cted 2. RilllOlt'l·ulaJ'. A reaction ill whieh two III01e-
hy ('xtl'rllal tl'mperaturl', prl'SSUrt' l'Onfillf'nl(>nt, ('lilt's (of 1h!' Slllll'> or of ditr('rent kinds)
('olllpositioll, pHrtil·le sizl-, l'()IIsoli(iatioll, and ollieI' rt'ad to yi['ld tlH' protluct(N).
illtt'rr!'latt-d fadors, is usually 1I,'st dl,tl'rmiul'd ex- :3. 'Tl'rmo!t>l·ular. A fl·actioll in which thre(;
Ill'ri!II('lltally. molt'(,II]es N'llet to form the product(s).

a-24
AMCP 706-185

TABLE 3-g
EXAMPLE OF THERMOCHEMICAL CALCULATIONS:
ZIRCONIUM-OXYGEN REACTION
THERMOCHEMICAL CALCULATIONS·

% Mol Wi IlHf Density, U/ml

REACTANT:::;
Zirconium (s) 74.3 91.22 o 6.49
Oxygen (g) 25.7 32.0 o
PRODUCTS
Zirconium Oxide(s) 100 123.22 261.5 5.6

REACTION CALCULATIONS
Zr(s) +
02(g) - - Zr02(S)
Stoichiometric: 91.22 +
32 -~ 123.22
Thermal: AHr o +
0
__ 261.5
Wt Reactants, gs 123.22
Theor8tical Densit.v (calc.), glml
Heat of reaction (ca.lc.), Kcal 261.5
cal/g 2120
Adi.abatic Temp (calc.), oK App. 4500
Gas Volume, liters/g o
EQUIV ALENTS
One g Zr 0.346 g O2 2860 cal
One g O2 = 2.89 g Zr 8250 cal

• All calculations refer to 298.15°K.

('l'here are few, if any, termolecular reac- tions, k is the specific rate constant, and the e:;r-
tillns. ) ponrllts m, n, and 0, arc:> empirically determined.
F'or gaseous rractions, concentrations are often ex-
The over. ~ll rractions oe!'llrring in the' burning of a
pressed in terms of partial pressurer Similar
pYl'otecllllic composition cOllsist of a sequence
expressions could be written for the disappearance
of Illany simple intermediate unimolecular, bi-
of othrf reactants or for the appearance of any of
molecular and tt'rrHuleeu!ar reactions.
the products.
The overall order of the reaction is the sum of
3-3,2 ORDER OF REACTIOli
thr exponents of the "eoncentration" terms. The
T!l(' illstantallt'()IIS rate of a chemical reaetion, ordc:>r of a reaction, with respect to one reactant, is
as Illl'a!;ul'('d by the rate of d isaplwaranc(' of one of the t'xponent of the concentration term for that
its rf'a(·tants. ('un be writtep : rt'aetant. Examples are:
-- dA
elt k/A/"'/BJ" [C]o ... (3.68) 'I
,,('ro 0 "(I fr:' -- - d[AJ
dt
--- =k. ( 3-69)

wlH'r(' che minus sign il\diea,~'s till' disappearancr 'l'he rt'aetioll ratt' is a constant and itl independent
of real'tllnt A, t:w sywbol r J i~ldicatt'S eon centra- of thf' ('oIWf'lItratioll cf the reactants.

3-25
AMCP 706-185

_ . ENDOTHERMIC

---'--r-
''''' - - EXOTHERMIC

- .. Nil ... - -tii--:.--i.'CAl

-r----
AHe..
..., . ~!!!

."" -r---'--
'00
AHi..
"'" ___1_.______ ~
I"" - Figure 3-9. rile Relclfion,hip Between Heat of Reaction and
Heat of ActivC:.fion
! 100
% The reaction rate is proportional to the px'oduct
,~
%
1:SO
of the coneentrations of two reactents or to the
concentration of one reactant squa.red.
I()()
Only a very few r~ctions follow zero, first,
second, or third order reactions. Most chemical
reactions, especially &t the high temperatures in-
volved in most pyrotechnic reactions experimentally
determined, are complicated combihations of many
simpler reactions. These complications include
TEMPERATURE. OK consecutive reactions, !'cverse reactions, and side
reactions. Hence, it is possible for the order of a
Figure 3-B. Enthalpy of IM·ll Incendiary Mixture reaction to br fractional. 12

Pirst Order:
dlAJ
----_. 3-3.3 INFLUENCE CF TEMPERATURE
~::: k I A. j (3-70 )
dt ON REACTI(JN RATES
1'h{' rea~tion rate is proportional to t.he concentra- 'The rr8ction rate is strongly dependent on tern.
tion of a reaetant. In thiR case, half-lift' (the time peratm·e. 11 qu.mtitative fplationship proposed by
l'equired for one-balf of the r~'actallt present at. any Arrhenius relating the specific ratc constant and
given time to disappear) is indeprndent of the the absolute temperature is:
initial eoncentration.
8 econd Order; K=.'lexp
-Eu]
[RT (3-73 )

- ~1/1J =~IA liB] (8-71) where k IS the :;pecitIc rate constant, s is a constant,
E'a is the activation energy, R is the gas constant,
or:
and T is the absolute temperat.ure. Another ~me­
--d,'AJ what more complicated relationship, based on the
-----;it-- = kfA I~ ( 3-72)
dwory of absolute reactions rates, is :18

3-26
AMCP 706-185

k= (~~'_)
(
. !lEa
exp [ -If-.
J)( [- J)
exp
!lII"
Rl"
In some cases, the reaction of a chain carrier
with a moleeule may produce more than one chain
(~arrier. This Ulultiplication of the number of chain
(3-74 ) carriers, or chain branching', can lead to an in-
finitely rapid rate for the reaction, Explosions
whert' It- is the specific rate eonstant, R is the gas
resulting from l~hain branching are definitely dif-
constant, N is the Avogadro'R number, h is Planck's
ferent frow thermal explosions. In a thermal ex-
constant, Sa is the entropy of activatior~, II a is the
plosion, br;!ans(' of the exothermal nature of the
enthalry of adivatioll, and l' is the absolute tern-
reaction and the difficulties attending heat removal,
peratllre. The relationship between the heat of
the temperature of the system rises rapidly Ilnd
activation for till' forward Imd revprse reactions
an l~xtrrmely rapid reaction or explosion may re-
alld thp ))('at of reactioll:
sult. A brandl!'d ehain explosion can take place
tllI (reaction) :0= AHa (forward)- till a (rpverse) ~~ven thoug'h isothermal conditions are maintained.

is illllstratt·d ill }<'igh r'e :J-9 f,)1' an exothermic 3·3.5 HETEROGENEOUS REACTIONS
reaction.
In heterogeneous systems, reactions ta,ke plac p
at phase bounds-ries. While the kinetics of chem-
ical reactions involving more than one phase is less
3-3.4 CHAIN REA(:TIOYS
developed than that. for homogeneous systems, the
'l'heoretical and e:;;:pel'imental I'e'>lllts indicate overall pro(;ess includes at least three steps:
that atom-lUolt'euh' and radical-molecule rel:'.ctions
1. Transport of re&.c:tants to the phase bound-
Ilorma!ly l'equire mudl smaller activatioll energies
ary.
than reaetiollS betw(,l'n two mole('ular sp~cies. A
2, Reaction at the phase boundary.
varipty of (~helHical processes procet'd by mech-
3. 'fransport of prodllcts away from the phase
anisms which involve free radicals or atoms
boundery.
in a "eqllellet' of rpaetions forming a ehain. These
pro(~('ssps indlide thermal and l~hl)to-ehem,cal de- As indicated earlier, a series of reactions will have
('olllpositioll pro('Pssc':;, polymerization and depoly- relatively simple kinetics if the rate of onfl step is
mprizatioll processes IL'lder the infhlt~nCe of heat mnch slower than any of the othel.'s. Heterogeneous
Hull light, as well as a variety of oxidation" and l'£actiolls, therefore, are divided into two general
halog'cnatiolls involving hydrocarbolls which ..:an types: (a) transport rate cOI'trolled, and (b) phase
g-ivt, ris!' to tht' production of flames ar..d ex- boundary rpaction rate controlled.
plosions. Reactions involving a gas as one of the reactants
I n a strai,:::-ht ('hain rraction, 11 l'haill earripr-- arp freq \lently phase boundary reaction rate con-
whie/J may be a free radieal, fre!' atom, or an ex·, tl'ollt'd at low temperatures and pressures; how-
('it"d JllOlt'l'ldp 01' atoJll-is pr()(L.(~ed by som(' ('vel', many of thes(' reactions become transport
~;!litabl(' primary readioli, Tlds (·hain carrier reacts ratr controlled at higher trmperatures. For con-
with a lllo1f'cul(, to produc(' anotlwr lllo1!'l:uh' and dpllspd phase reactions, t he transport rates will be
another elwin ('arrirl' "'hidl, ill tU1'II, I'l'acts with ('ven SIOWPl' st' that rea(·tions are often transport
allot/WI' molt'('ujn to PI'OutH'P anothl'1 chain l~arrier. ratp ('ontrolletl even at low temperatures.
As bllg' as thr chain rClIlains unbroken, the disap-
jWaralll'1' of ont' chain can'it'r is a('('ompanied by tll!, 3-3.6 IGNITION AND PROPAGATIVE
fOl'matioll of another chain carrit'l' T:le chain BURNING
('an hI' brokt'll by tlIP l'('ulOval of tl](, ehaill earriers, TIl!' hm'/,ilIg' of solid !H'opellants and eOllsoli-
as t!w r('stilt of reactions hetW('/'ll ,hai:1 (~arriers dat('(l pyroff'('hllie mixturrs are similar in many
or 1'l'tw(,1'1I thl' ('Iwill ('aITipr and ntlwr rf'adivl' !,(>sJlt'l'ts. W 11t.>Jl rais('d to thei I' ignition tempera-
/!Hlt!'rials, or hy tllP !'oliisi'Jlt of a ('haill HllTl('r tun., t hp), tllldt'l'g'o prri~/Jitioll reactiolls followed
wi t h tllP wa II of t hp ('011 tllillillg' V('ssP!. hy all igllition rt'uetion. If eonditions aI'(' favorable,

3-27
AMCP 706·185

the reaction front moves at a nominally constant


velocity. Propagative burning involves recurring M9- NaNO:,I
ignition as the reaction front progresses, therefort-:, 2.~%-78%

ignition and propagative burning processes must


10.0
be considered together. 8.0

G.O
3-3.6.1 Ignition (/)

The overall process of ignition involves heating c


z
a portion of the combustible--such as a propellant, 0 4.0
0
pyrotechnic mixture, or a combustible material in U.I
(/)
air-to its ignition temperature, the minimum tem-
perature required for the initiation of a self-sus- Z
0
taiuing reaction. While the overall ignitiol' process i=
can be stated simply, the mechanism of ignition Z 2.0
~
is not known in detail. An ignition stimulus, which
()an be reduced to the effect of heat absorption,
starts a. sequence of preignition reactions involving
...
0

U.I
crystalline transitions, phase changes, or thermal 2
~ 1.0 '--_ _-.1._~..I-1_ _ _ _......dL-_ _ _ _ _....
decomposition of one or more of the ingredients.
1.04 1.08 1.12 1.16
In many cases involving propellants and pyro-
technic mixtures, a gaseous phasl' is formed and I/T IC 10~ 0)(-1
combustion starts in tIll' gaseous phase. This is Figure 3·10. Ignition Time-Temperature Plots for a B:inary
true for wood and similar materials where cambus- Pyrotechnic Mixture
tiol1 starts in the gaseous phase after the formation
uf gM:eous combustibll' intermediates by thermal where t is the time to ignition at the temperll.ture T
decomposition of the fuel. Combust:on of liquid in degrees absolute; Ea, the activation energy, is a
fue~s also sta:!·ts and takes place in the gaseous cunstant; R 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 of propagatively reacting sYE,tems,
cation of the ignition stimulus and ends with the such as explosives, propellant:>, and pyrotf'chnic
start of sdf-sllstainillg combustion. During this compositions follow this type of equation. The
period, the' rate oi heat trlinsY~er to, the rate of value obtained for activation energy for the igni-
heat produ;~tivn in, and the rat~ of heat loss from tion proees.<; ean be considered a measure of the
that portion of the material being ignited, are sfl.sitivity of the compositi~n to beat. It will de-
important. As the temperature rises, the rate of pend, partly, on the speeific experimental ~ondi­
thl' heat producing reactions will increae2 as pre- tions.
dicted by the Arrh(>nim: equation (Equation 3-73). Time to i~nitinn is often measured 11l •1tI by
The rate of hea', less will also incrcase with tem- quickly immprsing the sllmple in a suitabJe con-
perature but, because of the exponential form of the tainer into a liquid such as molten lead mailltained
Arrllenius equatiun, Ii temperahlre may be attained at a constant temperature and observing' the time
at which the rate of heat gent'ration is greater than to ignition. As shown in Figure 3_10 11 the results
the rate of heat loss and ignition will result. obtained are presented in an Arrhenius type plot
Thl' time to ignition call be expressed by an in which the natural logarithm of the :i,n~ to ig-
equatjon similar in form to th<, Arrhenius cqua- llition i.s plotted against the reeiprocal of the abso-
timl. 18 • 14 lute temperaiure. An ~vcrage value fnr the activa-
tion energy for ignition can be obtained by:
Ea --= [2.:3(slofJe)]R

;1·28
AMCP 706·185

though the heats of combustion of metals are rela-


AMBIENT ATMO'SPHERE
tively high, most of the heat energy obtained from
this reaction is used up by the heat of vaporization
and dissociation of the oxide. Two models for metal
partic}!.' combustion which have been proposed based
on studies of the burning of aluminum differ mainly
in the treatment. of the condensed oxide formed by
the combustion reacti.on. 18
As hollow oxide spheres are formed in the (lom-
bustwn of aluminum, one of the models for self-
sustained combustion consists of a vaporizing drop-
let of aluminum which is surrounded by a bubble
of molten aluminum oxide. The reaction rate is
determined by diffusion through the alumina
shell. 19
The other model consists of a vaporizing drop.
let of aluminum surrounded by a detached reaction
zone where the condensed alumina product ap-
pears as fine droplets. The reaction rate is con-
trolled by the vapor-phase diffusion of aluminum
Figure 3-n. Model for Burning of 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 conver-sion factor for ment with the experimental data obtained for burn-
natural logarithms into comm:>n logarithms and R 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 of this model, it is pos-
By usi.ng the data plotted in I<'igure 3-10, the sible to predict conditions favoring vapor-phase
activation energy Ea for ignitiorl of the magnesium- flames, snrface combustion, or no combustion. For
sodium nitrate system can be calculated in the fol· those conditions resulting in vapor-phase combus-
lowin[' manner: tion, the burning rate of spherical droplets W car.
be expressed as :21
Slupe of line:
W = kr" (3-77)
M= Y2 - Yl. = 2.3 (log 6 -log 2)
X2 - Xl 10 3(1.118 -- 1.064) where r is the radius of the droplet, k is a constant
involving, among other factors, the latent heat uf
= 23 103(0.7782 - 0.3010) vaporization, and n is a eonstant normally having
. X 0.054
a valne near 1.
= 2.3 X 103 ( °O~5742 ) = 20.35 X 10: 1

3-3.6.3 Burning of Solid Propellants


Adivation energy: The burning of solid prC'pellants has been exten-
Ea =-.= (20.35 X 108 )2 sively studied and, in some cases, the mechanism
= 40.7 >~ 103 cal/mole of burning is reasonably well established. Solid
= 40.7 Kcal/moie propellants can be classified into two general
types, homogeneous propellants and composite pro·
3-3.6.2 Burning of Metal Particles" pellants. Homogeneous propellants are commonly
A primary eharacteristic of the buming of a called double base, or eolIoidal propellants, be-
metal is dIP limit~ltion of the temperature attained cause they consist of a coIlo:dal mixture of nitro-
by the boiling- point of the resultant oxide. AI- cellulose and an explosive plasticizer, usually nitro-

3·29
AMCP 706·185

glycerin. Relatively small amounts of other ma- T", • MAXIMUM REACTION TE'APERATURE
terials are added to improve the properties of the TI ., MINIMUM IGNITION TEMPERATURE
propellant. A composite propellant resembles a Tf • FUSION TEMPERATURE
pyr:>technic mixture in that it is an intimate mix· Ttr • TRANSITION TEMPERATURE
To .. AMBIENT TEMPERATURE
ture of a fuel (reductant) and an oxidizer. It
AZ'. AZ". AZ.... At·... LENGTH OF ZONES
consists of a finely divided, solid oxidizing agent I • REACTION ZONE
in a plastic, resinous, or elastomeric matrix which 2 • ZONE OF FUSION
normally provides the fuel for the eombustion 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 l • DIRECTION
to modify the properties of the binder or to change V .. VELOCITY OF 8URNING

the burning charaeteristics.


Combustion processes in solid propellants, as
in pyrotechnic mixtures, are complicated because
of the several processes involved in the transforma-
tion of the solid material, at ambient temperatures,
into gaseous, liquid, and solid combustion products i!'
at the flame temperature. In general, for all solid
propellants, the temperature of the propellant a
short distance below the burning surfaee is not 4 3 2
aifectf'd by the combustion of the propellant. In
propagative burning as the burning surface ad-
vances, tIle unburned propellant is heated, and the
tf'llJpel'uture of the material increases to the point
Tf 1j
where the propellant decomposes into volatile frag-
ments. In somp cases, liquefaction may occur prior
to the chemical reactions which ('om prise the COID-
bustion process. Figure 3-12. Model for Steady State ProgreSJive Burning
The solid phase processes for double base pro-
pellants, which take place in a 10- 3 to 10- 2 centi- as for a double base propellant, the burning of a
meter thick layer, are completed at relatively low composite propellant involves the formation of ac-
tive gaseous intermediates from the fuel and oxi-
temperatures, Ilea: 600°C. The gas phase reactions
dant, whieh then react.
can be considered as taking place in three zones.
The first zone exists adjacent to the burning sur-
face, and is calJed the fizz zone, where SGIDe exo- 3-3.6.4 Rate of Propagative Eurning22
thermic reactions may takc place. In the second TIlt' steady state burning rate of a propagative
zone, called the preparation or dark zone, activated burning sysh'm is detprmined, basically, by the
intermediates arf' 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 reaetion occurs to the unburned composition. These quantities, in
in thp fiam!' zon!'; this reaction produces the con- tum, are infiuf'llced by the ratio of ingredients, ex-
stant pressure combustion temperature. The thick- tt'rnal prf'SSlIre and tt'mperaturf', ratt' of chemical
nes.' of each of the zones increases with a decrease rt'aetion, t hel'ma) cond L1ctivity, particle size dis-
in ambient plCSSUrl>. tribution, and thf' porosity of tht' eonsolidated com-
'l'hr burning of eomposite propellants, as well as position.
pyrot!'cllllie mixturef. involving intimate mixtures I f it is aS8uIIIPd that heat transft'r by radiation
of fuel amI oxidizer, is 1II0rl' ('omplicated than the and diffusion of lIIatl'rial can be lIt'gleeted-and if
burning of a doub)!' base propellant. In genera), h('at losses from th!' side art' insignific,.nt-the

3-30
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 zone;; defined
by the limits of the maximum rea.ction 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 preigni-
tion zones is constant with time, and that thc posi-
tion of 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- FURNACE
Af.lD BLOCIC
ture ranges involved.
For this model, the following equation can be
obtained for the linear rate of burning V:

~ QN.n([Ada>, s exp [:; ] (3-78 )


V = ....:i_-=:-:::--,,:;-_-=_ _ Figure 3·13. Differential Thermal Analysis Thermc;oup/e
~DCm\7T Circuit
i
where () is the heat of reaction; s is the Arrhenius
frequen~y factor; Nt is the number of fuel particles thCfolC ('onditions, Ai in Equation 3-78 is equal to
per unit volume; ni is the number of molecules of the mass of a metal particle m, and Xi is equal to
ith species, which has an activity Ai; and Xi is the 0.67 (as the surface area of a particle is propor-
order of the reaction. Ea is the energy of activa- tirmal to its volume to the 0.67th power) plus a
tion, R is the universal ga.o.; constant, T the abso- constant h, dcfined by the equation.
lute temperaturr, D thr. density, Om the mean spe-
cific heat, and \1 T the temperature gradient. Ac-
dt'/dt = k(m)"
cording to thiR equation, the rate of propagative Other reaction parameters will remain essentially
burning is dirrctly proportional to the net heat of constant when the par~icle size of the metal fuel
reactioJl, sper.ifie ratr, concentration (If reactants, is ehanged, and:
and specific surfacr, and is inverse!y proportional
to the density of tlw composition, mean specific V"=V«-N -
N" (m,,) (h + 0.67)
(3-79)
• ~n.
heat, and temperature gradient acrOSR thc reaction
and preignition ZOIl('S. The rate of burning is also The SUbscript 1t refers to the mixture with an un-
proportional to thf~ thermal conductivity. known burning !"ate, and the subscript s refers to
The e+frct of particlr si7.e on :.1!' rat!' of propa- f.;tandard. 'rhe constant h ill the above equation
gatiw burning can 1)(' ,'stimaterl by aRsuming that oftrn has It value of about 0.18. More a.ccurate re-
the rate of thr chemical reaetioll is proportional io;UItf.; are obtained if II is determined pxpcrimen-
to the rat!' of dlangp in VOlll11W of HlP sphrrical tally for eaeh mixturf'.
partielpR and that til!' rat!' of change in the radius '~'ht' d!'rivpa rqllatioll dot'S not include a pres-
of a rra('ting partil'l.' ('all b!' expresscd as 1111 !'x- 1-;\1'''' term; how!'\,('r, spvpral of 1he parameters
ponential fUIJC'tioll of the partir]!' mass. Vnder whi('h il!fhIPJl("(, the burninh rat!' arr affected by

3-31
AMCP 706-185

changes in ambient pressure. 'I'he pressure depen-


dence of the burning rate v, for many similar
propagative burning reactions at higher pressureB,
is somet.imes given as:
v = bp" (3-80)
I
1'00
or by:
i; NoNa.
0.I00I,

where a, band n are constants, and 'P .is the pres- 100 I !

o 100 toO JOG 40(1 _ toO


sure. At the lower pressure normally ~ncountered TEIIPf:1lA1Uf11 I"CI
in burning of pyrotechnie items, the relationships
Figure 3-14.1. Thermclgravimetric Curve for the Ingredient
between the linear burning rate and the pressure Sodium Nitrate
may be more complicated.

3-4 THERMOANALYTICAL TECHNIQUES28


Mg
The thermoanalytical techniques of differenfal 0.2473,
thermal analysis (DT A) and thermogravimetry
analysis (TGA) are versatile experimental tools
I
i
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-
1 0
- - - - - -
0~~1®~~~~~1~--~~1~_~~~1~~~~1~~~~1~~~~~~~1~~'®O
TElll'tRATUItC! I"CI
terial to elevated temperatures at a eonst-ant rate,
while eontinuously measuring the temperature dif-
Figure 3-14.2. Thermogravimetric Curve for tf;,! Ingredienlt
ferences oetween them as a function of sampled Magnesium
temperaturc and time.
Although the techniques of DT A have been
widely used in the study of clays, minerals, and 0
~
soils, relatively littlc work has been reported uti-
lizing this method to investigate and characterize I
the thermal decomposition of inorganic; com- j
pounds. In Figure 3-13, a Echematic diagram W100
illustrates the basic measurements required in g
DT A. The temperature differential between an ...
inert referenee eompound-e.g., ig'llited AbOa-and
...
% LAMINJiC
O.I7M.,
i 110
the material under study is measured and re-
I , I ..J. I I I
eorded as they ar~ both heated to elevated tempera- 0 100 IOC. 300 400 100 400 700 100 MlO 1000

hIres at a constant rate. The d;,fferential tempera- TlIIINItATUIt! I"CI

turoe is measured at 1',) and the Ilample temperature Figure 3-14.3. Thermogravimetric Curve for the Ingredient
at 1'8. Laminae 4H6
Thl' referenl'L' mat('rial cho.-,en Rhollld be therm-
ally inert and undergo no 1'1ldotlt('l'lHa] or exo- temperature of the inert sample is eonstantly in-
thermal reaetiolls over thc temperature rangc lIIHI('I' ereasillg', an pndothrrlllal differential temperature
eo~jderatioll. Consequently, the inert ~ple heats ,·(·suIts. ConvprsP]Y.:l1I pxothcrmal reaetion causes
at It rate equal to that of the furnace. When the thl' ,;amp]p /.pmlh·ratllre to inerease more rapidly
sample !:Icing Itnalyzed undergoes all cndotlwrmal than tlt(' /'t'j'crPII('e tempprature, and the re~u1t is an
reaetion, its tplJlpcraturr remains relativel! eon- I'xotherrual differential. Whf'/l thl're is no thermal
stant or Ul(!rl'ases very slowly. Therefore, I:Illlee the reaction. the oorJlple and reference compollnds heat

3-32
AMCP 706·185

tm.'e under consideration. Oxidation of a material


such as Ii metal powder by a gas, e.g., oxygen or
nitrogen, involves the rvolution of heat and is,
therefore, an exothermal reaction. Oxidation-reo
o duction reactions normally are exothermal proces-
ses, partif'ularly when consiclpring reactants such
as metal fuels and solid oxidants. Since these types
I
,.0. of phenomena are indicated by the DT A curves
obtaiupd, these curves may be llsed to characterize
TEMPERAlV~E (OC)
the system under study ill terms of its thermal reo
Figure 3-15.1. Differential Thermal Analysis Curve for the actions, both physical and chpmical. Integration of
Ingredient Sodium Nitrate arras under endothermal bands also has been used
to obtain a semi-quantitative estimate of the
e ----------------------- amount of one or more of the ingredients present.
r::> Ma
Thermogravimetry cOllsistG of continUOUsly

~
wei~hing a &'lmph' as it is heated, either at a con-
stant tpmperaturp or to plevated temperatures at
~ Q o
a constant ratp. Curves are ubtained as a function
of temper8tllre ('1' time. Since thermogravimetric
I curves are quantitat.ive representatiulls of weight
L - - -_ _ _ _ _ _ _ _ _ _ _ _ _ J ehangep, they (~an he l'plated to the chemical and
TEMPERATURE (OC) physical changes taking place in the sample as it
is heatrd, and c~n often bp used to determine the
Figure 3-15.2. Differential Thermal Ana/y.sis Curve for t~e l1a+,ur(' of th£' intf'rmpdiatr and final reaction prod·
Ingredient Magnesium
nets.
Typical If'sults obtained by thermogravimetric
and diifp'fpntia.l thermal analyses techniques are iI-
LAMINAG 4111l
lustrat<'d by the results obtained in a study of the
479 pyrotechni(; illuminating mixture composed of 54
o
ppr('ent magnesium, 36 percent s::ldium nitrate, and
Hi IJercPllt I.JIl.minac.24 The thermogravimetric stud-
ies under normal atmospheric couditions indicate

--------
,
)71 J tha, all thh'e ingredients undergo thermal reac-
tions involving weight rhange as Ii function of
TEMPERATU(iE: (Or) furnace t(':rlperature, lik illustrated in Figures 3-
14.1 through 8-14.:3. Sodium nitrate exhibits a
Figure 3·15 . 3. Differefl1ial Thermal Analysis Curve for :he
Ingredient Laminae 4116 wright loi's at temperatures from 700°C to 1000°0
which corresponds to a eomplet~ (Jon version to
at the l,auw rate and no differential temperature is so(lium oxide. The curve al~;o fJhows a point ,)f in-
ubsrr-,'ed. Dehycirhti():1 of a hydrated or hygroscopic flection at about 8f>(l°C clue to the eorwurrent de-
substance is an (>ndothermie p~oce&., as are those composition of th!' intermediate product, sodiUl'1
of fusion boiling. Transitions involving hans- nih'itt'. Mllgneslm;l shows It continuous gain in
~ormations from one crystal latticf' to another, or -.veif{ht whieh beg-ins at about 625°C and continues
the free rotation of ions in a lai.tice are, most often, Oil pa.st the maximum tempI'ruture. '{'he C1E've
endothermal IH'oceSses; however, thf're are several varies in slope, becoming' pereeptibly steeper at
isolated exeeptiou!'l to this general rule. Decomposi- (ifj()OC, alld markedly less steep at 680°C. This
tion reactions may bf' eitlH'r endothermal or exo- weight gaill is attributed to tht successive !'orma-
thermal depending upon the system and -.empera- tion of magrw,ium nitride and lIla;:;-nesium ex:de.

3-33
Allep 706-185

40
MG""NaN~1
22"10/78"10

'- ---~

Figure 3-16.3. Differential Thermal Analysis Curve for the


Magnesium.Sodium Nitrate Mixture (Curve 11)
o 100 500 eoo 150
(OCI
Figure 3-16.1. Differential Thermal Analysis Curve for the
Magnesium-Sodium Nitrate Mixfure (Curve I) NaNO.- LAMINAe

,- 78%/22%

o
NaNOl-C
88%/12"10 ,
297

TEMPERATURE COC)

Figore 3-16.4. Differential Thermal Analysis Curve for the


Sodium Nifrate-~aminac Mixfure
...J
c:l 0
~
Z
I.LI
a:
U,I
-"'-- --- dotiwrmic crystallill!, transition at 270°C, imme-
diately followt'd by elldothe~'mic fusion at 306°C.
L&..
L&..
'rhe diff('r(,lItiul thermogram of magnesium shows a
0 20 (loublp cxothermi~ peak L~'b>illlling at about 565°C,
whi(~h way 1)(' dm' to thc formation of magnesium
o 100 200 300 400 nitride or magncsiulll oxide' Oll the surface of the
TEMPERATURE (OC) 'IlPtal, or to reaction with the glass tube. The
Figure 3-16.2. Differential Thermal Analysis Curve for the doubll' pl'ak l'ulmillates in the endothermic fusion
Sodium Nitr'.lte-Carbon Mixture of maglH'Siulll. The DTA tnrve of polyrr, 'rized
I;awillac displays only one bt'oad, endothermic
PulYillerized Laminae first sLows a "ontinuous balld, twgilluing at about ::~5tl°C, with a peak tem-
"'t'ig-ht lOBS, t'xtellding from about 100°C to 500°(,;, )H'l'atu!'(' of ;;71°C. IIowpver, it appPllrs as though
whi('h Illltr'kc'dly dlang"'s ill sloJl(, at :~50°C. This sevPl'al ovprlappiJlg' l'eadions are responsible for
1(I,'i;; is follow('d by <lnothpl' loss, endillg at 62;;°(" th" hl'at absorption. At a05°C, a colorless liquid
wltie!l ['f'PI'PSt'lltS II loss ill w('ight i'quival"'lJt to the ('(lHd('I1"t's on til!' uppC'1' part of the sample tube. At
illitial \H'ight of tlit' SilllliJlc'. 'rltis II)sS is due to :n~O{', tlw!'f' art' dl'Bs(', whitt· fUIllf's escaping from
,,1lt'lIlieal dq~radatioll of the IJolYlller to carbon, till' tubp. At 47!)0(\ aftpr the endotherm is over,
whieh is t1Wll eOlllpjptply ()xidiz('{l. tIll' ,.;ampl,· giws otf deww, yellow fumes and some
Thc' n'LA l~lIrv{'s for' th!' ingredients ar'p illus- ('harrillg' is o!JSt'!'vPt! in til(' tube.
Imtt'd ill j"ig-lll'(',; :1-I;i.1 thl'oug-I! a-L\;{. Tltt' ouly As showll ill i<'ig'llrl's :J- Hi.! thl'ougll a-16.fi, the
th(,l'lwti ,·Ifed t'xhihitl'd hy sodiulll Ilitl'lltf' is en- hiaary fllt'l mixtun', magllrsilllll-IJuminu(', gives
AMCP '706-185

Mg-LAMINAC
84.,./ IS'll.
/TlD I

-~:r-:r-
.J
of
;::
Z
W
0:
3!o t
641
• 0

Mg - NONO. - LAMINAe

......
W
~4'11./n%/IO"
I
6
TE!4PERATURE ('C) TEMPERATURE ('C)

Figure 3-16,5, Differential Thermal Anal)"s;s Curve for the Figure 3-17,2. Differential Thermal Al1alysis C,'rve for the
Magnc'lSium-Laminac Mixture Magnesium-Sodium Nitrate-Laminae Composition

Ilitratp art' vfry small beeause only very small sam-


ples Wfre used, Thf fUfl-rieh system 60-40 mag-
0'40
!!... MII-NoN03-C llt'silllll-sodiullI nitrate, ('urw n, lIsfd in the test,
w
12"1./82%/6% ignited at 5600C. Thp DT A eurvp shows the endo-
a::: thermic crystalline transition of sodium nitrate at
::>
~ 265°(" and its fW-lioIl at 305°(" in addition to the
[520 sharply pxothprmic ignition. ThE' stoichiometriCl
Q.
~ mixture, CIU\'l' I, for th(' reaction:
W
I-

..J
<{
Mg +- NaN03 ~ MgO + NaNO:z.
~
z 0 ('ontaining only 22 percent magnfsium, ignited at
w
a::: {il;3°C all(I displayed endotherms at noo and 310°C
w
I.J... whieh w('rl' ('ans('d, respeetively, by the crystalline
I.J...
Ci transition amI fusion of sodium nitrate. SodiulIJ
20 llitl'att'-IJaIlliJII!(' igllit~d with an apparently small
L I j---L--- 1'\,,)ItI~i()l1 ot heat at -!]7°C ~hat may have been due
0 100 200 300 400 500 600
to a ('olllbination of small sample size and forma-
TEMPERATURE (Oe)
tion of gasl'ous prodllets. Til!' difi'l'rential thermo-
figure 3-1.7,1. Differential Thermd Analysis Curve for the gram I'xhibits tlip l'rp;tallill(' transition of sodium
Magnes;L'm-Sodium Nitrate-Carbon Composition nitratl' at :~(iHo(, and its fusion at 297°C. A broad,
shallow I'l1dothl'l'lI1, during- whieh a colorless and
I)'I'A ('\'idpll(~t' of tilt> tlll'l'Illa\ tiP('oJllposition of the tlH'n a ,\"plio,," Jiqui(l ('ondl'lIst'S on thp sample tube,
Lalllillll(' IJI'est'lIt hy s{'\'l'ral shallow !'Ildotherms 1'\!llllillatI'S ill ignition. 'rill' sodiulIl nitl'ate-earbon
prim' to tilt' sharply I'lldoth,'rmil' fusioll of mag- systl'\Il l'xhibits tilt' l'rystallinl' transition of sodium
IlI'SiUlI1. Tltl' llI11gllt".;iulll fusioll pHdot hl'I'Il1 is fol- nitrate, sll('('('SSflllIy followp<i by sodillm nitrate
lo.\'(,d by all I'xotlipl'llIa\ ,'padioll, probably til(' fusion, alld tlWIl ignitioll at 467°( '.
oxidatioll of 1ll0ltPIi lIIaglH'si\llll, TIll' abst'\lI'e of allY D'I'A 1'\1I'\'\,S for thl' two t('l'lIllry (~()mpositj."Jls
,'xotllt'l'I11ilJ pI'ak pI'ior' to ItIltg'II('si 1,11Il fusion SUI~' al't'sho;m ill 1"i~\I\'(,s :1-]'.1 and :1-17,2, The mix-
gl'sts tbat, ,dtliollgh thl' Laminal' tltH'S Hot ('l'al'l tilt''' "tJIi1ailling lIla~Jli'sil\lIl, s>odiulll nitl'atp, and
Ilitil till' blllk of thl' llll'tal, it Jll'ot!'l'ts tlil' solid ('arbOll is \,I'I',\' siIllilal' to tlil' sodiulll llitratp-('arboll
Illag'IlI'SiUIIl hom \"('al'1ioll witli ail'. Thl' fUll)' hilla!'." llliXtlll't'; i.t'" it ignit"d at 4G;)oC immedi-
billilry fu(·I.oxitlallt Illixtllrt's did igllit". I<'or hll all'l,\' following tit,' ('r,\'stallillt' trallsition aIHI fusion
tilt' Igllilihl" sodiulll lIitrlltl' t'\)lllpositi(dlS I'\lll 011 IIf thl' SOt\illlll Ilitratl'. 'I'lte mixture (·ontaining' mag-
tlit' tiIlH··,basl' apparatus, tlil' 1'1lduth"l"IlIS l'O!T('- Jj('Silllll-sodiullI llitratp·Lallliutle igllited at 489°(.;,
"pol'(lillg to tit .. l'ryst,:llill(' 1ram:iliol! of sotii!llll 'J'ltl' fin;1 tll<'l'IwJi plH'nllll'''nli obser\'l'(l were the
AMCP 706·185

crystallinp transition and fusion of sodium nitratE' from the second exothprmal rpaction. These and
at 270°0 and 299°C, respectiwly. There was a relatl'd results iudicate that it is not feasible to
small, sharp exothermal I'eadion beginning at write preignition or combustion reactions for the
37:1 0 C, 'lnd another hpginning at i50°C, with peak systems containing Laminae due to the complexity
temperatures of 405°C and 485°C, respectively. of thp polynwr and the uncertainty of its com-
Ignition occurred as thE' systPIlI was recovering bustion products.

REFERENCES
1. M T. Howerton, Elluinccring Thermodynam- eation of th(' Absolute Rpaction Rate Theory
il!,;, Van Nostrand Co., Inc., Princetoll, N. J., to the ignition of Propagative Reaction Sys-
1962. tems. The Thermal Ignition of the Systems
2. Handbook 0/ Chemistry and Physics, 45th fJithill1ll Nitratr-Magnesium\ Sodium Nitrate-
Ed., The Clwmical Ruhber Co., 1964-65. l\Iagnt'siuIll," .J uurual of Physical Chemistry
3 G. Custard) G. :B~rancis, W. Schnackenberg, 60,8(j7-71 (19[,6).
SmaU Arms Incendiaries, A Review of the 1 'j, S. Gordoll and C. Campbell, "Pre-ignition
History u'fI:d Development, -i Vols, Frankford and Ig'uitioll RrHl'tions of Pyrotechnie Sys-
Arspual R:'port R1407, 1956. tPllls, Procfl'dillgs of thr Piftlt Sympo3iurII
<. Reilly anI Rae, Physicc "lll'mieal 111ethod, 1111 Com/illstio/l, Hpillhold Publishing Corp.,
2nd !i i., Van ~; ~~,. rand t d., inc., Princeton, ~. y" 1955.
N . .J", 1't12. 16. 11. IIpllkiu and R. MeGill, "Rates Explosive
f;. Wa' Moore, f'lI ,IIsical, Chemistry, 3rd J~:d., ])('('()lIlposition of Explosiws," Indnstrial and
i'ri~' .ial:, N. y" 1!)(j2. Eugillt'('ri ng' ('lwlllistry 44, 1:J91-;) (1952).
6, O. Kllhascl.~'wski and E. Evalls, Mrta urI', 'cal 17. l\L nilrol'd, l-<, Gordon, G,Weingartp!l, 'l'her-
Thcrmochemistry, .John \Vilpy & HOI' , N, Y., /IIai /'aralllci'l's Associa/rr{ With the /gnit1' m
1956. of till' Ma!Jllisilllll-8odium Nitr'ate SystC'J IS,
7. Irving I. Klotz, Ch ('III it:ol TIII,!,I1/, ,'ynG.:ics, Pil'atillllY Arst'llal 'rt'('hnical Notr 27, Dm .)1',
Prentic('-Ilail, N. Y., l!lfiO. Nt'\\' ,/t'I'>;<'Y.
H. Irving' Glassman, ,lIdo! C'mllbllstililt "roccsscs, 1M, 11. (', ('hristt'11St'1l, R. II. I(llipt', A, S. Gordon,
Pa:' IJI'pspntf'd at l.tth AllulIal l\lt'pting', 8111'/'i'1l ()/ Ail/lIlinlll/! Particlc C()mbu~ti()lI,
Amt'rl('UII Ho('k!'! !-io('il'ty, ~~()\', 1 (i~(', .195~1. Papl'I' (ll'l's('nktl at M. t'till~ of tilt· \V'stt'l'U
!). R Glal,st;l!IP lind D, Ll'wis, HilI/It ,: i of Phys- Statt's :-it'd iOIl of tilt' ('omhustioll Illstitute,
.,;al Chcmistry, V:lll ~()stl'alld Co., lit'" l'rill~(,­
I {'lIin'l'sity of t'tait, Salt Lakt' City. Oct, 26-27,
t.on, N .•1., 1!/t)O. 1!lti.t.
10. AMCl' 7()(i·~H:2, 1~llgillt'l'l'illg- I ('Sigh Huud- 1!1, \\'.:\1, l<'assdl. (', A, Fapp, D. )" lIill'nu1'alld,
book, I'r/lpuls~()n lind I'r()pdlall s. /lnd 1', /" Sl'l'lIka, Till' Kl'pl'l'illlfntal Natu/'I'
11. .J. B, Conway, A. '; Uross(', I', II'till'ed Melal ()f till ('oil/In/sholl of ,lfduilic l'OII'l:/'I'S, Roli.tl
J<'lllmts, Oflie(' of i\'aval Ht',';l' ,~h, Coutral't I'I'opt'liant HlH'~1'! i{.('st'al·('h, At'ad('lllit, Prt'SS,
N!l-ONR-H7:101, Washi;lg-toll, D I', :--:. Y, l!Hi(),
12. Kt'ith.J. IJaidlt'r, ('/lIl11i(,1I1 "ill I iI's, l\ll'Uraw- :!O. '1', A, BrzlIstl\\·ski. l'apor-I'hllsl' /)itJusi{)/I
Hill Book ('0., 11]('" ;,\, y" l~):;(i. PII/IIII s ill tli, ('/I/II,I,lIsliulI lif Jla!lll(si:l1Il allli
1:J, 8. G1asstmlt', K, .1, Laid 11'1', ;t11d 11. Eyrill~, . til/iii ill 11111, I'h,l>, 'I'ht'sj~;. Prijlt'doll I flliv('r-

The 1'h(,()TY of Ratl "ru!'1 sSt's, l\1dlraw-I1ill sit.". 1!I(i:L


Book Co., 1/1('" :-,;, y" l!l.tl. :!.1. J), K. Kllt'lll Till flllliliull /11111 l"omiJlIstioll
14, K H. 1"rt'/'lIulIl and S. <lordull ... Tilt' AJlJlli. IIf SIIII//l IJI"IIII il,. ~l/l1l/1il/l1l11 lV/tiS, 1'lljJ('r
AMCP 706-185

REFERENCES (coIlt'd)
presented at Western States Seetion of the 23. S. Gordon and C. Campbell, Differential Ther-
Combustion Institute, University of Utah, Salt mal A nalysis of ltborganic Compounds, Pica-
Lake City, Oct. 26-27, 1964. tinny Arsenal, Dover, New Jersey.
22. Eli ]1'reeman and Garry Weingarten, A Ther- 24. V. D. Hogan and S. Gordon, Pre-ignition and
mal Theory for- Rates of Propagative Burning, Ignition Reactions of the System Magnestum-
Picatinny Arsenal Technical Report 2596, SodilWt Nitrate-Laminae, Picatinny Arsenal
Dover, New ,Jersey, 1956 (DDe AD 2J.8 171). Teehnieal Note 23, Dover, New Jersey, 1958.

3-37
AHCP 706·185

CHAP'fER 4

VISIBILITY

4-1 INTRODUCTION and the COIlf'S, 'l'he eentral portion of thf' retina,
in the design lind dpvelopmt'llt of nditary the fnyca, is populated exclusively by COllI'S, and is
Ilyrvtl'ehnie <Iedeps for ill '!lllillllting a selected the ar('a of ('olor pNception, The region immedi-
arpa, /tnd for visnal sig'nalillf'~ WhPll othE'r methods I!.tply surrounding the fovea il' known as the para-
of communication an' imp;'a.·tical 01' impossible, fovea and (·ontains the rods, whieh do not recog-
an lIudl'rstandillg' (Jf humall visual performanei' nize ('olors, The f'y(' has two distill!'t states-t.he
is important. Thr ('olllpl('x 'asks pprformPll in lighr-adltpt.ed state and thp dark-adapted state.
Ill(,df'rn military operations rt'cjllire sufficient light 'fhe eye is ill the Jight-adaptf'd statr wheu the field
in ()I'(ipr that unfamiliar objpds can Iw located lumillanel' is about 10-:1 eandella pE'r square foot,
and r('('ognized against thpl1" hackgl'ounds and is dark-adaptrd at lumillaIwE's brlow this, How-
Sign'lling hy lIll'tho(is which dE'PE'IHi on sigh': Krc pV(,l', the (>ye is 1I0t fully dark-adapted until it has
t'OlllllIolIiy Ilst'd ill military tadi('s, in training ex- bE't'1l pxpf's(>(l t~) thp low level of luminancp for
ert'isps, and in eyaluatioH of lwrformanep of mili- about :~o minut('s, Only two to thrpp minutes are
tary items durillg deYl'I(,rHlHmt programs, ThesE' r(''Illirl'<I for thl' ~ransition for thp clark-adapted to
sigllals dt'ri \'(' fr,)1lI paekagNI units desigved to th!' light.a<iaptNJ stat!',
,'1,1;' ~'JlIok(', tlanJj', ()). light, or oth('rwise to give In tllP light-adapted state both thE' rods and
I'isllal i'ltli('ation of so ow eVt'llt, e,g" th(' marking of ('Oll('!, '11';' l'p('eptiw to li{!ht. In the dark-adapted

II par/i('lIla1' spot on th(· occ'all, 01' to trace the tra- 'itat!' only the parafovea, eoruposed of rods, is ac-
jPl'iol'Y of lIJissilps OJ' otll('r nlOvillg d"vicf'S, They ti VI', with t hI' rt'sults that color difff'rences art' not
m:ly hi' ('0(1('11 b,\' ('olo1' to \'0I1yey information re- 1,t'('og'llizl'd aIHI that faint sigllals are best Sf'en when
lating to dif'fPI':'lIt tYllt's of 1'\'('I'ts or a st'quPllce of off to a fooidi' (looked at "out of t!lt' corllcr of thE'
('\'I'llts For t'xllmpl!', a red signal mig-l·t be u3ed (,),(,") 1'atll('r thaI! Wlh'T1 looked at directly,
to i,:dieC\je tilt' arming' of II fuzl' and a greell lIignal
to indi('at(' ",1t"11 fHIH,jiollillg oe"lIfS, ~igll'lls for 4-2.1 BRIGHTNESS CONTRAST
IlHd killg" plIrpost's ('al~ hI' lls('d to aid in trd('killg fill objet'! pun hI' disting'uish('d from its back-
t'lll'llly sUiJlJIlIl'illl'S, to allow ;illlllll('l'g'e<! submarines
gr'olllld (01' from anotllPr object) because it has a
to III II k(' tllPil' positiolls known, to l(H'att' tow tar· tlifft'r(,llt ('0:01' or brightrH's;" rt has been shown
g-,'ts, lIlIt! to (all att('lItioll to slII'\'i\'UI'S of ail' ('rashes t'xpt'riIlH'ntally that difi'pr!'ll('(,s ill inightness arf'
oj' sinkil'g's,
IIsl l ally lIIu('h mOl'\, important than differences in
(,0'01', Tlw brig-htllt's).; eOlltnlst C is denllPd by the
4-2 VI"ION 1"lIlatioll :
IllllS!1llll,11 as VISIOn is f! s(,lIsatiOll rfcordccl by
tilt' t'yt', it is iJllportant to ('ol\sidt'r soml' of thf'
(' __ it --- H~
(4-1 )
-- If
propl'i tit'S alld dIHl'adl'l'ist.i('s of tht' (.'Yf', The
flllli'tIOllillg' of tht' .')'t. ill\'O!""s It ('OIllpll~X of \\'IIt,I'I' J: is tht' bl'iglJtll"SS of till' objf,(·t ll11d H' is
P hysi('u l. ph;.-siolof,!i('ltl, a tid psy('h()I()~~i('al factors, til" brig-htll('s,," of th .. ha('kgrolllld, If 1111 obje<'t is
Li:,.:lit l'a:liilg' IJP(lIl till' t·y" al'ts as '. ~tiJlllllus to 1I0t it" h";~:hl 'IS its bal'kf,!rolllld, th.· "1'l~htIH'sS ('011-
I'l'Odll\'" i\ s,'II"at iOIl ",hi .. ". ill til" S;lllpl":o>t ('a.-ito, is Ii tnl-':! i, lll·g-illil',. Hllti IlP)lI'OIlI.'h('s a "altlt' of -1 as
S('llsat i'lll /)f' hl'll-dltll"SS ;, !iltl:', W'll'l1 t h.· objPd i>.; bright,·" dl/1I1 its baek·
';'1..' ","(' ('("IL,illo.; 1\\'(. tYllt·" of ("'("·pt"!,,o.;, th,· "ods !!I'''lIiid. th,· "olltrast lllll~' Iw 1"'1)' lar/rt'. for t'X·

4-1
AKCP 706-185

(4.2)
where r:b is the brightness contrast, and Co is the
ar.tromatic brightness contrast, equivalent to the
dlromatic eomponent of the cont:!'adt. As chromatic
components of contrast are rarely over 25 percent
of the total llnd al'e invaliably associated with
brightness contrasts greater than 25 percent, visi-
bility, under field conditions, depends primarily on
the bright.ness contrast. This is especially true for
_3L-~L-~~~~J-_L-L-L-L~~~~~_~~ objects viewed at a distance since the scatterecllight
-6 -5 -4 -3 -2 -I 0 1 2 :I
LOG B (CANDl!S/"')
from all sources tends to stilI further dilute the color
('ontrast. Where brightness contrasts are limited,
Figure 4-1. ThresflOlds of Brightness-Contract for 80% as ill the case of signal flags or panels, color dif-
Detection for Five Angular Fields (Minutes of Arc)
ference may increase visibility. However, at or near
ample, a bright light on a dark night. The bright- the limit of visibility, the hues of chromatic target
ness contrast in daylight or in artificially produced are not perceptible. This is parijcularly true for
white light, where the differenee in brightness is violet, blue, green, and yellow stimuli, Orange,
due mainly to the amount of light reflected by rf'd-purple, and red appear reddi3!J or brownish
the oojeet as compared to its background, seldom under th('se circumstances.
f~xceedN Ii value of 10. If an area has been el',mou-
flaged, the brightness contrast may be 0.1 or less,
4-3 ATTENUATION OF CONTRAST
If the brightness ratio 11/ B' approaches unity,
The apparent c/.mtrast (both brightness and
a etage is reached where an object can no longer
neh romatie) between an object and its background
be distinguished from its ba(;kl!rOlmd.
is reduced when viewed through a medium which
While the thrl'shold contrast varies with each
indbidual, average values at> shown in l'-'igure 4-1 seatters and absorb light. For a homogeneous
medium like the atmosphere, containing both the
depend on the angle which the object subte'lds at
obsl'rver and' th,~ object, the amount of contrast
the ob!.erver's eyl' and the mean level of illnmina-
reduetion is governrd by the balance between the
tion. "'or daylight conditions, n value of 0.02 is
light transmitted from the object, and its back-
ger\('rlllly ae('l'ptl'd as an average value for the
thrl'sholll 1'(Hltrast or limen. ground, Ilnd thp space light contributed by the
Visual a(~l!ity is oftL'll expn'ssed as till:' rc- intervening medium. If the medium is stratified,
I'iproca! of this angl" in minutes of are. All acuity liS would be the ease when a smoke screen is locaicd
value of 1.0 is aeeeptl'd as a standard for lIormal between the object and the obsrrver, reflection due
yisillll e\'en though, undf'f id('al c(llulitiollS, much to IIluitiple-f'eatteriup, may still further reduce the
I!reatl'r tll'tuil (~all bl' rl'solved. appart'ut contrast,
Op to about ollt'-fifth sct'ond, tht' [)hot()t~hemieal III gem'ral, if tilt' inherent bright'1ess contrast
rl'ciproeity !IlW applit's and the produd of th" il- betw('l'n two objrcLs, or of an object and its back-
lumination tim!'s t.he duratioll is a (~Ollstallt. It hps grollnd, iH b,ri ven by EquatiOl. -1-1, thr apparent
LrightlJ(,s~ eOlltrast ('.t. when viewt'll at a distance,
lieI'll dl'lIIollstrated ill tlm'sholl! lll('aSllrt'mellt~: of
will be:
visual perfm'marwf' that. ill thm;!' eaSt'S where
thl duratioll is IOIlg"t'r thaB olll-fifth 8('("011<1 (as is (8 - B')f-{Jx
trw' f(,r most ('USPS of illter'.~st jll Jlyr·ott·dlJlics), Cr = --------
B'c- i3 ;r + (}
(4-3)
this is not applicable.
wiH'l"t' f{ is Hl(' hrightnt'ss of the first object and H'
4-2.2 OVERALL CONTRAST is til!' hrigiltnl'ss of the SCCOJl(l objpd or the hack-
Tilt' oVt~rall eOlltrast ('0 betwcen an object. and g'rolllld, ~ is til(' sl'atterillg' (~()dlkj(,llt, .r is th(' dis·
it...; ba('k~r()ufl(l is approximatl'l y : tallel', alltI (] is thl' glarp seutterl'd iJlld fl'fiected by

4-2
AJ(CP 706-185

(slat:lt) range 71 j 0 is their inllereut. contrast; B


is the brightness of the object; B' is the brightness

'-l
of the background (or second object); and ~ is
I~g the scattering coefficient.
110
1.0 If the atmosphere is optically homogeneous,
60
'.0
i.e., the apparent hright.ness of the sk,f is: not
~o changed by moving toward or away frOT.l the
30 horizon, this equation reduces to,

i (4-5)
I-
~
'-'
I-
20

:.0
1 wher~ Ox is the apparent contrast at a distance x.
The Pleteorological range, the horizontal range
Z 0.9
for which the transmissi(IU of the atmosphere is
i'"
~
oe
07
0.6 two percent, is given by:
0'
0.4 -1 3.912
0.3
Xl< = -~- In 0.02 - -~- (4-6)

0.2 The meteorological range is the distance at which a


large black objeet, which hM an inherent contral!lt
of -1, can just be recognizad against a daytime
01 Lo--IOOOL--2..JOOO'---:3000"L:-4..l000-,-.,..,.~-::L:---:-6000:l=~1000·
sky. Visibility, as normally reported, is about %
),ARGET DISTANCE IN YARDS
the meteorological range. The meteorological ranges
for t)' pical weather conditions are g?ven in Table
4-1.
if the object is viewed against backgrounds
Figure 4·2. Apportm' Centrost as a Function of Distance other than thr sky, the expressions are more com-
plicated. The apparent contrast at all effective
a cloud i:l the same ui1"eetion as thil light from the ,listance R of a target again'lt any background is
object. 'fhe object will be visible only if the ap· given by:
parent contrast is gl'eater than t~e thl'eshold con-
trast or "limen" for the particular total illumina- o (4-7)
tion level. 1 + (BH/B') (e fJB --1)
where C is the inherent contrast between the ob-
4-3,1 ATTENUATION OF CONTRAST ject and its background, B II / B' is the ratio of the
BY THE ATMOSPHERE brightness of the horizon sky in the direction of the
The apparent eontraf,t between two distant object to that of the background, and ~ is the scat-
objects, or a distallt object !llld its hackground, is tering coefficient. If the ratio B H / B' is one, this
reduced as shown in Figurp 4-2 wilen they arc equation reduces to the equation applicable to the
vicwcd thrul1gh an atmospheri(' aerosol. This re- visibility of an object against theborizoJJ sky.
duetion in apparellt (!ontras t limits the maximum The calculation of the visibility of an object,
distaw'r at whi('h t:.tr~tets and signals can he seen. whf'n viewed from above, is complicated due to the
The most grll!'ral ('x pression for til(> (eduction stratifieatiou of the atmosphere. If this stratifica-
of ('ontrast by the atmosphere is: tion ean be considered continuous, the scattering
(~oeffi(~ients will vary regularly aud in a predictable

(4-4 ) mannrr. Normally, however, this is not true, and


tlw effeetive optical range R is taken as the hori-
eJ! is Olt' apparNlt contrast between two objects, zontal distaTI('e containing as many scattering
or an objed and its background at the effedive particles as aTe found in the slant path R. The

4-3
AMCP 706·185

TABLE 4·1
METEOROLOGICAL RANGE FOR TYPICAL WEATHER CONDITIONS
-----_._--- -'.._------
Daylight A ttenliati01I
Visual Ooefficient, It, Tr(1,nsmission,
Weather Range, r Per &a Mile Per St'a Mile
Dense fog 50 yar'ds 156.4 0.0240
Thi~k fog 200 :19.1 0.0210
Modera.te fog' 500 15.6 0.024
Light fog ]000 7.82 0.022
Thin fog 1 spa mill"" 8.91 0.02
Haze 2 1.95 0.141
Light haze :1 1.30 0.272
4 0.98 0.376
Clear ;) 0.782 0.457
6 0.651 0.52J
7 0.55!! 0.572
8 0.488 0.614
9 0.434 0.640
Very clear 10 O.a91 0.076
11 0.356 0.700
12 0.326 0.723
14 0.279 0.756
16 0.244 0.783
Exceptiollally clear 18 0.217 0.805
20 0.196 0,823
24.1 0.162 0.85
:37,1 0.105 0.90
7l,~ (J.051 O,!J5
1'heoretica lly pur!' air 167 0.02:14 0.976

• 1 ~ea mile cquaig 1.151;'7 ~tatute miles or H080 fed,

I'ifpl'liw opti('al rang!' If is r!'latt'd to adual path the smokt' may o(~('lIpy only a relatively narr(l'\·¥
Ly: rl'g-ioll bl'twPt'lI tlw target and the obsen"er. Undt'l'
thest' ('irl'ulllstallces, the iuten,;ity of illumination
_.-; ___~~,7~( 1 - /. [_~_J( Sill~"~]) (4-8)
h - ~lll (..) 21,7(J() lllay vary gl'patly depending on th!' r;:lati\'e loca-
tioll of thp objPei, the observer, thl' smoke cloud.
whl'r" (..) is ill!' Clllgl(' that tlIt' "hemt pat,h Jl makes
wit It th" horizolltal. Plots of this !'<lllation for lind tht' SOlll'I'e(S) 01' illumination, sO that til<'
\'lIriolls \'alues of (>o), applil'abl<' fOl' ilitprIrIl'diatl' quantity of ;,l1lokp c!'qllil'ed for obscuratioll i~; a
\'allll's of tht' slaHt rallg!' R, ar(~ prt'spHtpd in Pigurp highly variahl(, quantity. Bpealls!' cf thf' comp!i..
4-:1. 'I'ht' vaIIl!'s of thp tl'll(' altitnilp ar!' ill(lil'atl'd l'atl'd way in wldeh Hw inl'idt'llt light is !'.('attpred
hy till' dashl'd lill('s 011 this diagralli. liS a flllH'tioll of angle and beedllSP of muitiph·
;;/'attpl'ing, till' <It'gl'P!' to whieh light will pellt'-
4-3.2 OBSCURATION OF VISION triil!' a 1'10lld l'l1n only bl' approximatp'l. While a
BY ARTIFICIAL SMOKE CLOUDS lllajor' fral'tion of tlip light scattned by partiei<'s
TIll' of artifil'ially pl·()(ltH·l'd Slllok('
ilIflIll'lll'1' llt'ill' ti'" optillllllll sizl' for a sel'!~('nirrg smoke lS
('Iolld~; 011 \'isihility i." ('()lliplil'ated by th(, fad that sl'attpl'l'd in thl' fOl'ward dirt'l'tiou, S()Jll(, light is

4-4
AMCP 706·185

0
,0,.000 00
,0, 0
~25,OOO

----- .00,000

-·575.000

l?n,OOO
350,000
II~.OOO \

I
"O,OO()-~ 325,000

'05000 J
t
t=
-300.W'J
IOC,OOO

I
::::: 1 ~.~
~
85,000 -I ~ -'.' , -----f 250,000
I/)
r-
Io
-.: FO,OOO ...
Z

~ 225,000 :r.J
n,ooo-
~
!AI

-
I
-,
I 2CO,OOO
'"
~

I '"
1'1
...
(/) ~O,OOO
I ;j

t
175,000

55,( ~O-
I
. -i---- t
I
i --_. - ISO,OOO
~O,O(,O·
t
I
45,000

40,000
I I i

i -J
I
+-- 125,000

~5,OO('

")0,000
-.
-l-I I
____ .1.- ,00,000

,,I I
I
I 75,000
25,')00 .
t
20,000
I
50,000
1~.vOO
t
10,000
I 25,000

5,000
0
0- '10 0
.00
0

Figure 4 .. 3. Optical Sinn' Range Diagrclm for the Optical Standard Atmolphere

.. 1
Allep 706-185

reduce the illumination on the tar get and back-


ground, will ill crease the effectiveness of a smoke
screen.

4-4 VISIBILITY 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 signa) can be seen against its
background depends mainly on (!) the perceptual
.Z
eapaeity 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
o 10 20 30 40 !!(l 60 TO 80
CONTRAST I'll.) and the angle it subtends at the eye of the observer.
'I'he angle, sub tended by a target area, depends on
Figure 4-4. Brightneu Requirements as a Function of
Acuity and Contrast the size and shape of the object. For a circular
target at a distance of X yards, the angle cc 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 of the light not absorbed by the cloud will re- IX = 1293\/:::1 minutes of arc (4-10)
t.urn to and be scattered from the same side of the X
cloud that it entered and the nloud will behave as Af] 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. of the target against its back- the target or signal, or the observer, must be ele-
ground, in this ease, is: vated for sighting long rlistances. The geometrieal
range for various hpight~ is given by:2
eli = 100 - f) (M - M')e- (JR (4-9)
X = 1.325(H +h) ( 4-11)
where 10 is the effective intensity of the incident
light, M is the reflectivity of the target, M is the where II is height of target or signal in feet, h is
reflectivity of the background, ~ is the scattering height of observer in feet, and X is t.he distance
coefficient, R is the effective distance from the tar- in miles.
get to observcr, and f is the fraction of inci-
~lent light which penetrates to the target. The 4-4.1 VISIBILITY OF TARGETS
amount of light reaching the target, as well as the UN1)ER ARTIFICIAL ILLUMINATIONs
<lllCnuation of the contrast between the target and It is impractical to require that normal visual
its baekground, depends on the number of 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 hy
of the concentration of the smoke and the thickness pyrotechnic flares since there is a practical limit
(If the cloud. to thE' intensity. The intensity should be such that
The dfectiveness of a smoke screen also depends targ-l'ts, having a size and a I!ontrast with the
Ull the relativ(' lo'~ation of the smoke target baek· baekgTound that is typical of field conditions, can
ground and I;ght soun~e. The effect of thpsp changes lw readily located awl reco~nized. Intensities
in relative locations is eomplicated, and has not greatE'r thall this minimum are pxc('ssivc. As shown
been worked out in detail. In gpneral, anyt.hing in I<'igure -i--i, illuminatiolJ levels between 0.1 and
whieh tends to incI·easp the effpctiv(' brightness of lO.O foot·laIllberts (FL)·, which can be obtained
the smolcl' doud, as weU as anything that t!'lIds tu * NOTE 1 milliJambert ::::: 1 foot· lambert.

4-6
AMCP 706·185

TABLE 4·2
REFLECTANCE VALUES (IN PERCENT) OF VARIOUS TERRAIN
FEATURES AND BUILDING MATERIALS

Object Wavelength in Microns

I. Natural Terrain
a. Soils,' 0,4 O.!3 0.6 0.7 O.H 0.9 .1.0
Dry yellow earth 8 16 37 55 69 76 82
Wet yellow earth 5 9 25 42 58 67 76
Dry sand 18 28 il7 45 52 56 58
Wet sand 10 15 26 32 37 41 43
Dry red earth H 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 browll earth -l 6 11 14 15 17 19
Dry loam )ol 12 18 20 20 21 22
Wet loam fi [> 7 9 10 11 11
h. Vegetation:
Grass 6 8 10 13 55 67 70
Evergreens :1 4 7 6 24 24 24
Straw 7 15 24 33 3!J 44 46
Dead grass 7 13 20 26 31 35 37
Dead brown leaf 6 9 11 27 43 51 69
Dead yellow leaf Ii 10 23 39 45 48 51
('. Terrain as seen frum ·4,000 fect,'
UrcPIl field 4 7 10
BrowlI. field 3 4 5
Y(>llow.grren vegetation 5 8 15
Light ;Jand 12 16 21
l-iandy ground 8 12 14
Wet mud 5 8 9
'\1!Hi eovered with water 4 7 6
Pond water 3 2 1
Watl'r with sllsppnoed material 3 4 5
Dark vol('anic rock 6 6 7
BIa!'k asphalt rllllway 4 4 4

II. Bnildiu/! Materials


1/. j'aints; 4 4 4 4
Black 6 6 11 12
I~arth brown 9 15 45 47
F~arth yellow 6 7 19 21
Earth red 15 ?A 42 43
Sand 16 21 37 41
Dpsl'rt saud 7 9 16 16
J<'il'ld drab 4 7 11 9
Olive drab 4 6 7 5
Forpst /!reen

4-7
AMCP 706·185

TABLE 4·2 (cont'd)

Object lVa1Jelength in Microns

11. Building Materials (Continued)


a. Paints ((Jontimled): 0.4 0..:; 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
Red 5 5 25 75
b. Materials:
Concrete tiles (uncolored) 28 35 37 37 37 37
Concrete tiles (black) 9 9 9 9 ::} 9
Slates (silver gray) 19 20 21 21 21 21
Slates (blue gray) 12 13 14 14 15 16
Slatps (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
AluminulCl 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 r('adily with pyroteehnie iliuminants, should 4·4.2 VISIBILITY OF SIGNALS


bl:' adequatp to detpet and identify objects sub- The requirements for visibility of 11 signal vary
tending approximately 5 minutes of visual arc considerably from one application to another. It
agaillst a terrain baekground, provided the con- is not always possible, uor necessury, to provide
trast is grpatpl' than 0.1. When the targl:'t and its a signal which is visible at extreme ranges. How-
haekground are iliUlninatpd by the same light {'vel', it is desired that a signal produce the maxi-
souree, this eontra.'>t will (as is true for daylight mum visual effect over as long II. distance as pos-
illumination) dl'pend Oil the reflectauee values for sible and, in some eases, for as long a period as
the targl:'t and backgroulld. "alues for typical possibll:'. In addition, it is often necessary to
materials wliieh might be fOllnd in thl' field are modify signal performance to meet practical size
given in 'rable "'-2. and \\'(·ight restrietions. Th'!se restrictions are

4-8
A)[CP 706·185

~::~n-rT-r : --- l--~-T-Ir-l


i :; -~-I_ __ - t _1- .~. +··1
I
~
I I
I
"-,I
J
:;:::! 0.3 - - j'
~~

t-- -- -
I

~g
~~ 0.2 j 1 g:: I
io~ ~=:1~ Jn~
'1
I'

,..
C;::+=:jlt:'-:=:' I. u •••• '"
~
8
O· 20"
ANGLE
40· 60·
BETWEEN INCIDlNT
100·
LIGHT AI
I ,rl" 140·
OBSERVER
160- 180" '"Ci

Figure 4-5. Effect of Direction of Illumination on the 5


o 20
_ II
40 60
1
80 100 120
l.~._.
14U 160 180
I.uminance of a Smoke Colum, ,ANGLE BET'N~EN SUN AND OBSERVER <DEGREES)

Figure 4-6, Effect of Relative Direction of Sun and Smake


f'xtremely imlJl)rtaJJj' for signals earried aboard
on Time of Di;;covery
aircraft or submarine~;.
of vi \~bility, will be I ~I)ctively the s.ame iloJor as the
hOI :nll,
4-4.2.1 Visibility of Smoke Cl'-"Jds
Thp visibility of a relati vely ~:mall dellse smoke
doud, sueh a:, waul,1 be produeeu as a signal. dr- 4-42.2 VI: .y of Light Sources
pmlds all the ahilit of the smokp palticle, to ;"H~tors I('h infhll'nee the visibility of a light
scatter light, or 1'1 tieet hy multiple seattpl'ing, lUI', 'lrp \:: i\>lltially the same as for any other
the dir('ctioll of tli(' obs('I'ver. ~'actors whith d,'- (>cj"eL"hl'il hilitJ IIf an illumiu'lted visual
tl'I'min!', to a large "xtent, the visibility of a slUok" ang," or i,ppm. Ill, <'I. lIle degree or Jess is de-
dow! illl'jud(,: (ll illumination Il£ the smoke doud, p('wlellt pl'incipally .IpOr thl' total light emitted
and (2) ('Uld rast of the cloud against a back- 1111' area. ~'or a stl'llIly "oint source.
gToulld.
F' =-.f~·
e = .
:J.5 )( 10- 11 Hl/2I m ;tens/cm 2 (4-12)
The ('treet I \'(' brightness of the cloud d!'pcnds
011 the relative location of the observe I awl doud,
as wpH as the int.ellsity awl (li.rectio(1 of the inci- wll<I'e P is the thl('shold value of flux density (in
<lI'lIt Jig-lit. This cffeet is illdieated in F'igure 4-fi huneWl pn square centimeter), C is the threshold
fol' ;1 1'!'latiVt'ly dilute, laboratory smoke column. int!'lls:ty of ti::' SOlll'Ce (in candles), X is the dis-
'l'hese !'('sults, dur to the tendency toward forward tance fn'lll soul'ee to observer (in centimeters),
scatterillg', illdieate tha a smoke ('oIUTnIl is many amI l' is the background brightness (in candles
timrs as beight in th!' lJ'(,('tiolt of the SUli 11.<; it is Ill'l' S ,'lart> centimeter). The illumination pro-
opposite to thl' sun. Ie rffect of the relatl ve d i- ,ltwl'd at thc observer's eye i3 reduced because of
reetion of thl' SUII a! ;lIloke is also illustrated iI' ,tmospherie attplluation in accordancp with the
}<'igllI't' -t-fi wiler!', ' ·xpectell, th,' tim of dis .Ilowing t'quation:
l'o"~'ry is thl' h'as! \ en the relativi POSil iOI srI',
sill: ill a maXilltlll1l ioud brightness. ('ldl.'I' of Ii 11),. = .~.":. I'Xp [ - 3.912 (-_~)] ( 4-13)
re1atl\'('ly deliS!' ,'101 results frl'lII multi pie scat
tpriug Iii abso"p' 11. The ('0101' intpl''id.v ill wher!' III is the ill teJlsity of the source and X R is
dilur,' "I"lId IlIIi less bl'('ause of tilt' : ('(hI('('11 thl' ml'tpol'Ological range. This equation is valid
'Hut Ipl(·.;eattf'l'illL' ,·tlieirney. If thp particles mak- ollly wh!'1 .\' iii la "gl' {'nough that the light may be
l~ up th(' 1·ll1Iti art' till' 'HOI sizp (tf small, ('onsiderl'li "a POillt s(}Urt'P. The maximum angu-
.In mall,\' ), tli·· I· dol' prodlJ('pd ,ly bl' ;tnged lar iz!> of thp light /lource, which can be con-
;til, /01' Sllpprl'S~ i '/'111' appan'llt ('0101' of the sid!'l d 'lS a point S'J11I'(,(" variff' ',"lith the adapta-
,·jolld will ('hllll~1 'I it Ii distallPp alld, Iwar the limit tioll bJ'i~: htllf'SS as givl'll ;1\ T~: 'Jle 4·3,

4-9
A)[CP 106-185

'fABLE 4-3
MAXIMUM ANGULAR SIZE OF LIGHT SOURCE AS A FUNCTION
OF ADAPTATION BRIGHTNESS
-------_._-----------
Arlaptatio'n brightness i~Jaximum a1tf)l.llm· .~izc
(foot-lambc1·ts) (minutes of arc)
1,1:00 0.708
100 0.70B
10 0.750
1 0.8!H
10- 1 1.30
10-:; 2.82
10--~ 6.68
10- 4 B.5G
10- 0 15.0

.A flashing point-source light, wherp t.he flashes values of l' as low as 1.0 second) because of the
!l.re of short duration (le';s than D.2 second), must lower visibility of short flashes (according to
have, in general, a hi.r~her candle power than a Blondel and Rey). If T is greater than 1.0 second,
steady light in order to be seen. I t has been :'ound tlll' finding ti,Hf' is also longer because t.he eye
that the threshold intensity F', requir\~d for visi- Illay pa:;s over the light Joeation during the off
bility of a light of duration to sflconds, IS given illtel'Val. It was found that a light of ten times
by:· threshold intensity was almost always located at
the first flash while three flashes were need0d if the
l't. == Fa (tv + 0.21) ( 4-14)
light wpre only five times the threshold.
where /I'. equals tile threshold int.ensity of a steady TIt(, eft'ed of selective transmission by some
light.. Thus, WhfIl a flash last:> sew'ral seconds so type~ of htmosphere is also important when con·
that 0.21 is nef,ligiblt', the threshold is the same sidering ('olorl'd lights. Table 4-5 indicates the
&'1 for steady light. However, as shown in Table mag-nitllGI' of selective absorption of components
4-4, for small values of to, whcl'c P will be' larger of sunlight by thp atmosphere.
thUTl /11•• this is no longer truc. These ratios are not
changed grl'lit!y for ealldlepo\\,prs up to 50 times 4·4.3 ESTIMATION OF VISIBILITY
thre'lJlOld for flash durations from 0.05 second up '1' Ill' ('stirnation of visibility ean be simplified
to 1.0 or 2.''> seconds. by the Ilse of nomographic visibility charts pre-
1"01' sit.Iatjull:'. in whieh it is not known where a pared for this purpose. A (~hart for circular- tar-
fla.;h will appear in th,; field of vi,'w, til(' filldin~ gets, which has hpl'll adapted from the morc com-
t.inw is quite important.. 'l'he two varigbles of rna. plpt(, ('liarts it vailable, is given in I"igure 4-1. To
jor imp/)rtaw,(' ill t/)(' (·onspicuity (short findh.g IlSf' this e1lal't for deit'rlllilling' visibility along a
tinH') f.f a flashing- lig-ht of II ('Il11(lIepowrr well horizontal path, a straig!tt('dge is laid across the
ahoy!' thrt'shold intt'l!sity art': (1) thf' timp interval ('hart ill slH'h a manlll'l' that it connects the value
betwt~f Ii flashl's 1', and (2) til\' dun.tion of eneh of th(' llllIt'rt'nt tontrast b('tW('l'1l the objeet and it.s
flash Ie, in St eOl.lds. A flw.;hillg light is most (~OIJ­ bm·kgTolIlHI with tilt' yahw of the sky· background
spienous Whl'lI l' lips betWl'l'II n.1l alltl l.() s('('olld hl'ightlless ]'atio (this sl(y-baekgroulld ratio is uIlity
lllHl t" is 1)(·tw('('11 O.2;j I!I)(] O. ?;i owc"uJ.:1 Decreas- if t Itt' h1wkl!l'Ollild of ! Ii(' targd is the hori.zon
ing l' or irwrPllsing t o /l' illl'I,;'aSes the fillding tiult' sky). t'xil'Hded to intt'r~('d tht, Zf'ro liminal tar-
lx'{'ausp of redudioH of Ih('kl'f. If (; is Iwlow U.fi god <li:·tlll1l·(· liTH'. Tht' straightedge is then re-
s(>cond, til(' aVl'fll),{I' fil'riillg' tillH' is im:n'hsed (for IOl'lItl'd SLl that it l'OIllH'l'iS this point with the
A)(CP 706-185

TABLE 4-4
VISIBILITY 0]' FLASHING LIGHT COMPARED 1'0 STEADY LIGHT

}I'['lShDuration, Ratio of Flashing Light


seconds to Steady Light
1.0 1.2
0.5 1.4
0.4 1.5
0. 3 1.7
0.2 2.0
0.1 3.1
0.05 5.2
0.025 9.4
0.01 22.0

'fABLE 4-5
ABSORPTION OF SUNLIGHT BY ATMOSPHERE

Wavelength, Angstroms Percentage Transmitted


4000 47.5
4500 55.3
5000 62.4
6GOO 68.2
7000 75.6
8000 80.1

These, figures lepresent the relative transmission for th(l difterent


wavelengths during the day under average el'lar conditions ",;th the sun
at the zenith, and they lIIay vary greatly under other conditi<ms. It must
be remembered thl\t a light signal can be seen at a much greater distance
than the distance at which its color can definitely be distingUIshed.

value for the meteorological range. The intersec- .1can be calculated, for targets which 8ubtend a
tion of the straightedge and the curve for the small angle lit the /)bservp;,'8 eye, by the equation:
('orrect general illumination level locates the lim-
inal target distance. (A sin 8) (4-15)
The procedlll'(' for l'stimating the visibility for
slant ~)aths is som"'vhat mort' complicated, espe- whpre R IS the first approximation of the optical
!'ially if the atmosphl'l'e is stratified. If no optically slant. range estimated by use of the nomograph, R
dissimilar strata are presl'nt. thf' optieal slant range
is thr eorresponding slant range for a sighting path
ean be df'termil1f'd in thl' sam" mannf'r as the visual
whieh makes lill angle e with t.he gmund, and A
rangr, along Ii horizontal pl'th. TIl(> aetual slant
t!U1ge cun thl'll bt' approxill1at('d by thp lIS(' ()f Equa- is tht' Itl'eli of tht' target. 'fhis value fur A ill now
tioll 4-18 or I<'ignrt· 4-;~, Bf'eanse tht' slant rang" lls('d til ('1I 1"111':!" II better value for the optical
is 1I00'mall), grplltrr than tIt" optieal slallt rang!', slallt "ILII !!(' H and I',~rr(,spoll(lin,~ slant range R.
t IH' I'tTf't'ti v(' art'a of thp targf't is It·~~ thall its aetnal TIll' lJolllOgl'aphs art' aiso useful when stratiti-
art a and th(' prl'liiett'd slallt rallg!' will he high. (~atilJll of thl' atlllosp!H'rt' ('RUSt'S an effective di&.(lD-
,\ ht'ttl'r valliI' ('11II Ill' obtllillt·d. if 'III e/fedivt' area tiul!ity in th!· Ilit'tt'orological l"angt'-altitude rem-

4-11
AMCP 7(}6·185

~L-~£--.£,,L _ _ _ _ _ ._ _ _ _ _ _ _ _ _ _ _ _--1

---~~----~---~--~~~~---------------.------------------~
CONTRAST
11).,,., ('II 80 S S 0
OC'> 0 C d 06,j 0 '"
~~LL~~__~~~~~~~~__ru~~J__~J-~-uIIUI~IUI~I_I~I~1~~IUI~IILLI~I~I~I__~I~LL-~IL!lUI-L~-L~~__LU~-Y

~~L==~-_- --_--_--~ __ __--_-=-__-_--~=~-=============~ _ ----_ -----


...

-----------..-----.- .. -------.- ------ -------------------------l .,.!


"

--_._---"--- ... -.------ -_._-._--_._---_.-


--------------------------
~ ------~------.- --~-

I---I---,f-f--H--.---------------------.-----------------------------
+---+-;-·7~·----------·-----------·----------------·------· - - - -..-.-------------
r-t----nf-+------·--.---------.-..-=-----::..--:....---:-----.-----....:----.-.-------.:::.:::.:::-----------. -.------------=-=--=-=--====1
----------------------_._---_._._-----_._--------_.-.-----

(;)

'"
.
METEOROLOGICAL (,..fI.ES) 1. Pfi
fit/ure .,·7. Viubilifr Nomograph

4-12
AMCP 706·185

TABLE 4·6
SKY BRIGHTNESS

Ambient Brightness,
Condition millilamberts
Hazy· 10,000
Clear 1,000
Light Overcast 100
Heavy Overcast 10
Twilight J.
Jeep Twilight 0.1
Full Moon 0.01
Quar+,er Moon 0.001
Starlight 0.0001
Overcast Starlight 0.00001

* The maximum brightness condition which is likely to be (>lcoun·


tared is that of the sky on Ii slightly hazy day at noon.6

TABLE 4-7
SKY·GROUND RATIO

Sky·Ground
Sky e01lriition O/'ound Condition Ra,tin
(h~r~ast Fresh Snow 1
Overcast Desert 7
()vercast J;-'orest 25
Clear Fresh Snow 0.2
Clear Desert 1.4
Clear }<'or('st !)

tiollship. Ll't it lw asslIlllt'd, fol' t'xltmplt', that ther!' otf, Bp('allst' ,)f til(> problems involved, the estima-
is II grolllld hHZP whi('h has a top at ;;000 fel't. and tion of !'lunt rHngpl-' i~ It>ss satisfaetory than the esti.
that thl' mt'tt>orologil'1l1 rang!' is fivp tiJll{,fj goree.h>r IIllltioll Ilf horizontal rangt', Where experimental
aho\'!' thp hazt' bOlllltlary thall bplow it. J<'Ol' this \'l\l1ll's a 1'\' lIot Il\'aiiahlt', typielll valllps for thp- sky
typt' of \'isibility prohlt'JIl, II lilll> is ('ollstrnetf'd brii!'htllt>ss art> given in Table -t.() for "ariou!! IUD·
till thl' optit'al slant 1'1i1lg'P diagram, !<'igul't> 4·3, bi t'llt ,'(;llditiulIS, Typi!'al valll{,s for tilt' sky·
frolll tht' ol'igin to thl' illtt>rsP('tio/l of th!' ('urvp for ~~rolllld rutio al'(' givPIl ill 'rabl!' 4·7,
thl' (iPsil't'd v.i{>\\'illg allg-It' H, with tht> dasilpd lillt' It is to bt~ noted that. the nomograph predicts
rt'pr!'st'lltillg- tilt' trill' altitudt> I)f fl(100 ft'!'!. A It distalll'(' <'it "hil'h tilt' tarl{t't is liminuliy v:sibl('.
>;\'\'olld ('UI'"t' (whi('h has tiVt, tilllPs tit!' slope of tht' If till' ('OIl! 1'11:;1 vulue is tlivitll'd by two \)('1'ol'{' llsing
orig-illlll t· II r\'(' ) is dl'awlI stlll'till~ lit fhi:.; poillt. th,' IlOlllOg'raph, the result obtained is tht' sighting
Tht, rt'llltiullship IH'tWt'PII il, tilt' opti,'al slallt )'ang!', I'll llg t' , tht' distaq,·p at whi('h tilt' nbj('('~ '.'IHl be
allt! H, tht, slHllt rllllg'!" full!)ws tltt' !'t'sultallt ('un'p, ~""Il witb thl't'"hold ('oltfid('Jl('p, For HI" obje(>t
If th\' udllal boundary of tht' groulld 1'lIzt' i~ dil'· t () hI' ,'asil)' St'I'lI, till' ('olltrast valllt'>.; ."hould h(>
rust', tltt, sharp ('!JlIlIgt' ill slop!' ('1111 hI' roulldpt! di"id!'d hy lit !t'llst fOil 1'.

4·13
AMCP 706·185

INTENSITY (CANDLES)

-----
---== =====--
---==----=:------- l
.",

l
l
I
"o~
------------.<+----+-----J/'----,,----;''---7.Y'-:~_,._.--------v~
-----;"'/

~ ~-~--~~~.-~~~~~~~~~--~--~~~
..

-------------I-'-----n---r
+-t--+--+---I-y"'"yf------------------
--------------- $"
3

-+----,;'--.#-c~~-\------------------
~
I..
.f~~---~~~~~--~----------------------~

--~--~~~E~-=-==---==-==--==-
-~- ~-~-~~~ -~= --\--.:--=--:.-- -------------~-
---- -,--- I-
""
C>
--r-~~~~~~~-----------------+_----------- ----~ II:
,n ~
\-
1----+-f----I--I-I-7H-,L-------------------L----

\
l'

g
...<>

IoInrOROl.OGICAL RANGE (YAROS)

Figurt! 4-8. Visibility Nomograph for Signal Lights


AMCP 706·185

TABLE 4-8
INCR.EASE IN ILLUMINATION REQUIRED FOR
POSITIVE RECOGNIT.ION

Pi(:ld Factor
Applied 10 ThresJwtd DetectibiUty uf
Cnndlcpow!'l' Light Source
Lig-ht somcl' difficult to find even if loca·
tion is knowlI.
Tlight SGurCe modt·ratcly difficult to find if
location is approximately known and ob·
Sfrwr is on steady platform and has long
tirrH' fer search.
;;·10 TIi~ht sourN' I'asy to find lind!'r circum·
stan('es aboy!'.

Light sotlr(~t" pasy to find under reasonable


('JI'"CuI}1stI:lJlees at night, for example,
,,"arch field 110 greater than 100 dt'grees,
ob"ervl'r can gi VI' his full attention. Diffi··
('ult to find in daytimp unl"ss obsPrver
knows Whl'f(· to look.

Li~ht sour('(' CIl!! be found ulldE'r strenu-


OilS cir('l1mstallet's at night, and under
lIlost ('ir('um"tallcPs ill the daytime if the
s,'arch fif'ld is not too large.

Squat'" objl'l'Is 11.1'(' as visibll' liS (,irl'ulal' obj('ds foot·lamberts will be liminally visib1.e on a clear
of til!' sallll' arpa. ()hjt'i'ts of othl'r shapl's art', ill day, when the meteorological range is 20,000
:.rt'II!'I'al, ll'ss visihlt,. yards, can bp es·Umated in the following mann!.'r:
j<'i~lIr(' .t-t' is II \'isibili1~' "hart fot' prpilietilll! As sky brightness 011 clear da!' is approxi-
th, l'Illl~1' at whit'll si)!lIal lamps IIlId olh,'!' point mately 1000 foot·lamb!.'rt:., the contrast of ta.rget
SOIlI'\'I'~; of li:.rhl will til' r minally \'isibll'. To \I",' against sky as background is:
this ('hill't, 1\ strai)!hl<'(I~1' ,>' pl,I('I'(\ a('ross tlH' eh,trt
I ""I it "Ollllt'('ts Jill' 1III't\'orolo~i('al rtl!ll~\' with
10-1000 _ !)!j
-lO()O-- - --., .
til" Illtl';lsity lit till' li:.rht slIlIr("('. Thl' illtprsPl'tiun
of thi" st raight lilli' with 1 b' ,\11'\'1' for thl' pro»!'!' Thl' sky-~rollllll ratio is 1.0 sillt'e the oLjert is being
>iky ll!'ightllt'SS 1,,\",.1 is Ih.· liminal targl'l distlllH'e. vil'Wt'(l agaillst sky. To obtain liminal target dis·
\<'0" "i~lIIt1i!lg plll'I)tIs\'~' .Il this distant'" \\'hl'f!' I'o.-i. tall('\' 1'1'0111 lIolllograph, ('Ollll!'('t (I\S shown in }<'ig.
IiVI' l'I'('Ol!lIitioll is rl'quit't,d. tilt' illl1lllilllllioll vallI!' ,I/'(' .t.!I, will. a st rHi~htpdg'I' /I sky-~rolllltl ratio
~llOlIld ht' in"!·PIl.s,.d a:" jlldil'atl'd ill Talil .. .t-t'. of 1.0 wit h It ('olltrast of 0.99 alld Illark iutersec-
tioll of strai~htt'd~(' with till' zl'ro liminal dis-
4-4.4 ILL USTRA TIV:t; I:XAMPLES IIUlI't' lillt'. (''''IIII'd this poillt with th,' Illeteoro-
l.a. Tht, distalll'l; at v'hieh a un;forlll circular I,,~!i,'al nll.~:" of :!lJ,(I{\f) yards. 'rl\t' lill,illul targ·t
t!!r~l't of 100 squure fert wit), a hrightness of 10 d isUtll('~' is rl'ad wht' rt' this sl raight IIIit' ill t ('Nil'('ts

4-15
AMCP 706·185

/"" I A I \/ -', /"" /' L/£


V V \1 'L I V ~ LLL£L ._-
~---'/"------7"/"--f- ' 1\ . . . . . . . . . , / _ ...... c.. ZL"Z I I
./ /' I 1\ -1.-\/ I~ ------L-- L-L"~ I
i)""
/ /' \ ~'-- -', / __ L LA"L... '

G:
.
• en~ "
w
..
:::I
..J
>

METEOROLOGICAL RANGE (MILES) X f¥


Figure 4-9. Visibility Nomograph Showinp Calculation
4-16
AMCP 706·185

~-------+--+-.;--t~hH~'-------- ---------{
-~-~-. -. -~- -..-- -~ ./1
ii>
~ ~
~

g"
o· ._._-- - ._-------------1 !
I~
."

- -- .---.. ----~------.--; I l-
If)
is I
I:
I-

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CI
cr
.,o·
" I~a
¥ :!

,"
I-

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..o· :::i

i
::; .,
"
,.~~

------.-----------------.-------------------------~
I
!

ME.TEOROLOGICAL RANG" ,YARDS)

4-17
-----,

AMCP 706·185

witn the curve for the ambient illumination, 103 ditions is approximately 6,f)(lO yards. The sight-
foot-Iamberts. 'fhe liminal target Jistanee, in this ing distance and tilt' distanee at which the target
I' a." r , is a.pproximately 11,000 ya.'ds. ('ould b~ seen easily would also be raleuluted in
1.b. TL, sighting range is ealculatt:d in the thl' sa~lie lliunner as illustrated for Example l.b.
samp way f ~It that the effective contrast is: and I.e.
a. The distance at which a signal h:lving an
. 0.:9 = 0.495 intensity of 2,500 candles would be liminally vis-
iblf' on u fuggy II ight when the mf'tcorological
The sighting range is approximately 9,000 yards. range is 5,000 yards, can be estimated JIsing the
I.e. 'l';" distancp at whieh this target could signal light nomograph. A straightedge is placed
hI' seen easily ulldrr field conditions: aeros,'l the nomograph for signal lights so that it
I n order for a target to be seen easily, thl' conneds the rr:eteorological rangl', 5,000 yards, with
('{lIltrast v·tlues must be divided by at least 4.0. the cnndlepower, 2,500 cdudles, as shown in Figure
Under difficult field conditions, the contraf'lt value -1-lO. The liminal distane(' is given by the inter·
might have t() bp dividpd by a number as large as sectioll of this line with th(, eurve for the iUumina-
WO. The effective contrast range, therl'fore, is j ion level 10-:1 fooi-Iamberts.
4. The illt.el1Bity required for a spotting eharge
0.99 -- 021': O.9~} 1
f rom-T ..), tl) 100 = 0.0 to be Sef'/l at 2,000 yards over water and toward 11
rising sun on a clear duJ', (~an hI' estimated by
and the distance at which th(> target eould be seen us~ of the siglH::I light visibility nomograph. Un-
easily might bl' as low :is 2,000 yards (2,00(1 to der theNe conditioIW, ihe illumiJiat i oJ1 level would
7,f/OO yards). approa{'h W 4 ~:::;::t!:llL~,'; :... 'Phr meteorological
2. The distanee at whi('h the same target w()uld J'ang-e is assumeu to bl' approximately ;jO,OOO yards.
hi' Iiminally visible un<!t'r the same conditions, if a ('!par day. The intrnsity requirrd for a light
it werr to br obsrrvrd against a background having sourcl' to be liminally visibl!' undpr these condi-
a brightlH'ss of 200 foot-Iamberts ean be calcu- tions is obtain I'd from the signal light Jlomogldph
latrd. (SirH'e till' target aIHI baek~~round are both by connecting thl' D1et<'orolog-ieal rang<', 20 miles,
illuminatrd l1y thp same light soure(', thp rpfipetallcp with tht' point of intersl'ction of a liminal target
of the baekground is approximat('ly 20 timps that distall(,(' of 2,000 yards, and the eurve for the gen-
of tht' target.) I II this ('asp, tht> sky-ground ratio I'ral illuminatioll Il'v<'] (approximated by dotted
is WHO 1200 =- :1.0, and t hI' ('ontrast is: l'urV!' on Figurp 4-10). 'fhr intersection of this
linr with the zpro liminal distance line gives the
..!O-200
200
= __ II .9!i t'alHllepowrr requir('d, /thout 4,000 ('andles. In
ord('r to bl' spen readily undrr these field condi-
As indieatt·t\ ia Figur,· -t-!I, thp dt'tt'rmination of tions, HI<' ill!t'llsity valtH's should be multiplied (sl'e
tht' liminal rang(' is tht· saul(' /1." outlined for Ex- Tabl.· 4-8) by 100 to 150, yil'lding a required in-
arllplt· 1.1t. 1'1.(· limillrll dislall('1' 1I11<11'r thesi' eon- tpllsity of -t X 104 to Ii X 10~ candles. lI

REFERENCES
1. '·i.~ibilily 8t1/dil'.~lind Nomf Applications in :1. R. ('. CaSI'I'l'SOIl, II. P. J1PJlz'y('k, R C. Ch~nnel.
tlrl Pidd of C'UII/Oil!laul', ~ummary Technical I'i,~ibilil!l Data 1M;;' Applin til Fy"otf'chr.ics,
Report of Division 16, ~1~tiolJal Defense Re· ('olltl'al'i DAI-:!8-017-50]-OHD-(P)-1294, Dun-
sear('h ('omlllittl'P, Vol. :!. lap and Al'su('iat..s, SI::rnfurd, Connecticut,
.)
1<'. E. ('ady and H. B. Dat(·s, J.'lllmillatin!J En- 1955.
!Jill/ainu. :!.;<i gd., .10hll Wilt·y & Sons, 1'1. Y .. 4. A. Bloudl'l und ./ H<,y, J(HU' dl' Physique,
HI2R. Radilln~, ]911.

4-18
AMCP 706·185

5. n. D. Dwiggins. Fadors AlJeding SigMUing Sources for Night A.erial Reconnaissance PltO-
by Ftliual Md Ii ods, NA VORD 603<;:, Bmea.u tography, Final Report, Contract OA·36-039-
of NavdW~\1il<)u~, Washingtoll, D. C., 1957 SC .. 78333, Denver Research Institute, Univer-
(DDC-AD '16:~
QHJ). sity of Denver, 1960.
6. R. '1'. Eckp.!1fode, .Tht! Spottin:) 1'.fcnniqua. II. 8. Aerosol and War (}ases, Summary Teehnical
EfJeet of A mbit~ni IlluMill(J,hm Sj:ot .:n,:eM;ty Report of Division 10, National Defense Re-
(md Colf}r: Memory Sc'refn l;rl-w'mA~rv;n, r84- rearch Committee.
~020, Frankford Arsenal, !?hiladdpnia, Pa., O. H. T.J. Greene, W. R. Lane, Pa1·ticulate Clouds,
1955. Smokes, and Mists, Van Nostrand Coo, Lon-
7. It. M. Blonnt, G. Francis, Study of Light don, 1957.
AMCP 706-185

CHAPTER 5

PRODUCTION OF HEAT

5-1 HISTORICAL SUMMARYl,II,6,7,8 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 J.9th century. The
combustible material was used for both offensive United States Army had incendiary items of
and defensive operations, Ineendiary-type com- ordnance issue in the early part ,Jf the 19th cen-
positions were used in fireballs, pots, or crude tnry. 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 bow ar- and fired against Vicksburg, Charleston, and
row!), 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 flamf' thrower. These flame throwers
an incendiary mixture which prc.bably 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 thf' 17th century against ships, tents, In general, however, from the beginning of
barricades, cities, and personnel. It was espe- modern times down to World War I, incendiaries
dally "aluable as an incendiary because it was were not extrnsively used due to the increase in
difficult to t'xtinguish since as water reaeted with batf:le distances, re8Ulting from the introduction of
thc quicklimt' and also spread the petroleum, firearms. In addition, the defensive use of armor
These types of incendiaries were of definite value and f'arthworks left little material that would burn
ill all of the wars fought during the Middle Ages on the battlt'fields. 'i'hese problems were not solved
and their importance was not diminished until until the advent of the World War 1.
gunpowder was introduced in thf' 15th century, While both the French and German Armies
During the 16th, 17th, and 18th centuries, had tit'velopf'd incendiar.v artillery projectiles be-
the basic ingredients in incendiary mixtures con- fort' World War r, these projectilt's were not used
tinued to be sulfur and saltpeter to which were to an\' f'xtt'nt in thf' t'arly days of the war, prob-
added a number of flammable maierials such as ably iWt'ausl> th!'y wrrt' ineffeetive against military
resin, pitch, tallow, bt'eswax, linseed oil, H'1d tur- tar~rts. Tht' first ineendiary munitions used in
pen tint'. 1<'01' many years the recognized incendiary this wal' t'vidt'lltly wt're int'f'll(liary bullets and
projt'etilt's wert' known an "carcasses," In their antiaireraft artillt·ry projeetilt's directed against
('arliest form th('y ('onsisted of cylindrical bags observatioll balloons, and flame projertors against
or cO!Jtainers of !'allva..'! coated with pitch and ground troops. Thest' df'vi('ps, along with in-
bound with iroll hoops. The namt' wa.q sugg~ted l,t'Hlliary bOlllhillg frolll Ilirt'raft, Wf're first used
bl'callst' of the likt'nf'ss of thesf' iron hoops to thf' by tilt' Ol'rllllllls in J!)15,
ribs of a I'orps('. IJ8t('r, tht'ir shape became spher- I ntl'lIsi\'!' researt'h and dt'\'f'lopllIt'nt programs
ical; however, their filling remained the same- Wt'rt, f'stl1hlisht'cl by 1111 thr prill!'ipal bl'!iigerl'nts
11 mixture (If salt Ilf'tt'l' , sulfur, rt'si II I antimony ill ordt'J' to obtaiJl improved ill(,pnd.iary muni-
sulphide, 111111 tallow-lIlltil t'arClViSes bt'(~ame obso- tions. 'Vhitr phosphorus \\as t,tf('di"t' agaiust
lete toward th,> l'IHj ot thl' lHth t't'utury.
:-W~D. Milt'H, "Thi' Ci\'i1 War," Part I, Chemistry alia
R{)('kpts with ill<'l·ndiary ('hargf's werr rm- Enllitleering News, Vol. 39, No. 14, April 3, 1961.

5-1
AMCP 706·185

readily combustible material such as balloons, It a limited ftmount of research and development
was also very effective against personnel as it pro" was performed on irwendial'Y munitions in the
duced painful burns and hence clJ.w:ed a de- United St.ates, 'l'!w white pl){)i,phorus filling for
moralizing etfe(~t far in excesg of the casualties ealiber ,:~O inecw.linQ' ammunition was rE'placed
produced, Thermit(; and modified thermite mix- with a traecl' eomposition. DewJopment work on
tures wer!' widely employed, especially in COll- irwendiary eompmlitions was actively resumed in
nection with an additional incendiary material the United ~'Hates inlfi36,
such as "solidified oil." Other mixtures contain- O(,l1l:"ral jllt~rest in small arms incendiary am-
ing an inorganic oxidizer such as potassium or munition was renl~wed during tIl .. early years of
barium nitrate, barium ur lead oxide,. or potlll:'- World War TI. The Dp'Wilde-l<wLt'man bullet,
sium chlorate, and a fuel such as earbon, sulfur, designed in Switzerland ,'l,)' 193:), l'(,presented a
magnesiulll, aluminum, 01' organic combustibles, major step forward ill the development of "mall
were used in small arIlll'; incendiary bullets and arms inC('lHiiary ammunition in that it would fune-
with less sueeess in drop bombs, tioll as ,desil'(~d agaillst reali"tie targets. To elim-
Solid oil (oil mixtures solidified with colloidal inate t:1I' SI'.riOllS manufacturing and hal' q;ng
additives) and flame projector liquids consisting probl,'ms; a8sociatl'd w;th this design, it w."s ·Il",di-
of a heavy viseo ll !,! oil or tar and a more fluid and fied b,Y British scientists to use the U,S, .dew!oped
flammable liquid were also developed but saw only IM·] 1 incendiary mix, Modifications of the British
limited use during the war, design WE're IIHtdl' 18tl:'r by til(> lJnit:'d Std;!(S O:.-d-
In spite of the tactical and strategie possibili- l1an(~(~ D(-'pal'tment to improve fundionillg char-
ties associated with the use of aerial incendiary ;wtpl'igties and 1.0 adapt thl' drsigll to IHanufllctlire
bombs, only a limited amount of the development by llW,SS JH",HJUI" ion t('eillliquE's, 'I'h\'~:e modifi(·t·.
work on incendiary munitions was direEted to- tiolll" indndillg S'Hne ehauges in HlP ineendiary
ward design of improV('d munitions of this type, (~Olnpositi()lI, l'psltltL'd ill the n.s, 1\11 Inef~ndiaQ

1'wo general types of aerial incendiary bombs PI'oj('dill' whi('}l playrd lill importlUli: role ill Will-
were developed, The first was the relatively large Uill,'! thp B"ttlt· of Britain by defrating' the Ger.·
bomb filled with all incendiary mixture, often HUI!) ail' attal'ks. 'fhe devf'iopmcnt ofwodifipd in-
thermite and solid oil, designed to penetrate and ('l'lIdiary ammlJllitj.on, inl'llluillg' t!l'lllor.pi(,l'cing
set fire tv buildings and heavy eOllstruetion, 'fhe ill(,l'u<iilu'y Clillnlllliitioll, was stl1rt('(/ ill 194:3; how.
seeolld was tIw scatter typP of illcendiary bomb PVI'/', olll~' a small quantity of tlwst' itt'Jrls had

which ('ollsisted of ilH'cndiary units ill a Ial'gt' hl'f'll protiuI·pd hy tbe "lItl of til(' Wltl',

bomb, or a dustt'r of small bombs (the hi-Her being III it\!' Battll' of Britain, HlP Gt'I'llliins used a
tht, mort' sllcct's"ful of HIP two techniques), to 1··j,ilo mal-('lH'siuIH homb agaim;t British eities with
start fir!'s over Ii n'lati"l·ly largt· ar'ea, g'/'t'at "ft'r·l'tiV(·llt'SS. A \'I'ry ,·f;,,('tiVt· 4-poltlld mlll~­
The inert'asillg' uSP of military aircraft resulted IIl'siUIlI bomb had IH'PII dl'v,>\opt'd by thl' British;
all illcreasl~d illtl'rt'st ill slIIall arllls incelldinry howt'Vt'!', the hlitl'd ~tatl"S did not Its ,Y('t have a
1.llIllllunition sill('I' tlip 1'lIIpioYUlt'lIt of illtl'udiary .'.;ati~f;H~t(l\'Y illl:(,lIliiary homb. As a COllst>(l\lt'Jl(~(',
IUlIlllllllitiulI WIIS l'ol!siui·!'I·t! to be o Ill' of tiJ" l)('ttl'j" tilt' British !ilK-II [ 1I111~.(1h·hitllll bomb was reo
ways for dt'Stl'Oyillg ail'l'I'aft. Tht' first sJllali arIllS d.·~~igll(·II
for mass prutiudioll. :\ ·t-pOlllI<1 tht'l'Iliite
I'OlIl\d tit'sig'lll'd 1'01' ail'·I'hlil' I'olllbat was pl'Obably bomh II'IIS dl'Yt'lopl',l a,>; :1 ~Hllistitnlt' for' tht· some·
thl' British POIIU'!'OY [lJ'ojl'I,tilt' with ;i kit's('lgllhl' \\hHt .'illp,'riol' Illag'o\,si\J)l: bomb awl W,IS used in
dYlllllllitl' ti!1t'!' \\'hil'II had both high t'xpio"j\'I' U,'IH'l'nl Doolin\., ',., hi,..;lon' rait! Ull ,lapin. ill April
alit! illl'('/Id iury I'IlIH·t iOIlS, alld \l'Wi Vl'l'Y I' Iff' I"! i v,, l~lr,:~. ,\ slIIlIlI :.l-pnlill<1 lllagll,'~;iUlli bowb was al~u
a~aillst (J,'rlll/ill airships. Tltl' l'arlit'st i!I('('llIiillJ') d,.'vdop,'(l ilwl \IIII'll Ilsl·d ill (,lustpl'" was ,'ollsiilt'CI'd
Flllall anns jll'Ojl'l·till' US\'d by tht· ('lIil.·d t-Hal('s, t() h.· IIlUl'l' I'lr.",tiv,· ill,(Hllist urban (It'l'IllHll 'Iaq~t'ls

adH pI I·d frolll a Bri 1ish d('sigll, ,'mplo.\'t'd phos I Ira II 111" hl'arlt'!' .IlII'l'lItiiari .. ". whil'h had tH'ell dp·
p!ttl.l'll.~ as Tlli' iIH'\'lldial',\' llIat.,,,ial. \ ('Iop,'d !'or ill.i;lsi rIal tllq{I'tS. 'I'll:)' WI·!'I.' a]""
III tht' IJl·riot! hl'twl'i'li th" Iwo W(lrld "'a.rs, uilly .-.,III·,·.'s"fl/! 1I~~giIlSl .Iapalll"';(' imillstrillt largo!'bi LUI

5-2
AMCP 706·185

penetrated too far to be highly efi'ectivp ag'ainst Starters, igniters and first fires, 11.', adjuncts to
.J apanese dwellings: othl:'r pyrotechnic devices, have had a history
'l'he development of a small petroleum iu- ch)sely associated with such devices, Information
(,pneliary bomb was started and led to thp develop- drscribing the development of early Chinese fire-
ment of the 6-pound napalm bomb which was llsed crackers includes Jescriptions of fr!ses containing
with spectacular success in the strategic bombing potassium nitrate (saltpeter), chareoal and sulfur,
of .J ap~m. Other pptl'oleum incendiary mixtures In the 18th c{'ntury mixtures of potassium n~t!'atG,
wrrr dweloped, including tlll' 1M mixture which sulfur, charcoal, and iron filingo were widely used
(~()ntailled finrly divided mag'lH'sium, Against both for pyrotechnic purposes, They were readily ig-
Europp and .Japan, incendiary bombs proved to nited and for this p'lrpose a type of quickmatch
br vrry efi'l'ctiv(' wl'apons, esppeiaily when ap- was employed,
proximately one-fifth of them eontainl'd pxplosivl' The quiekmatch was made from cotton thread
eharg,,;: to diseouragr fire fightprs, or string, moisten~d with vinegar or brandy and
}<'l<trn(> throwl'rs wrrl' first used in thl' Pacifi" eoat{'u with a mixture consisting of 16 parts po-
t heater on Corrrgidor by thf' .J apanese against tassium nitratt>, :{ parts charcoal and 1 part sulfur,
Amf'l'iean troops who were not equipppd with the The mixtur{' wa~ worked iuto the thread by hand,
wpapon, Dth' to its provpn pffeetivelless and the aftl'r which it was dried and cut into ..uitable
dpvplopWdlt of napalm, it was SOOI\ llspd by thp lengths, It was theh connected to the pyrotechnic
Ii II i tpd Atate's for pombaL (J pl'ratiolls in all theaters deviee and llsed as its igniter
of !lflPratioll, ritlwr as a portahlr IlI'It or mounted At thp brginning of the 19th eentul'Y phos-
Oil yphiclps, phorus-tipped sticks, that could he readily ignited
A fkl' 'IVorhl 'Var II, l'psNlr<'f1 and df'vl'lop- by frie1 iOIl, were mad!' available and WeltP the fore-
Il\t'nt directed toward the improvement of small I'Il111Wr of prrsl'nt day matches,
arms incendiary ammunitioll were continued, Em- li'J'i('tioll starters weri' drvelopcd lat!'l' in the
phasis was dircc:tp<i toward developing improved 1!Hh ('('Uhll',v, Tilt's!' employed as II h"ad a !lli)cjure
ammunition with all in~reasl·d efTI-i-,tivl'ness per of i,otassiuHl ehlorale and slIgnr with g'um arabic
I'olllld Ilg'aill~t ,i(>1 plai.\t's at hi;,d}('r altituli,', This a:; il hilldl-r. In til!' form of JIlateli(-s, thl'se wer{'
\\'orl, prov('d valllubll' during the Ko"eall (;ollfiiet ignitl'd hy dl'awing thrm throu/>{h a folded 'piece
whp n sllIall arm inl'(,IHiiaries ":('1'(' lIs;'d in the air of sRlldpapp/',
('ol\tlid, a~Hillst (,IWIll;,' jpj Ilir('raft.. Other in. 'l'ypi,'ul PYl'ot!'ehni,' llIunitions i \! Hit: 19th een-
('PIJ(lial'Y Wt'H\IOIIS, ilH'lu(ling illl'(,lJdiary bombs and tu!'y ('ollsisi.>d of rol'ht;;, flar!'s, and tin>balls whiph
tllllnp throwprs. cd,.;') WN(' \.i~('d \\'in('iy an, i eft'ec- t'mild Ill' i/.!lIikd by a mixtul'I' of potas,'iium llitratt·,
ti',"'I,I' ill thi,; l'\)lltli,'1 hy tIll' ! !.llilt'd N~l1ions forces. sulfllr, Ilwl III'S(,lIi,' s\llfidt" whidl, ill turn, was it~­
'l'!;\· "Ir"r! applil'd i:'\ till.' (l,'\'plo)lnlent of in- lIitl'lt by a Ijui('klllat<-h,
I'!'lldial,\' wl'apon,.; has ['t'·;tdt"d ;11 J1t'Ii<'I·.time nses Durill/.! "'oJ'lt! Wal' I, 1I.\'l'ott""'l\i(· lIlunitions
fill' tli('s,' l\'i'a jiOll I;, I'YI'og-.>1 (01' goop), wltil'h con .. \\,,'1'1' ("','('\o)h'd whil'h IISI'I\ "olJlpositioIlS more

taills till<'h tlividpd lilagIH~SlUlll. alld wl:i('i1 VIa;.; t1ifti"u!t to igllitl' than !'urlit'r "(Impositions, In
IIsl"d ill til" 1:\1 pl'lr'o]PlIlIJ illl'PlldillJ'Y mixture, has I h., jWI'i"d hl't W(-PII \\' ol'lll \\' ar I alld \Vorld \Vux
h(,;: t'olllld 10 aid ill tl!" burllilJl! \lilt of forest 11. lillJitt'd 1'Il',,~t W!L"i Dlllell' to prn<iul'(' lIIort' satis-
">liiltlf,!'s. Th,' tlHIJU' til!,(lII't'f is of "allit' ill fighting' l'al'tIlI'Y i:.!lIitioll lllixtlll't'S for P~'I'\ltt't'ill1i.· lIIuni .
I\'r. sj til'I'" '\I\d ill d",,,tr •• ,'>'ill/.! illiwalltpd v{'grtu . tilllls, A (-()lJsidt-l'ahll' pal'l III' t his ('!Tort WIl.S
tl"lI. :--:twli,'" into tli., t'all~p~ (lr ,It'ath hy flame tl i l'l'dl'd t"WHI't! i iI(' dl'\'I'\lIplllt'1J t of satisfadory
I <lIT!".! ,)lIt d\l:'il!~.~ W',rld \\'.\1' II IlilY" din'l,tld ~tal'tt'I' 1:lixlllrl's for' lit' ~l\Iokt' lilil!.tlll'I'S and fot'
att"lilllll, (,If "i,iliall firl'flil'J1 ;'1 IlIlSUSP,,\,t"d hazards tllt'l'I'litt·.tYI"- illl','II(\illl'il'», ])nrillg World War II,
ill Ii!!htln,.,r :Ir,'''- (If Yilriotls l,iIHb. Also, J'1·se.1H'(,h "111phw"io.; \I'll!' Hg-aill dir,'d,'11 maillly, toward Je-
1111 Ihi' dT""lil'I'JiI'SS u1' iIJI·,'wii:U'y ,1I11l:HllIttJIJII I'l'lopirt:.! \'olliposit lOllS wlJidl wOllld IIlpt'! tht' llU-
<lg-lIlw;1 HI' '"l".'I.t"l llits hl"'ll III' 1'1\:111' ill ,'oJ\Il{'l'!iOII nJ"diall' Ill'''<\S (If th,- t!'lUll's A rf'latiwly slilIllI
with ai!""I",!'t fir!'s <l1I1()IIJ\j 1)1' • /fort hit.; hl'l'lI ,'xpt'udt'd Silll'(> \Vorld

5-3
AMCF' 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 erude delay traius were developed
In addition to their value as a souree of heat, for incendiary and other projectilt's used in eJlrly
the utility of combustion processes as a means for naval warfare when ships were made of wood.
measuring and controlling time intervais 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, erode to further delay functioning so as to maximize its
candles, and similar devic!!s, to ignite either ex- effectiveness in damaging tt:e enemy ship,
plosives or flammable matprial at a distance or With the development of improved amllluni~
at some delayed time, In addition to their mili- tion, more complicated fuse systems with imprvved
tary applications, such delaYl:'(l reaction8--Cul· reliability and timing a~curacy were required.
minating in the sudden produdion of fire, smoke, The earliest pyrotechnic delays which Wf'J''2' rela·
or a minor explosive phenomenon-were an im- tively accuratp consisted of carefully produced
portant part of many early religious ceremonies, black powder trains or black powder rings. 'fhe
The introduetion of gunpowder stimulated the delay traiu was used in fuses requiring a set
development of somewhat more sophisticated delay del8Y 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 wpre some use. In spite of the many pro~lemc assoeiatild with
uf the earliest pyrotef'hnic dplay trains. Present the use of black powder delay compositions, due
Ijuickmat(~h and firecracker fusps are of this type, mainly ~,) their hygroscorjl' nri corrosive nature,
Q

however, they are normally used as transfer media they served as the basis of most pyrotechnif~ delay
rather than timers. Fuses ('onsisting of an in- trains throughout Wodd War l J .
gredient such as black powder, ('(mtained in a Burning black powder liberatrs large amouuts
tubular cover, will bunt relinhly and at reasoll- of gaseous products which, in most fuse designs,
ably reproducible bumin/! ratl' Hai't·ty fuse is of are vented to the atmosiJherp. In the development
thi~ typc. It is a lightly 'Tapped tl'uin of potas- of amnll.nition, psppcially antiaircraft ammunition
sium ni t !'ate all(i blal'k l:owdl'l' bUJ'Iling at a rate during World War 1, it was found that the burn-
of 40 to 120 seconds per yard. 'I'ht tubular cover ing ratt' of black powder was affected considerably
now is oftt'll imprpg'llated t'llbrie, An effort is by the rotational speeds of the projectile as well
usually mllt1p to spal against 1ll0istlll't' by the use as the varying ambiellt pressures. Theref0re, the
of wax uud plastie eoatillgs. Thl' dewlopmellt of dl'veiopml'ltt of a more satisfRetory fuse powder
tht's!' fllst's madt' possiblp lavish Hr,'work displays ('ompositioll WhS sturt('d with a low priority after
by crudely I illlillg thl' st'q 111'11('" of Ht'll ts starting World War I,
with tilt' prll(lagatioll of tilt' display illh thp air 'fhe rirst nongh<leOUS delay powder-col18ist.
followt'd by It ::iPqUt'III'" of hursls IIl1lkillg' lip tIl!' iug of r('d lead, sili('on, and glycerin (84/15/1)-
firt'work displ::y. In ati,litioll. tht'ir liSt' providf't\ \ as developpd in 1931. ~ince this composition
th,' 1lt'('I'ssary rilll" rt''1l1ir,'d i'm' sut'd,\' of rhl' per· L Irned too fast, slower bunlin~; powders contain-
SOli tll'l igllit illg ('x tl'n"j VI' ~I'()llIld displays. ~'ust's ing lead ehl'omate, silicon, and linseed oil (89/10/1)
of t'ss"lltially tht' ';III1H' tn)',' \\1'1''' also lI" .. d III ,'Oil, were dpwloped. Lack of personnel and funds, how-
Wo'd iOIl wiTh tht' .. arly "Oll/fllI'I"'lal •. ~ "Iosi",'" IIs,'d pyer, prpvented 11 comprehensive, systemat.ie study
ill nlillill~ fwd ('OI/SII'IH'liOIl of tht' lIIallY possiblt' inorganie exothernuc reactions
'I'h,· Ii.(' "I' projl'f'! iiI'S "II/lt/Ilf\ ill~~ "X I'losi "''', befor!' the sLnt of World War II. As a relmlt,
WI" st,\:kd .'iOIlIi'tilll!' art,·!' : II.' IlItf'odlidiolt '.I bla('k powlkr was ltg'aill widely used in delay ele·
Ilrldlt'ry ill Illilitdry IIpl'l'at,ol, Ellr'!), i,roj"('lile, 1Ilt'lIts during World War II.
W,'I'.' tillt'd wdh glll:puwt!,'r 1111(' illSt'd with a III l!q~, a ('olll/ll't'hem,ivf' study of possible
""",tIt'lI plug' ("'Iltllillili~ /1';1111111 l"III,·tl'l' holt', l~asl,·s.'I dt'lay mixtul'('!'> was stJ\rted.~~ While this
aLi" lill"d \\'1111 .'lowd,'1' 'l' 'I" I'I'U, flls(' \\ as ig. st lid." WllS ill pl'ug'n''Is. lUI urKent "e('d developed
IIi "'.1 by tIl(' PI'I' ,"'Iill~ ('h'(I'~" III1.i hurrlt"l slowly for elf'lay jluwu('n; to hI' llSt'U ill the bombs used
AMCP 706·185

in "skip bombing." A composition-containing by mechanical, ehemical, t~lpct.rieai, or other stimuli


manganest', harium chromate, and sulfur--which of low energy and produce sufficient heat to cause
had been prepared on a laboratory scale, proved tht' ignition of otil{'r, less sensitive mixtur~s.
satisfactory in spite of the many difficulties en- b. Pi!"st fires, starters, igniters, and similar
countered in proceeding from a laboratory to a less S(,llHitiw, but rdatively easy-to-ignite mixtures,
production scale.23 The Navy deVeloped, under '.ormally activat\ld by the heat produced by an-
eon tract, a delay mi"!{ture containing nickel, 251'- uth{'r ,!H'l'lual source. The sensitivity level of these
conium, potas~ium perchlorate, and barium mix.tll!"fS is sneh tha.t sufficicnt quant.ities can be
chromate which was used satisfactorily in hand USI'll to ;;:lppl;,' tht' heat nec{'&sary for ignition of a
grenades. While these delay "powders-developed third mix tUft' Hr main charge ('ollsisting of a pro-
under wartime conditions----were used operation- pt'liant or pyrotechnie composition. A similar se-
ally, they w:~rp far from optimum. 24 (!UPlwe of ignitiolls is also wmmon t.o pxplosive
Work after the end of World War II wa~· di· items,
rected toward the development of more satisfactory ,', illeem.liary mixtures whieh He used for
gasless delay eompositions, The availability of d":ltrll<'tivf' ignition of ('ombustiblf' ma·cerials.
eertain powdt'red metal fnels--e.g" zirconiuJII- ~. ('ompositions which produce hrat at a low
nickel alloys and boron-not available earlier, ratc:
helppd ill the de\elopmcllt of the prf'spnt!r used a. Heat powdrrs -vhich produe p a controlled
more sati,.,fadory delay powders, amoullt of heat for applications such as the activa-
The development aIHl use of thermal bat- tion of hl'at battt'ries or a eontrollf'd pvolutioll of
teries~··'~" requin>d a controiable heat sonrce to goa!>', and for other purpost's.
melt til(' eleetrolyte which is solid at normal tem- b. Dcia~' mixturcs which are used t{) ac-
peratures and to aet.ivatp the hattery. Early ('urately t'ontrol the time intrl'vai between initia-
tlwl"Illal battt'ries were al'tivatcd by weighed quan- I iOll and final flllletionillg.
tities of loost' heat powdpr, similar to delay compo- 'rhl' ratl' allii eontrol of the hpat output from a
sitions, introduced direetly .. lto the battery cases. pyrott'l'hllic mixturp, as well as the heat transfer
~iightly impro\'Ni rl'suits ,n'rp obtained when the 1Il1'('hanisllls inyol\"pd, 1l1'(' "Ny imJlLlrtant in the
battery was divided into eompartments and th!' IWI'fornlalH'p of its fuudioll. In this ('hapter, these
JOOSl' h!'at powder added to ,'al'h eompartment, :~haradl'rist it's a!"!' emphasized as regards existing
Bettpr l"t'slilts w,'rt.' obtained whl'll thl' heat powder ht'at pro<ill('illg pyroteehlli(' dpviees.
W'IS mix!'.! with illor~alli(' fib,'!'s and made illt.o
h,'at. IlIIJl!'1' hy ('ollvt'lltionai IlllJ>l'r making tel'h-
lIiques.~fl,n
5·3 THEORY
'I'hl' two impol'tant mrans by which t'lll'rln' ean
bl' Irltllsf,-.·r"d aI',' heat and -Nork. Both of I hest'
5-2 INTRODUCTION t'lIl'r~y forms IIfl' transipnt ill nature since they
Pyrotechnic mixtures, when burned, release (>xist ollly \llIl'n tlwrl' is an ('x(>hang,' of t'nergy
l'lH'wi('aI I'll"!':.!,\' ill till' forlll of h,'at. Th" heai I)('t Wt'!'ll 1wo syslt'ms or II systt'lll und it~ surround-
('Ill'!·:.!,\' rt'Jt'as"d is IIspd for thl' pwtilldion of li/,"ht, il1~s. If this trulls!"t'r tak"s plut't' without Ii trans-
sllIok .. , ~IIS. IIlId SIIII!hl. Although tilt' heat I'ffeds fer of lIIass, uJI(I 1I0t as /I rt>fiult of a tempt'rature
prodllt·t'd ill thl' Sllr!'Oll!lllill~'" by tltpSI' itt'lIIs art' ditL'rt'tH't', tilt- t'n('r~y is Mli(i tt, hay!' ht'en trall8-
Iisually IIlt"itit'lItal hilt! 1.Ia~· ht' 1I1ldt'sirabil', t);"!"I' ft'rrl'd thruugh tht, pt>rt"lIrlllltllt·t' of work, If the
111'1' II 111I~llbt'l' of P,Vl'o/t't,hnit· itt'lll~ ill whidl tilt' t'X..tWIl!!t' is dll,' to a It'tlllll'l-at urt' ditTt'!'l'lIce, tiu'
protiudioll of IIl'lIt is tht, prilJl1Il'.I' i'twdi:1l1. ,'lIt'!"gy is ,.;aid to hl\\'" bl,,'l1 transf,'rrt't! ill tht' form
I'yr'.ltt·dllli,' ht,ltt pro(illt·illg' llIixtUrt's t'all ht, of ht'at.
di\'idt'd illto t \\11 !!'''I,'rill t'att'g'(Il'i,'s, 11llllll'ly, 'I'IH' I!Il!Ollllt of t'lll'l'g-.\' trllllsfl'rrt'ti as IlI'at from
I, ('t111i11l1~il illiis wLi('h )ll'lItill'·,' ht'at at a hi!!}1 it l)\ll·llill~ pyrtltl'l'illli(' Illixtllrt's d"pt'lltIs 011: (l)
I'al,' ' th,' itlllllllilt Hldl raIl' of t'llt'rgy rt,ll'llst'J, (~) thl'
:1 L!llIti,," 1111\tlll"" whidl ('i111 I", illitiatt,d ill'"dllds fllrlll"d, 1:11 Ih, !"lll!lt'ratllrt· rt>lId1f,d hy
AMCP 706'135

the products, (4) the method by which the energy dizel's which have been widely u3ed in incendiary
is transferred, and (5) the characteristics of the compositions are the inm:ganic nitrates, perchlo-
material being heated, whether unhurned pyro· rates, and peroxides. The total and aVhilable oxy-
technic mixture or other combustible. gen for some of these oxidizer~ are given in Tllblea
5-2,>! 5-3, and 5-4, Many of the potentially good
oxidi7.,·rs listeJ. in these tables contain laloge quan-
5-3.1 AMOUNT OF ENERGY RELEASEDl
tities of water in their normally occurring crystal-
The energy released by the reaction of a pyro- lille forms. This reduces the available oxygen from
technic mixture can be calculated by the methods a given quantity of oxidizer and can affect burn-
outlined in Chaptl>,r 3 (Paragraph 3-2.2.1) of this ing (as an inert) as well as stability in storage.
handbook or can be Jetermined experimentally by Approximate decomposition temperatures are also
bomb calorimetric measurements.
Certain generalizations can be made frvm the TABLE 5·1
results of thrse calculations involving metals and HEATS EVOLVED FROM REACTIONS OF
oxidizers which might tlr 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 the01·pticaJ density for the mixture) depends Reaction Callcc Cal/g
on the oxidixer used, as is indicated in Table 5-1
which is a summary of the heat evolved when alum- Al + NaCiG 4 7,000 2,600
inum rracts with various oxidizing agents. In Al + NaClOs 6,300 2,500
general, for a given oxidizer action the heat evolved Al + KClO. 6,100 2,400
dcpPllds on the oxidizer anion in the following de- Al + Pb(NOlih 5,800 1,500
('r!'a;;ing order: Al + KelO a 5,400 2,200
AI-+· PbO:! 4,900 700
('10., >CIO:! > NO:! > l\'n(). > ~04 > Cr207 > Ai + CuSO. 4,700 1,400
Cr04
Al + CuO 4,600 900
As abo slll.Jwll ill 'rable Ii- I for a given oxidizer Al + NaNOs 4,1Of) 1,800
allion, ('oPlwr salts yield mol'l' ht'at than lead COIU- Al + Ba(NOah 4,200 1,400
pounds and t'itlwr of till'S!' yit'lds more than so- Al + PbSO. 4,200 800
diulIl,lotassiulIl, ('all'ium, or barium eompoullJs A' +- KNvs 4,000 1,800
wlh'1J 1'('11<'11'<1 with till' sault' flH'1. While COPlwr Al + CaSO. :l,800 1,300
salts 1:PllI'1I1' best, th!'y HI t' l1(,t ('omll1only u8~d Al + KMllO. 3,600 1,300
brl'Hu'w of tilt' difti('ulty illvolved ill thl'ir ignitioll. Al + Fe20S :i,500 900
'I'hl' n'a(·t iOllS a l'l' Iist!'d ill ord~r of tllt· ilrat (~volved Al + MilO:.! 3,400 1,100
h <11 lorit's lH'r ('ubi,' (·t'lllimpter of mixtur('; the Al + BaSO. 3,400 900
hl'at ('\'e!Vt'd pl'r grllIll of mixturl' is also given, for Al + FeuO. :l,'!OO 800
(·OIllIJlll'isol1. III t'aeh (·II."\t·, tl\t' (·alt·ulat.'d hl'at of re- Al + Na2SO. ;1,:~tlO 1,200
adioJl is has.·d Oll a part it' ilIaI' (most ('omrnoll) Al + PbsO. 3,aOt\ 400
stoit'hiollH't I'Y for I h., rl'lil'/ iOIl; t ht' illdieated val AI + Na2O:. :1,100 1,600
III'S would vary wlwrl' ditT('rl'nt Htoiehiometries are AI + K 2 SO. :1,100 1,200
possiblt'. Hill('(' lilt, oxitiizl'r t'x!'rts tllP grt'atrst Al + NH.NOs :l,OOO 1,600
in flul'll(·t' Oil tIll' hl'a I of /'t'IIl't iOIl. t hI' rppll/eenlt'Jlt AI + Na2('rO. 2,HOO 1,000
of alullIillulII with otlh·r I·t'dllt·illg' ugt·nts would AI f- K l Cr 2 0 1 2,HOO 1,000
rt'sult ill all IIrralll~I'IIH'llt ~iillilltr 10 that showlI Al + BuO:! 2,600 600
ill Table 1i-1 AI + PbO 2,500 300
Tht' HlIlOlwt of oxygell Ii\'ailablt, fr()m It givrn AI + BaCrO. 2,400 600
1l1ll0unt of ()xitiizt'r is tht' ba.-;i(· ('I'itl'rioll UpOIl Al + K~Cr04 2.200 800
whic'll oxidizl·rs are jud/!t'd. Thrf't' l'IliSbl'S of oxi-

5-ti
AMCP 706·185

TABLE 5·2
OXYGEN CONTENT OF VARIOUS NITRATES
--------, ------~--------------.-----------....
A.pprox.
-------....------....---------.....--
Deeomp. Oxygen Oxygen
Dens,/:ty l'emp, Contained A.vaiktble
Nitrate glee 0(1 gig alec g /g glee
----_._---- ------------
Liquid. O2 1.14 1.00 1.14 1.00 1.14
I~iquid 0 3 1.'71 1.00 l.'il 1.00 1.71
Aluminum (+ H 2 0)! laO .77 .32
Ammonium 210 .60 1.04 .35
Barium 600 XI 1.19 .31 .99
BeryBium (+ IhU)1 100 .7i' .3ll
Calcium (+ H 2 0) I 2.36 560 .59 .48 1.11
Chromium (+ IhO)l 100 .71 .32
Cob/l.lt (+- H~O) I 100 .59 .44
COPP~l" (-+ H 2 0) 1 150 .;)1 .42
I ron (F'rrrie) ( -)- H 2 0) I 100 .47 .;)9
LNMi 470 .29 1.31 .24 1.10
(+ H 2 0)!
t,ithiuDl 2.:18 260 .69 1.65 .58 1.3H
Magnesium (+ IbO) I 100 .75 .62
Mallg'alH'Sl' 180 .54 .40
Potll.";sium 2.11 400 .47 1.00 .40 .84
Sodium 2.26 aso .56 1.2H .47 1.06
Strontiulll 2.99 600 .4;, 1.:lH .88 1.18

1 (H"O) indicates that II hydratt, of the nitrate is Il C<ll\lmon form of thp Halt. All dl\ta
I'resellt~ in the tablr, however, arl' for thl' anhydrous salt.

g-in'll ill thl's(' labh's. TIH' thermal dt'I'Olllpositioll ust'd as a IIlt'Il.~lIrt' of the rt·dueing power of thest'
of iIIltlly of th!' possible oxidiz!'rs has b('en studi!'d I'om pounds.
ill d!'tail.:l It should bt' llOtt'cJ that ,'ombustioll of liquid
III 'I'll hi!' ;1-;', rt'llt'tiflllS !In' shown hl,tw~'!'11 var- hydl'Ot'lIrli<lll flll'ls Aueh as gasoliut' and kt'rosene,
iolts III !'tll II i,' awl Ilolllllt'tallie rl'(ilH'iug' ag't'lltA, and whil·h WI','I' with-I:; lISt'l! as ill"elliliarit's during
hariullI lJf'roxid!', Tht' Iwals ('\'olv('ti from rt'al'tiolls hoth World Will' I I HlId tht' Koreall Conflict, rr-
of Ihl's!' lIlatprill)s with otllt'r oxidizing' agents suits ill till' ('\'olutioll of about 10 kil.o('alorit's per
would g'I'I\I'rally nmk ill thl' SIIIIlI' on"'r. gram. 'rhis is l'()J}sitit'rably bt·ttt'r Ull a wright
:";0 II l!' of thl' I'olllbilldtiol\s iJlt,llHlt·d ill Tabll' basis thun for tht' Illt'tal inl'(>ntliar~' matt'rials:
;1-;1, '''\It'lt as IJU1'iuIIl Ih'roxi(lt' with till, dlromiulll, t hprm itt', O.H kil(lt'a!orit':' per gram, lind mag-n/:'-
/lutl Zilll', Ilr!' so insl'lIsiti\'(' that tht' pt'roxidt' WOllitl :o;ium, IHi kilot'a!ol·il·:O; pt'r gnull. HO\\'t'vt'r, th!'
tll'l'OIil POSI' Ilt'fort' i~lIit iOIl tH'('1 rrt'll. ( '0I1\'I'rsl'ly, tt'mpt'raturp rPllI'llI,d by tht· hydrot'lIrboll-oxygen
rt·t! phosptorlls /ll\d :O;\llfllr with pt'roxitll's l'ar. bt' rt'lldioll is \t·ss thall that I'pa('ht'd by illl'Plltliarips
st'llsiti\'I' 10 Iht' poillt of Spolltlllll'OliS dl'I'ompositioli ilh'oqlOrat ill~ Hll'tU! ftwls.
IIlId ('ollstitlltt' a hllzard, 1'hl' t'llIlindt'lIt ht'at vulul'
gi\'t'll ill tit .., lahl!' is til!' ht'at P' .. ol\'l'd for thl' rt'- 5-3.2 HEAT TRA1~SFER
/Idiom;, a>; i'in'll ill tht> t'quatiolls, tli\id!'d by tilt' Tht' dlit'it'llt,y /l1H1 Iwrforlllllllt't' of pyrott,('hni('
1I11l1lbl'l' of' 'q\li\'ltlt'llt wt'ig'ht:o; of redlH'illg' agl'llt tlt'"it'e:o; IIt'I' "I)/lsidprllbly infiuPIIl't'(l by tllt' various
ill thl' t'qtl:!'iOlI. TIlt' I'quiVlllt'ut ht'II1 has bt't'll modI'S lIud ralt's of hpat t rallsft'r prl's('nt through.

5-7
AMCP 706-185

TABLE 5-3
OXYGEN CONTENT OF VARIOUS PERCHLORA'r'ES

Approx.
Decomp. Oxygen Oxygen
Density Temp, Contained Available
Perchlorate glcc °C gig glec gig g/ce

Liquid O2 1.14 1.00 1.14 1.00 1.14


Liquid 0 3 1.71 1.00 1.71 1.00 1.71
Ammonium 1.95 0.54 1.06 0.27 0.53
Barium (H 2 O)l :"j00 .as .33
Cobalt (H 2 0) 1 3.33 .50 1.65 .40 1.34
Copper 110 .27 .16
Iron (H 2 O)1 .62 .29
Ilead (H 2 0) 1 2.6 100 .:31 .~)9 .24 .63
Lithium (H 2 O)1 2A:l 410 .60 1.47 .5:~ 1.28
Magnesium (H 2 0) I 2.60 .57 1.48 .50 1.30
Potassium 2.f)~ 400 ·Hi 1.16 .40 1.02
Sodium (H 2 O)1 2.49 4S0 .52 1.29 A·6 1.15

I (H 0) indicates that a i1ydmte of till' percilloratl' iH a common form of the salt. All data
2
presented in the table, however, art' fur thp !lnhy(lrous salt.

TABLE 5-4
OXYGEN CONTENT OF VARIOUS OXIDES AND PEROXIDES

Appro.r.
[Jrcomp. Oxygen Oxyyen
[)rnsify, Temp, (' 011 t ainul A uaila,blc
O.ridl iiI' }'(T().rit/(' !l i 1'1' °C I
(J [J Y! cc g /a 9 Icc

Liquid ()~ 1.14 1,00 1.14 I.()O 1.14


Liquid 0:. 1. 71 1.00 1.71 1.00 1.71
Bal'iulIl Pi'roxidt' (I I~O) I •. % .l!I .!l-t .WI .47
,',dt'illllJ I'l'l'oxidt' (H 20)' ;!HO .1-1 .22
,)
('''l'llllliullI 'l'l'ioxitit' (IbO) I -.1
~
1!H) AI'- 1.:W .:!4
lodill" 1"'lltuxid,' .1. HO ;WO .2·1 1.1 f, .~·I
I rOil (}<",:o1)3 I ;-).]2 .:10 }';i4
!.,'ad I>ioxid,' !I.:!H 2!HI .1 :! 1 21; .07 .63
:'II a 111-('<1 lit'S" 'I'riox illt' .-17 ~:!
POI lI'>si II III l'l'roxi,l" 2.'i'l .29 .Ii] .14 .:10
Sotlilllll I't'rt,xitl .. (B~()) 1 21'\) .n 11;) .:!O .fiH
Strolltium P('roxidt' (lhO) I .27 14

I (lioO) illdirate~ tliat :t ""dral,' of tilt, l'l'rt·,;d,· j,: a "OIl'IllUll fuml "f tlli, lIlaltori:.i. All
dutu pr;sent"d ill this talJh-. I;o""\·l·r. art· fur Ill,' al!llyJruus tUrill of !Ill'S<' 1"·'U-'IJl·'.

,l-H
AMCP 706·185

TABLE 5·5
HEAT OF REA"::::LION OF REDUCING AGENTS
WITH BARIUM PEROXIDE

Ileat of E!JltLvalent
Reaction Ileat
Equation (Kg-cal) (Ko-cal)

Ba02 + l\lg -'> BaO + MgO 126.7 63.4


2Ba02 + Zr ~ 2UaO + ZrO:! 219.:3 54.8
:WuO:! + 2Al ~ :maO + A1 0: 2 l :321.H 53.6
:; BaO:! + 2red P ~ 2UaO + Ha. (P0 ):! 4 487.6 48.8
:ma02 + 'ri ~ 2lhO + Ti0 2 186.2 46.6
2BaOz + Si ~ 2HaO + SiO:! 162.(i 40.7
BaO:! + Mn ~ BaO + MilO 77.1 aH.6
:maO:! + ~('r ~ ;maO + Cr2()~ 21-UI a5.H
BaO:! + Zn-.. BaO + ZnO 64.1 :l2.1
~ma()!! + SII ~ 2BIlO + SnO:! 99. :~ 24.8
GBaO!! + CaSi!! ~ 5BaO + CaO + :?RiO:! 2:{6.7 2:3.7
:ma02 + 2Fe ~ :maO + Fe20S 14'1.:{ 23.4
Ba()!! + ('(\--> BaO + ('dO 4il.H 22.9
:maO:! + W ~ :maO + WO;j 1:37,5 22.9
:lBa()!! + Mo ~ :WaO + MoO: 1 llH.:1 19.7
:maO:! + 2S --> BaS + Bal'.;o~ 11)1).8 1!I.il
'BaO:! + ~i ~ BaO + \TiO :l!).O HUj
BaO:! -I- Co ~ BaO -I- CoO as.l 19.1
:IBII()!! +2Rh ~ :!BaO+ ~~h:!():1 107.K lK.O
:IBI10~ + +
2Bi --> ;!BaO BbOa 7H.!I 1:1.2
Ba():! +eu --> BaO + ('uO Hi.-! B.2
:!BIl()2+ 2St' - BaSt· + BaSt'\)4 ;',-1.:1 (i.H

Ollt tilt' sys(t·/Il. .\I(hollg-h t'xtrt'IlII'I~' (·olllpli"lIt!·t! t l'Illl'.;ft·rl'l'd hy this Ilwthnd i: uSllally small when
Hlt·,·hi\lIisIIIS t'xi"t in SlIl!lt' t /lSt's. a kllOwlt'dgt' of Olt' t'olllpllrl'd with th .. amoullt t fallsft'rrt'd by other
!'!'tIblt'lIls ill\'lIlvt'd is illlportllllt ttl thl' impro .... ·- IIlt·lIlls. Tilt· rllk "I' ht'llt t rlllIsft'r (I, lit whieh heat
IIlt'lIt of pyrot"t'hllit' t'OllljJtlSitiollS alld hUl'(iwart' flows IItTOSS all 111·,'11 A, is gi\,l'll hy:
d,·sign.
dt
llt'llt is lntllsft'rl't'd by Ollt' or by II t'olllhilllltioll (/ = k,l _.-- ( !l-1 )
dr
:d' til,· thl't't' IJII"it· llH,(·hallisllls: t·Plltitlt'tion. t'OIl-
I,,· .. tillll. alld radiatioll, DlIl'illg' Pl'oplIg'lltin' hurn- wht'/'p k is tht' (h"rllllli t'olltiul'tivity, 1I1It! tlffdI
i'IJ:. "Illy 011,· of th,·,~,· IIltld,'s is ,·tllltl·ollillg. is th .. tt'lllpt'l'atllfi' grlldit'llt lit tht' pnillt of ill-
tt'n'st, Tilt' rilt" t'xl'rt'ssiollS for II gl'llt'rlll thrt't'-
5-3.2.1 Cond uction dilllt'llsiollal "IISt' art' lllOrt' t·olIlpl,·x.
Iii ·("l<ludioll. tit,· !:t'lIt 1'llt'l'g-y i,,, tl'lIl1'ift·lTt·d TIlt' tllt'l'lllal t·ollt!llt·tivity of tilt· pyrott'('hlli('
It." IlIolt·t·u IIII' Illot iOIl alld 1'1',.,. t·lt·l·t rOllS. ~III tt·l·iab Illi~;t ur,· hilS b""11 ShOW!1 ttl illtlllt'IIt·,· tht' hUrtling
likt' tilt' Illt'tllls, whi"1! iiI''' good t·tllldllt'lors of ht'a!, ratt' dllt' to 11 I'r..tIl'lItillg' of th., IIllburrll'ti eompo-
hal't' Il l':dl-lIrdt'('f'd ,·rystllilillt· st l'lli'tlln' alit! art· sitioll (I'aragraph f;-:!.:)). 'I'ht· IIIlHlllllt of preht'at-
rit·1I ill fn·t· (·It·t·trollS, All Illatl'rials t'Olldlld Ilt'lIt illg is IlsUltlly II funt·tioll of th .. lllt'till ('Olltt'llt of
ttl ,~()(II" ,·X(t'lll. III liqllit!_~ alit! gll".·_,. tht' 1I11l0UIlt th,' Illixtun' duo' to it-; hight'r tht'rmat (·()llt\udi\'ity.

5·!1
'rhp dt'g-n'(' or ('on,.mlidntioll also f1tTt'l'ts tilt' rate of the IIr(,1l of Ihl' ('lIlittillg SUI'fll("', alld T the absolute
heat t!'ll!a"f,'I', 'l'lH' IIl'ut ,~ol\(hwtioll ,dollg ~'olid (\'lll(l('l'atlll't'. A gl'aybody, 01' llo11s('lectiv(' radiator,
flares has bp('11 llll'Usllr('IP by imlil'ddillg' thPI'lllO- is Oil,' ill whil'!1 its (,lIIissivity is indep!'ndcnt of the
('0111>1(,,, ill thl' ('(Illlposition at lilt' tilll(' of l'umpae- wa\"('ll'll~th . •\t a gi\'('ll tL'I\lIWratur,', the amoullt
tioll, F'I'OIll thest' (!llta it was possibl(' to ('Ollstruet of Plll'I'le,,- ('mittl'd lwr nait I!I'l'a at any wavelength
a IIHl!h' I for rl'latillg the illstalltHlll'OIiS tempf'ta- ii'i I(,ss thall that fl'OlIl a hllL(·kbod~'. The net heat
tIlre at a poi lit ill th(' flar\' to that of the l'eaetipn ('.«'hallg't' brtwl't'r; two bodi,·s ill y;hil'h both the
zone, hot and ('old hody ,!I'I' graybodies is:
Conductioll heat transfel' as w('ll as radiation
intilWn('\' thl' on-taqrl't ('olllbustioil pfficiency of
(jnrt = 1/1, -- (j,' (5-4)

(~ertain tyP('S of inel'ndiary Illixturt's. The rate of ",hpre thp lid heat ('x('hangp is the difference be-
cnl'l'gy r(·leasf' of tlH' fuel-oxidant l"'iH'tioll, inti- t\\"!'('ll tlIP amount of heat 'I transferred by radia-
macy of ("Jntal't, and <'iH'mi('al-phys;eal propl'rties I ion to t lIP ('001('1' body, II'S)' the amount q trans-
of th(' targl't influPll('(' tlip heat transfer rah', fl'rr('(l frolll tltp ('ooll'l' to th(~ hotter body. Tjlis may
I1pat is trani'iferrNI by conduetion as w~ll as be writtpll also as:
by thr othrl' mo<1ri'i in ignition trains, (klays and
(5.5 )
heat powdel's, and should be takrn into t'Jllsidera-
tiOll in ('stahlishing drsign l'ritpria. or by application of th,' reciprocity theorem:
(jnrt = Eh~cP"-+cAh(l(Th4 - 4
Tc )
5-3,2.2 C, Dvection and Radiation (5-6 )
COllv'~divp and radiatin' modI's of heat trans-
wll('rl' g is thl' pmissivity, cc is the absorptivity, P
fer in pyrot('(,hni('s are more dosl'ly associated
is th!' fraetioll of thl' ,'nrl'lrY l'lllitt..'d by a radiating
with post-('()Illbu:,;tioll plH'1l0IIlrlla. ('ollvedive heat
bo(ly that is absorbe(l by th!' absorbing' body, A is
transfrl' t'ff"ds arl' It'ss impurtan t and will only
thl' arl'a of tit" I'mitting :mrfa(~l', fJ is the Stefan-
he mentioned bri('fiy. Transfer of heat ('uergy by
Boltzmann ('ollstant, and T is the absolute tem-
eonveetioll rpslllts from thl' groi'iS movpment cf thl'
jll'ratllr('. TIll' subseripts It !'l,f!'r to the hotter body,
fluid transfp/, Illpdilllll. Th!' amount (/ of hrat
alJ(l thl' suhs('I'ipts (' rl'f('1' te the eooler body.
transfprrt'd hy ('ollv(,<'tioll l'lUl be t'xpn'ss(,11 by th,'
Hadiation hl'at trallsft'r is important in post.
general ('qllation:
l'Olllbustioll plH'1l01lll'1l1t of pyrotechnic flares since
q = hA(tlT) ( 5-2) it is HII' primary nlPehanislll by which heat is re-
turned to tl\(' I'f'aetioll ZOllr, This fcedbaek is im-
wher,~ h is tllP IH'at transfer ('orfii('i(,llt, whi('h may
porUll1t to thl' maintaining' of propagative burning
be a eomph'x flllldioll of a largot' numb!'r of prop-
alld maximnm possibll' rffiei(,Il('i('s in the;;e type
ertirs inl'llldillg those rplating' to til(' fluid mCltioll;
r('aetions. As Illl'l'ady indicat('d, radiative heat
A is thl' ('ross-s('l'Iiollal art'1l; and ~T is thl' tem-
transf(·r 1Ill','hanisllls also inf\u(,lw!' the efficiency
pcratllrp diff't'r('llee. ('oll\"('('tiv!' I\('at transfer ef-
of "l'l'tain 1."lwS il]('I'IHliary mixtur!''l. In thi:> case,
feds lIiay ;'Xt'I't an infiul'lI('p Oil tht' 11lIninolls out-
it is I'xp('liient to produl'(' radiating" spr(,j"s whieh
put and ('flit'it'll(',\" of tiallll plllllH'S hy moving' oxy-
will 1)(' rl'adily ahsorlwd by tIl(' target.
gell into till' ('ombustioll area 'lIld/or by ('ooling'.
Tht'st' .'tft'd~; Ilrt' Ilsually slight and th,·ir lIIeasul't'-
mPHt l'xtr"nlPl~' t'olllplieatPfl. 5·3.3 HEAT EFFECTS
llt'at transf"l' by rH(liat i,lIl dol'S lIot l('qllirt' a If h,'at is t ransfl'rl'l'd to or from a system, the
transft'r lIll'dilllll. Tht' aH10 1 lJlt of ('lll'I'gy pmitt(,ll tl'lIllH'J'alllrl' of till' systl':l: uSllally ('hanges. The
from a heatt'd SUrra('(' whi('h has hlal'kbolly (~har­ magll il \Ill" oj' I h(, t"iIljll'wt urI' (·hallg(' dl'pl'nds on
ad,'risti('s is: I he lIIass of a ~,\'i'itl'1II alld its h('at ('apaeity. These
(ilialltitif's art' dis('llss('d ill Paragraph :l-2.1. Trans-
(5-:~ )
fl'!,' of Ill'al llIay also ('ausl' ptJllSl' eilallg'l's su~'h as
whetI' !.'t is thp ~tt'fall-B()ltzmallll l'ollstallt, A is (·rystallillt' Il'allsitioll, Ilh,Jtillg' (or frpt'zing), vap-

5- ,.
I- ----------------------------------------- ~--------------------~ -----~--------------- -- I

Al1CP '11l6.185

I Grization (or sublimation), and (lis'ioeiation, The ('raft structnrl'S, It is important that the bullet or
I'/H'rgy in\'o\wd in tIH'St' ('hallgt's ill st!"tt' may be Pl'oj(,l'ti!p provi(;(' a holl' ill a self-sealing fuel tank
lar!!p in t'omparisoll wit!l thost' inyolvpd in th" ~;o that ~iOlIH' fupl is tlpilled and ignitpd by the
raising or ~owerinl! of til(' temp('ratur,' of d.c huminl" in('endiary material. This pmphasizes the
systPlIl, Challf'es in state brought about by th(' illlp()rtall~f' of widf'!>pread distribution of burning
absorptioll of ht'ut may hI' pxtreniply important in partil'ips and long burst dur'ation, l\lost small arms
initiatillg' ('cmbustion si:J('p til(' fllPI and oxidizer in('('lIdiary ('fllllpos;t ions al'P l'1ixturl:'s of metal, or
must ill SOIlll' ('ases iw ('onYl'rted into thl' ga.s('ons IllPtal ;1i!OYs, alld 1111 oxidizing' ('ompouncl, These
sta«(' for thl' l'Ombll~ti(lll prol't'ss to proept'll. mixtur('s WitI'll initiated, in ('ontrast to some other
il1f'l'ndiarips, Ilsuall~' hurn rapidl:!; often with ex-
5-4 INCENDIARIES plosive violence, Unf'lzed incendiary rounds up to
hll'elldiat'~' devil'('s are used to initiatl' drstnH'- 20 lIllll ~izp", Ilrt' usually initiatpd by thl:' ht'st PYO-
ti\'(' fir!'s in a lar!!e \'ari!'t~, of targets. Whih, air- dUl't'd from Ow ('rushillg' of th t, metal nose oy im-
('1'aft, buildillgs, il~dl\strjal installations, ammuni- l'a<'1 whill' ~() mill dnd lar~l'1' sizps arp providea
tiun, and flwl (ll1l11ps HI'(' arnOllg" tilt' pt'illl'ipal tar- with fuzps whidl are initiated by impa('t.
g'pts for itll'f'ltdial'Y attat'k, itH'l'ndiari('s ila\'(' proved Tht' fundio~lillg of a thin metal nose, nonfuzed,
to bl' plf(,(·tiw against pl'rsonnel, armol'l'(l vphicles, small anllS illl,pndiary bullet ('an be divided into
and tunks, In many ('ast's, the psyehologi('al fear thre\' sf'paratl' <;tages:
of firl' illl'reasl's the f.'tft't'tiwlless of all ill('('IHiiary 1, \pitidifJlI uf in('('l\(lii1r~' ('Ollipositions by bul-
atta('k dS persollnel llla~' ab'mdoll rplati\,ply safe \pt illlpad 011 target.
positions and \'('hides thus I'xposing' thelll!';elws 2. Hapid bUl'Itin,,; awi lrl'atillg' of till' cJmposi-
to thp adioll of oth('r weapons. tioll alJ(l its l'ombustioll produds until a maxi,
!rH'PllIlial'Y ('ornpositiolls and ill(,t'lHf:al'Y dl'- ilium tl'I'Jprratu!'c i,; I'('a('hl'd and the burniug
\·i(,(·s ('all bp f'lassifipd ill many Wllrs depelHlill~ 011 ('Ollt('lItS bUl'st from tl\(' bullet jacket,
tlwir l'ompositiull alhl liSP. ;n this handbook, in- :~, Coolillg' of tll(' PI'O<iucts frolll tht>ir m8J.imum
l'l'llfliaril's al'l' g'l'fJlllwrl into lhrt'P largl' ('Iassps tt'mpP!'at 1t!'t' to t h\· minimulIl ('/ft'etiv(' temper&.-
hased on t Iwir ll~l': till'(" i.l'" th(, minilllulII lPlllperaturl' neces8sry
1, Small arms inl'f'ndiary ammllnitiun IIsf'd pri- for f1lP\ ignition.
marily against air('rlift all(l fuel dumps,
The ehaill I)f reaction with fuzed incehdiary
~, Oth('r illt'('n<iiary mllllitions inein<iing' hombs,
l'OltlHh, sll('h as 20 mill, is simil!!!' to that described
~r(,lwdl's, mortar and artillel'Y projt'etiles; to
t'XCl'pt that t hI' sellsltiv'.' fuze starts ignition upon
initiat!' fin's ill bllildings, i.ndustrial insta\la-
impact,
t iOllS, allllllllllition, fllPI dumps afld other targets
'I'ltl' d('g'l'('p of (ll'lIptrat;on h'foTe initiation of
ill thp ('OInbat WI\(', ill urpus llt'h!nd tIll' ('ombat
t hI' burst is dl·tl'l'milled, jll'imarily, by the sensi-
al'pa, and ill tilt' ZOlll' of illtprior of till' l'lH'my,
tivity of thp bull!'t and its ability to earry through
:L :->p"l'ial ilt('('IIflial'y d,'\'i('f's IIsf'd for eovert
purpusps, ill ('ollllPetioll with gucrrill::. operll- til ['g'!'t ,1l'('IIS to thf it~tl'rior of t hl' aircraft. The
tions, and for ttll' df'struetion ,}f material and physi('al sizto of th!' illepwliary hurst produced also
(IOl'uments, alf!'l,ts its bUl'st Itwatioll in the aireraft, This has
h!'PlI fOlllltl to Ill' I'slwt'ially important in the case

5-4,1 SMALL ARMS INCENDIARY or sparkilll!-typ(' illl'l'ndillry l'ompositions since they


AMMUNITION6 slll'l'!!d throug'hout II targ'et area and produce a
:->lI1all al'lllS ill\'(,IIdiaril's a[,I' w,;pd primarily for \,I'\,)' la!'g'!' lind l'/ff'etive burst volume,

stHrting' lit'strul,tive fires ill aircraft fuels, The FI\I' m:tlly ill('('lIdiary ('omp(witionR, for which

hUl'st prodl:('!'(l "er\'('s, basi('ally, as 1111 ignition tl\(' blll'lJillg" timp is vpry short, tl,,· effective burst
SOUI','I' f,}r till' fliP] l'uI'I'il'<I h,\' th(, ai~('raft sin('(' it dlll'at ion IS till' tilll\' rl'fjllirpd for tIl\' products to
is 'llllikl·ly that a sll.all arms in('('llIli:ll',\' hurst of 1'(lO] to tlrf' minimllm tplIlTH'ratlll'e ['pquired for fuel

..,unit-il'llt illtl'llsit,\' 0[' dUl'atioll would \\'('akl'lI air- ig'lIition, III otlwl' mixtllrps whieh f'oltain relatively

/l·11
A:MCP 706-185

TABLE 5-6
SUMMARY OF UMITS OF FLAMMABILITY OF V AR!OUS GASES
AND VAPORS IN AIR AND IN OXYGEN

Oxygen Percentage Below


Which Nu Mix!ure is
Limits til Air, l:;. Li'lr.it.1 in Oxygen, % Flammable

Nitrogel! as Carban
.Diluent of dioxide as
Ga. or Vc.por LoU't'r Higher I LoU'Cr Higher Air Diluent of Air
-----.-.------.----. .--.--.--.- -··---1--------- --------- .-----1------ - - - - - - - - - - - - - - - - - - - - - -
HYDROCARBONS
Methane.. 5.:~ (5.0) 14 15 5.1 61 1:~.1 14.ti
Ethane.. 3.0 12.5 15 3.0 66 11 0 13.4
Propan~. 2.2 !).5 2.3 55 11.1 14.3
Butane.... 1.9 8.S 1.8 .1' 49 12.1 14.5
lsobutane 1.8 8.4 1.8 48 12.0 14.8
Pentane 1.5 1.4 7.8 12.1 14.4
lsopentane. .. 1.·\ 7.{)
2-2 Dimethyl propane. . 1 .4 7. Ii
Hexane..... 1.2 7.5 11.0 14.5
Dimethyl butane. 1.2 7.0
2-Methyi pentane 1. 2 7.0
Heptane. . . . . 1. 2 1 .1 6.7
2-3 Dimethyl pe::ltane. . 1 .1 (i. 7 .
.....I' ..
'"

Octane. 1.0
lso-octane 1 .1 1.0 6.0 ..... ' "
.8 . .. , ....
Nonane ....
Tetramethyl pentane ..
Diethyl pentane.
.8
.. .7
4.\)
5.7 . .... .... I' .
.
5.4

f
DecaDe .. .8
Ethylene. 3.1 2.7 32 34 3.0 80 10.0 14.7
Prop} lene .. 2.4 2.0 10.3 11 2.1 11.5 14 .1
g.o 53
Butylene. 2.0
Bl>tene-1 1.{j !l.3 1.8 11.6 14.0
Butene-2 1.8 9.7 1.7 58
55 I'.
llK'butylene. 1.8 .... 88
b-n-Amylene . 1..'> 1...1 8.7
Butadiene. 2.0 115 ., . .. . lOA 13.1
Acetylene .. 2.5 81
Benzene. 1.4 7.1 11.2 13.9
Toluene .. 1.4 1.3 6.7
o-Xylene. 1.6 0.0
Ethyl benzene .. 1.0
Styrene. 1.1 6.1
Butyl benzene ... .8 5.8
Naphthalene. .9 5.9
Cyclopropane ... 2.4 10.4 2.5 11.7 13,0
Ethyl cyclobutane. 1.2 7.7
Ethyl cyclopentane .. 1.1 0.7
Cyclohexane .... 1.3 8
Metbyl cyclohexane. 1.2
Ethyl cyciohexline .\1 6.6

MIXTURES
Water gas ....... . 7.0 72
Cllrbureted water gaB. 5.5 36
Pittsburgh natural gas. · 4.8 .' 13.5 12.0 14.4
Other natural gases .. .3.8-6.5. 13-17
Benzine.
Gasoline ...... . ·· 1.).
1.4 I' . 0.8
7.6
5 ......I. 11.6 14.4
Naphtha .... .
Kerosene. .......i .7 5 '" .
Coal gas ....... . 5.3 n 7 70 11.5 14.4
Coke-oven gliS .. 4.4 34

~
Blast furna~e tas. 35
Producer gas .. 17 70-·80
Oil gas .. 4.7 »-35·1 . . . . 1.

;')-12
AMCP 706-185
i

s!ow-burll:ng metal fuels, tht' burning time is an The l'IWl'gy I't'quil'l'd to vaporize a giV!'1l quantity
apprcciabh' part of tht' total burst duration. of kt'l'osI,'ne is sOlllPwhat less than that for gaso-
lint'. Thl' PJlf'rgy must bp availablp, howpver, at
5-4.1.1 Ignition and Combustion of Aircraft Fuels sOIllPwhat high!'r h'llllwratul'l's bN'ause of the lower
It is generally accepted 9 •10 that the combustion volatility of kProspne. The PlH'l'gy mIHI!' available
of a hydrocarbon: (I) occurs in tht' gas phase, for eYClporation of fupl by tht' tianH' of It self-
(2) illvolvcs a chain-reaction mechanism which in- propagatinl! tirt' is roughly the SIUlll' for gasoline
cludes the formation of unstable species such as and kt'rost'lH' inasmlll·h as heat of l'omhustion for
free atoms and free radicals, and (:3) can occur hoth fll!'!;; lit·s in til(' rang!' of 20.000 to 22,000
only when till' concentr~tion of the hydrocarbon BTl' per pound.
yapor in the air falls within certain well-defined It is wf'll <,stablisll(-d I6 that fires ean be initiated
limits, as illustrated in 'fable 5_6. 11 Normal varia- by an incPlldiary bullet pl'netrating self-sealing
tions in atmospheric pressure do not appreciably aviation ftwl ('ells abow the liquid levpl, if the free
affect the limits of flammability; and, for most mix- spa('t' ('ontains air, pprhaps be('ause of a previouf.1
tures, therc is a straight linc rf'lationship betwecn purH'turt' or air leaking into the tank. Rarely, if
the limit of flammability and the initial tempera- pwI', has a firp bpen started insidp tIl(' tank by an
ture of the mixture. 12 illeendiary bullet "triking below the liquid level.
For fuel concentrations within the flammability In faet, during developmf'ntal tests of incendiary
zones, a firt~ or l'xplosion t'an result from contact ammunitioll, care wa..<; always taken to strike the
with an ilH'l'lHhary SLurce wlll'n the temperature of tank below the liquid level with a speond shot if
this souree is sufficiently high. Various methods tlH' first shot failed to ignitl'. All effort was toward
haye bl'en tried to detcrmine tht' minimum igni- drw!oping an illl-,pndiary bullet with one shot ig-
tion temperatures for various liquid fuels. A popu- nition ('apability below liquid level as this was
lar experimellt:il pro('f'durC' for ~;uch determina- most diffil'ult to achieve. Sueeess was achieved
tions involws confinl'IIlent of the fuel vapor and whpn incPlldiarif's of long burst duration and long
air mixturl' in a Buitab!e l'ontainer and a:-,plication parti('If' burning time were developed. These long
of l'xterual IH'at until thl' mixture,ignites. In gen- burning particles ignite the small spurt of fuel
f'ral, the hydro('arbons of a higher molc('ular weight whieh is forced through the bullet hole aftf'r 30 to
tend to ignite at lower temperatures. There ex- flO millisrl'ond~ by the prpssure wave set up inside
ists, h Jwevcr, an ignition lag 1S (Paragraph a-8.6.1) thp tank by the bullet.
whirh is dependent upon several variables. Flaim' will propagat(' in kerosene mist-air mix-
Grades ,TP-I and ,JP-3 aviation fuel have mini- tUl'es for 11 wider range of (~oncentrations than in
mum ignition tl'mppratures bl'twpen 400°F and kerosene vapor-air mixtures. It is impossible to
i'iOO°I<" with an assol'iatl'd ignition lag from 100 to obtain u eoneentration of kerosene mist in air
200 s!'l'onds. A "iation gasolin{'s have minimum too rieh to be ignited if the temperature is be-
ignition temperaturps of 800°}<' to 950°}<' with an ig- low the flash point of kerosene. However, at
Itition lag of 2.0 to 2.fi SPl'ollds. H The ignition lag tempf'ratures high enough to produce a vapor
for all hydrocarbon fuels becomes less with increas- ('onl'f'utratioll in air near thf' upper limit of
ing templ'raturps. At the minimuIll ignition tem- flammability, thp mixturp may be so rieh that it
Iwrature of gasolint', about 900°F, th£' ignition l'lg fails to propagate. The initiation of a mist ex-
fUl' kPrr)sell(' is in the range of 2 to 10 seconds. 11I plosion takl's plaet' after tht' evaporation of mist
Firps, tht'rl'fore, can bl' initiated and propagatpd droplets nf'ar the ignition source from a loeal vapor
in a flammable kl'rosenp vapor and air mixture as l'OIl('elltratioll within th" pxplosive limits. This
rpadily as in It !!:asolillt' vapor and air mixture if vapor ignit('s to form thp initial tianlP front. Propa-
both mixturl's are within ill!' flammability zone. gation of the flame pro(,t'l'ds by I'vaporation of
t 'ollf;l'qu('lItly, factors whieh ('oHtrol th(· formation droplpts whi('h form aI' influmlllubll' ~as mixture
of flld vapor art' of primary importanep in de- in tht' prelwating zonp ill advam'!' of thp flame
tt'rmining igniiion eharaeteristics. front.

5-13
AIlCP 706-185

r-~"-'-"--~~-'-"-'i-'I-'i-'I·-ri-'I~i-'~
depends strongly 011 the ambient pressure and the
:::I!
o 5 ~-_ _ _- - .
_x supply of oxygen from the atmosphere since these
factors are important if a self-sustaining fire is to
~W~~
o 0
3 ;~~- ~-~
-::'':;A 9, Oclonl Gasoline
result from the action of incendiary bullets, In-
formation obtained from tests in partially inert
Z~ I

i
ct atmospheres, both in altitude chambers and in actual
t- en 0 Alis of fUll "11
----~--------
flight tests, indic'ates that damaging fuel tires can-
o~- ~ I I<.ro..nl

~~ ~:::~~!----------1
not be started at very high altitude. Studies with
3 several pure fuels indicate that the relationship be-
~~ ~x----------~~ t.ween spark minimum ignition energy Hand
~ 5 pressure for a fuel-air mixture can be representt'd
x • 25% ... 00% ~ , 70% by:1R
o 2 4 6 B 10 12 14 16
k
INC'~ES 11= (5-7)
pro
Figure 5-1. Constant Ignition Probability Regions About C!
Fuel Jet of GaslJline or Kerosene where p is tilt' pressure, k is a constant which de-
pends on th(' nature of the fuel, and n is another
Studies of phenomena associated with the pene-
constant having a value of about 1.82, Even if
tration of liquid fuel tanks show that hydro-
fires arl' initiated at high altitude, the nature
dynamic forces resulting from the impact of a
of the firf's, ('spp('ially at the higher airflows, might
projeetil!' on an aircraft fuel cell product' a pres-
be diffusPd and low in temperature, thus limiting
sure wave in the stored liqnid. A high, positive
thp rlamag!' produced.
pressure is Iwar the point of tank penetration a
few milliseconds aftpr impact by the projectile.
The fuel spray emerg-illg from the hole made by 5-4.1.2 Nature of a Small Arms Incendiary Burst
the projeetile has tIw normal cha.acteristics of As already indicated, the burst produced by
filampnt jets with droplets forming at thp leading tht' functioning of small arms incendiaries is funda-
t'dge of t.he filament. . mentally an ignition source for starting a destruc-
Thf' basic factors whil'h account for the ditTer- tiw fUt'1 firl' in lin aircraft. The amount of
enc!'s in flammability characteristics of aircraft t'nprgy trallsfprred to the fupl dppends on the
,rupls arl' th" rplative volatility and viscosity of the naturl' of thp ('ombustion prot'ess (the temperature
fuels. TiH' relatively low volatility and high vis- rt'IH'I)I'11 alHl t hI' eharat'teristics of the products of
cosity of ker(l!;cne make it considerably more diffi- l'ombnstioll ), ttl!' modf' of {'nergy transfer process,
cult to ignite than gasoline. Results of tests (with and tIlt' I'ffi('it'IH'Y with which thp t'nergy is ab-
fuel jets designed to simulate the fuel spray made sorbed by tht' fupJ.
as a proje(·til,' penetrates a fuel tank) presented 'I'hl' maximum tt'IIIIwrature reached ill an in-
in Figure 5-1 indicate that the probability of a ct'ndiary bUl'st is a mt'liSurp of both its relative
positivt' ignition is greatt'r for gasoline than for intl'lIsity alHI duration, as a rt'sult of chemical
keros('lW at any point. in the volump su-rronnding rt'adions whil'h OC'l'ur within the burst to the end
the axis of tht' jpt. Th~ type of fire oc('urring with of its l'oolil1~ <'yt>if'. A ('onsideration of ttlP hurst
the gasolilH' jet is usually different than that oc- tt'mppratur(" and thp p!fe('ts of the physical and
curring with kProsPllp. Most gasoline fires propa- t ht'rmodynllllli(' propprti('s of in('pndiary mixturp
gat.e r~ ~idly through thp fUl'l spray. I,ittIl', if any, illgrpdiPl1ts alld th"ir rt'ac·tioll prodlH'ts, com prist'
unhurIlt'l! fuel is left in th!' ar~a. In contrast, IIIl important art'a of study ('oncprning an incendi-
nparly all kproselJe ignitions arp localiz!'d, scldom ary bUI'st. Thl' tpnllwraturp produl'cd by an
propagating mor!' than a few ilu'ht's from the point illl't'lldiary burst ,'an bl' t'!>timatt'd hy caltulations
of i~..'IIit.i()ll so that most of tIlt' fut'! is It·ft Ull- IlSillg' thl' ll11'thotis outlillt,d in Paragraph ~-2.5. It
burned. is IIt'I'('ssary to assu III 1', arbitrarily, the amount of
'j'h!' l·tTt,(,tiv('IIt'~; of illl'('l\lliary ammullitiou also II t llIospht'ri(' OX)'/!I'II II "ai lablp for combustion of the

5-14
AIICP 7()6..185

incendiary mixture. 'I'hf' I'xtl't'tlll' ('OIHlitioIlS are [ll'odul'ts from til(' maximum t('mperature reached
either: (1) that till' only OXn~l'lI Il\'ailable for by tit!' ill(~(,ll(iiary hurst to tht' minimum effective
('ombustioll is that containe(l ill til(' mixturr ('om- tl'lllpt'ratlll'!' divided by the temperature differ-
POlH'llts dul' to insufficient tiult' for the difl'usiell of t'1l"('--IlIHI 11\ ·g!e(·ting 7'8 4 siJlc(~ it is very much
atmosphl'ri(' oxyg-cn into thf Ham!'; or (2) that "mallt'l' t hall Til \ integration yields:
till' Slll'rOllIHiiug" air supplieR tlIP additional oxygen
requirNl for ('ompletc combustion of thl' reactants.
0:: = (_1__. _1_)~a .0'8·/- Es -
T} T 1a
EBEB)C
(j}!JSEBA
'rhe actual condition is prohably somewhere be-
(5-9)
tween. Limitl'd I'xperiml'ntal data obtained for
bursts jll (·oJltrolied atmosph('fl's indieatl' that tile If it is assumed that the radiating area A and
surrounding atmospherl' dol'S I;ot ('l1te1' appreciably emissivities Ell and E.~ have average values which
into thl' incendiary rt'action so that condition may lw Ilssumed constants for the various bursts,
(1) is thp bl'ttl'r assumption. The diiferrnce in the th£' terms outside of the parentheseR may be con-
fl'SUItS is small, however, becans(' of ,he necessity
sidered a constant K and:
for hl'atillg t!1P nitrogen Gi th,~ air nndrr assump- 8., = kC(--'!'-- ___1 ) (5-10)
~ion (2). (Sle also Example 4, Paragraph 3-2.5.) - T/' Ttl',
The rate of heat transfer from the burst cloud [f k is assumed to be 108 (A 2:; 2 X 10"cm2 • EB =
to it~ surroullding-s depends also upon the method 0.9, E8 = 0.1 and m:..=:: 1), the curves in Figure
by which the heat is transferred. Heat can be ;:;·2 result where it is assumed that the ll1inimum
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-
temperatu!'e of aircraft fuels, heal' t(an~fer by culated or experimentally obtained and if the heat
radiation is probably the dominant methc,d. Hadi· of reaction is known, Figure 5-3 can be used t.o
ant enrrgy emittrd by thr liquid, solid, and gase<)U& pstimate an averagp specific heat. If Figures 52
species in all incendiary burst is a complicated and 5-3 are eombir..ed, Figure 5-4 results. 1.\s CBI1
function of wavelength, pressure, geometry, and he S('('.I;, the eoolinr' time varies directly with the
chemical composition of the emitting molecular aVl'rage speeifie heat. Thc curves also indicate that
aggrr?atr, as well as of trmperature. However, any in('rrase i,l the burst temperature above 20000K
based on pxper;mental results, it can be assumed results in only II small increase in the cooling time.
that the illcrndiary hurst cloud raiiates as a gray- Changp in cooling times resulting from transfor-
body with a rplatiwly hig-h c.nissivity. mations is diffieult to determine becawse tbe details
The rate of h~at transfer from an incendiary of th£> eooling mechanism are not known.
burst doud, radiating as a gray body may be ex- Experimental cooling curves for incendiary
pressecl by: mixtures arc given in I<'igure 5-5. 111 IM.ll, 50
percent barium nitratp and 50 percent magnesium-
dQ IdO = ElIEs!T(!~~__ Ts4)A (5.8) aluminum alloy, is one of the litandard mixtures
I Ell -1- E.~ _. };IIE8
llsP(l ill incendiary bullets. 1M -2a, 50 percen ~
wherp A is thE' total raaiaGing 8relt of thp eom- potassiullI pt'r!'hlorate and 50 percent marnesiun
ponents ill t hI' burst lloud, d() is quantity of heat alloy, eon tail's no bariUll' nitrate and it.s calcu-
radiatpd by the irwl'ndiar,v hurst eloud during tim I' latl'd temperature is higher than that for IM-ll.
intl'rval d'O, (j is 11)(' Stpfall. Boltzmann eonstr.llt, 11\1-63-50 percent calcium peroxide, 45 percent
E is tiH' ('missi\'ity. and T is till' absolutp temppra- rl'tl pho~pborus, altd fi percent aluminum h~r­
tUrt'. 'I'hr subsl'ript 8 refPI'S to the burst and the droxidl~do('s no~ contain either barium nitrate or
subscript 8 l'efl'rs to thl' surroundings. By com- allny, and has a eonsidprahly lower theoretical
bining' this pquation with the equation dr.) = mCdT maximum temperature than IM-ll. It is to be
wlirr<' (' is th., u\'('rall aWl'ag"e specific heRt-i.e., Ilotf,d that IM-to:l, fiO percent red phosphorus and
eqUals till' heat ('\'oln(1 F'r graD!, ind\diq~ that ;-.0 lH'rcent magnesium-aluminum alloy, does not
fr,)IlI phasl' ehang'es, in thl' (~oolillg of the reaction ('ontain 1m oxidizer.

5-15
AMCP 706·185

---,- I
C=2.0
en
. 400

~
0
.. 7000
E
!i::
. oK
W 0
a::: 0
300
~
I- 0
<t CD
ffi 5000
a..
:E
W
- 20J
0

CD C=1.0

I- I.IJ
l!
:E 3000
::>
... C::O.7

~ <!)
Z 100
X '.::=0.4
<t ...J
:E 1000 0 C=0.2
0
U
o
o 1000 3000 5000
HR HEAT Of' REACTION,cal/g MAXIMUM TEMPERATURE ~, OK
0
Figure 5·3, Cnoling Time to 800 K ar a F'indion of
Ten,peratur. and Heat Capacity, C
Figure 5-2. Maximum Temperature, T, al: a Function of
Heat of Reaction and Average Specific keat, C
plosiv{' Illlttl'rial in addition to its incendiary fmer
mate!"ial.
5-4.1.3 Small Arms Incendiary Fillers :\Iag'llf'sinm-alllmillum alloys haw been an es-
Small afllls ilh~l'ntliaI'Y ammunition, which IlOW sl'lItial ill~rl'(lil'lIt ill most of thl' successful incendi.
illellilit's amlllullition through ·W mm, has been ary mixtllrt's, auel haw r{'placed both whitt, phos-
dt'Yl'lopcLi, like otlwl' amlllunition, to meet the par- phorus illl'l'lHliarips and traCf'r compositions,
t il'lIlaI' llPl'ds of tht' using Services. Important Trll.('(·rs, first \18('(} as ilwendiari\.'s, emploYf'd a
1Il0difil'atioJls amI illll,rO\'('IlWlIts wert· mudt, through fillf'r l'onsistillg of two parts magnesium and seven-
thl' Yt'ars ilJ n'spolHw to changes if: Service needs t{,(,11 parts barium lH'roxidl' for inct'ndiary pur-
or aJltil'lpatt·d l'!lall~t's in Sen'ie(' n'quil'l'lllents. poses, I fntil thl' d{'velopment of thl' highly satis-
garly dp\'('lo!lIlH'lIts in small arms incendiary alIl- t'lidory ilH'j'lldiary fiUf'r basf'd on a magnesium-
lllullitiolJ filll'l'-; han' bt'{,ll discus..-;I'd ill the his- aluminum alloy (50/50) fuf'!, with barium nitrate
tot·il'al rp\'il'w of illt'plI(iiarics (Paragraph 5-1), as tht' oxidizf'l', changf's in trae('l' mixturf's used
SPllsit i VI' l'X plosi \'('S-ille!udillg' Illl'r('ury ful- as iw'('ndiarit,s Wl'rt' limit{'d to tJI Jse which would
millatl', lead azidt', and PET!\--wl'r{' employed in improv(' tl.~ Iwrformanl'e of Jlletal-oxidant com-
SOl'It' l'al'ly illl'l'n<iiary fiJI {,I'S, Other t'xplosives- positions, ;\'ullH'rous inc ... ndidry mixtures haY{' been
ineluding- tetryl, MOX, TNT, lIaleite, and EDNA test!'d for \lSI' in small arms ammunitio!l in the
-1'.]0;0 hav(' bet'll t:-ied in smaller nonfuzed in- IJpriod siJl('p th{' beginning of World War II, A
l'{',Hliary ammullitioJl but haY(' not proved satis- detail"d (~lird file listing of the inl'entiiary mixtures
fador,\', IIi~h l'Xp!OSIV(' ilH'('IJ(liary ammunition whieh haVl' bf'en given !ill 11\1 number (approxi-
i. 20 IIIIl1 and !ar~{'r siz('s ('ontains It purf'ly ex- lIIutl'ly 1000) is mllilltained at Frankford Arsenal.

5-16
AMCP 706·185

.---, figure indieat(' that an in('rpas(' in bUr!;t duration


40

---e= 2.0 ilnd copling tim:) results with eoar"er and with
en C. col 10 p.tomizd or spherical partich·s. Piring tests con·
E... firm these results. Evaluations of magnesium .
~ aluminum alloys other than 50/50 3how that the
0
50/50 hlloy is superior for a varietr of applica-
0
0 30 tions wheth('I' gro l.lIld or atomized.
Q) In an attpmpt to <i('v('lop improved small arms
! iilc('ndiary mixtur('s, a large numbe ..' of metals and
0
t- alloys Wl'rp evaluated for their effectiveness as in·
Q) e = 1.0 cendiary ftH·ls with several oxidizing agents, as
rcport<,d ill detail in Ref~rence 6. Some of these
llJ 20
:E mixtures producl'd incendiary bursts which have a
l-
e = 0.7 longer duration than those produced by IM-ll.
Thl.'se mixturps also have proved to be more effec-
(!)
tive than IM-l1 in comparative tests against air·
Z
10 ('raft targets.
...J
0
0 e = 0.2 5·4.1.3.2 Oxidizers
()
A wide variety of materials have been used
as oxidiz('rs in inc~ndiary mixtures. An oxidizer,
for ur;e ill maSl>.produced items whi('h are loaded
by automatic mlleh~nes, must meet a variety of
HR HEAT OF REACTION, col/g requirements in addition to being able to supply
tht' n('cessar,); quantity of oxygen.
Figure 5-4. Cooling Time to 800 0 K os 0 Function of Heal The effect;; of oxidiz('r partid(' size 011 in-
of Reaction ond 5rwcific Heat, C cendiary bursts have been stani('d. lilCendiary
mixtures containing oxidizer particle:; of compara-
5-4.1.3.1 Fuels t~vely Iltl'gp sizp (100 to 200 me3h) could not be
Incendiary cOfl'positions containing magnesium- ignited ullless the mixture ('ontained finely divided
aluminum alloy have beell the basis of most of the (less than :125 mesh) alloy f\wl particles. Mix·
standard incendiary (·ompositiom; investigated un· turt's ('ontaining fill!' or medium-sized bhrium
til reeellt years. Studies have indicated tbat an nitrate particles would not burn except when
alloy of 50/50 proportions, prepflred by grinding mixed with coarse alloy. Alloy particle sizes in
with a partiele size rauge from 60 to :325 mesh, tht· range specified fur IM-11 r('acted erratically
is optimum for a wide variety of applications. with either It narrow range coarse or a fine barium
The effects of variation in the granulation of the nitrate powd('r. Specifi(~ation ~~a(~e alloy reacted
magnesium-aluminum alloy were evaluated early bpst with barium nitrate which eonsisterl of both
in the program, Ipading to thp development of fine and coar~e particle sizes. The cooling dura-
IM-ll (eomposed of 50 percent magnesium-alum- tions of the incendiary burst for th(' few mixtur<ls
inum alloy 50/50, and 50 pereent barium nitrate) whieh eould bl' ignitt'd incrpased as the particle
which was tht' basil' ine(·ndir.ry mixture used in size of the barium nitrate was ilH'l'pas('d, but these
World War 11. ~~igure 5-6 shows ti".e cooling ('hang('s wpr(' rplatively small.
eurvei; and burst duratiun (til\' tinlP from ignition Some of the alkali metal and alkaline earth
until burst eioud eooled to 1540 0 K) curves for nitrates have bt'en more widely employed than
mixtures which contain eith('f thl' ~roullil or ether types of oxidizers because they are available
atomizpd alloy in a vari(·ty of mesh sizes with at low CO!;t, contain large quantities of available
some bari nm nitrate. The results pr('s('nted in this oxygen, are saft', and .:!an be bandIed easily.

5-17
-~
,

AJ(CP 7()6.185

2600
2500
2400
~
~ 2300
". 2200
W 2100
0::
...::>~ 2000
ex 1900
0::
W 1800
Q.. 1700
~
W 1600
I- 1500
1400
1300
1200 I I
0 50 100 150
TIME, MILLISECONDS

Figure 5-5. Time-Temperaturil Histories fa,. IM.JJ, IM-23 and IM-103

Barium nitratp has been ineoryorBted in over 200 trat!' but exhibits a lower decomposition tempera-
incendiary mixtures, including the widely used tun'. Mixtures ('ontaining potassium perchlorate
1M-II filler, and has bt'pn utilized in proportions tend to btl mort' 3t'nsitive and to burn faster than
ranging born one percent to 65 percent of the llIixturt's whi(·h ('ontain only barium nitrate as the
total mix. This oxidizer js st.able to approximately oxidizt'r< Ammonium perchlorate has also been
6oo o e, 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 t'xplosive sincp the hydrogen contained
compositions in whieh barium nitrate is used as in the compound ean be oxidizt'd rapidly as the
the primary oxidizer are improved, from the stand- del'Ompoflition of ammonium perchlol"ate takes
point of incl'ndiary functioning. by thl' addition plact'. 'rhis oxidizer-explosive has been uoed ex-
of a small quantity of a more reactive oxidizer trnsiwly in the l\IOX series of metalized ex-
such as ammonium nitrate or pota."'-'1ium per- plosiv{·s and probably ('ontributes to the explosive
chlorate. Ammonium nitrate has been used in I'ltergy of thest' ('ompositions, as well as providing
sevt'ral ineendiary mixtureg as an oxidizer, how- oxygt'li for th!' burning of the metallic fuel which
pver, it has a relativt'ly low dCf~omposition tempera· providl's thl' major im'('ndiBry effect of MOX-
ture and tends to sensitize incendiary mixtures loadt'd ammunition. Ammonium perchlorate is a
in which it is used. Other nitratt's are pot!'ntially rather sensitive oxidizer and, therefore, is some-
good oxidizl'rs, but art' not widt'ly ust'd bt'eause of what hazardous to handle. Othpr perchlorates have
soml' undt'sirable ('haradt'ristic, such as bt'ing rt'la· het'll used: but, in g'1'1It'ral, tht'y art' hygroscopic
tively hygroseopie nr uneconomical. Ilnd, therl'forr, arl' diffh'ult to handlt> in production
The alkali metal perchlorates are the second lORding t'quipment.
most widPly uSl'd group of oxidizers for inre!1dlary SOIllt' [wroxides and If'sS stahlf' oxides CRn bt>
mixtures.~ PotassiuIll perchlorate has been used in used as oxidizt'rs in ill('ellLliary mixtures. Lead
marly inet'lHliary filll'rs in proportions varying dioxide is probRbly tht' most important member
from 2.5 percent to 75 percent of the total mixture. of this group, all(l it has been us{·d in several
PotassiulIl lH'r(~hloratl' has t'ssl'ntially the saml' i/l('t'ndiRrr fiIll'rs. It tt'llds tu sellsitizp mixtures
total /lnd availao)l' oxygrn ('.ontl'llt aN barium ni- in whi('h it i~ IIsl·d. although by itst·lf it is safe

fj-H~
AMCP 706-185

5-4.1.3.3 Binders, Lubricants, and Other


50% At_Iud Alloy
Incendiary Mixture Additives
2400 -100 _200 • 9lI.3% The first metal-fuel incendiary compositions
:.: , , \ ; 2 0 0 +325. 67%
o
W
~
~2200
to-
2000
\: .'.~
~.-
~
\
' •••• j.,.
-
-
eo%
-.-.- •••.•• ,
f.
Ground Alloy -100+200

......
IIsed in small arms ammunition contained only the
metal.fuel and 11 suitable oxidizer. The mass pro-
ducti'JII of small arms incendiary ammunition dur-
~ ~::;,t-··.,., ' .... ing 'World Wal' II created problems concerning
0:: 1800 500/0 Ground~·::---.., ' - . , ..... -l
W Alloy • 325 '-"" • • .... 'a., ....... pellt'ting of incrndiary mixtures, sticking of com-
Q. '" ~ I""'w. ·'e
:JE
W
1600 ',.
,
'- ..., pression punches, lumping of mixtures during
I- 1400 50% Ground Alilly '50% .:lround Alloy
handling, and failure of mixtures to flow properJy
(Standard) -200.325 in the automatic loading equipment. These prob-
1200
o 50 100 150 200 lems were met by adding binders, lubricants and
TIME ,MILLISECONDS flow promotrrs to the then standard ('om positions.
Thc 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 of Magnesium Alumi- functioning of the ammunition, and they were es-
num 50/50 Alloy
sential to the successful mass production of in-
eendiary ammunition. Without these additives
and easy to handle. Less oxygen is available from it would havl' bepn impossible to achieve the high
ll'ad dioxide than from many of the nitrate and It'vel of ammunition quality that was maintained
pen'hloratt' oxidizers. Its high density has made during World War II. SineI' then, the require·
kad dioxide useful for appliclltions where an in· ments fo!' ruass produced ammunition have become
('rt'aSl' in bull!'t weight is desirablp. ('vrll more stringent.
A few additional oxidizt'rs that have been eval· The two most frequently used binders in small
uatl·d in incendiary mixtures are worthy of men- arms incendiary mixtures are calcium resinp,te and
tion. These inelude potassium chlorate, which is asphaltum. In iilcendiary filler compositions, cal-
a rPlatiwly good oxidizer except for its sensitivity cium rt'sinatt' is used in amounts varying between
alld illcompatibility with certain fuels, notably red 0[1(> d/ld two percent, and asphaltum is used in

phosphorus; strontium l·hronl8t.l·, potassium di- UIIIOUIl t'l varying between one and five percent. A
('hrolllate, and potassium Iwrmallganatt' have also tllllnbpr of other hindeJ'fl have been tested in sev-
h!'!'lI used. ;...rolle of thl'sl' has bel'I1 found to ht' ('ral t'olJlpositiolls from time to time. These include
full.\' satisfactory as oxidiz!'rs for inc('IHliary mix Acrawax, dpxtrill, starch, nitrocellulose, gum
applil'ations. arabie, polyvinyl alcohol, red gum, vistar.ex (a
One uf the lIIost intriguing applications of rubb!'I' preparation), and AP-2 (a jellied gasoline
oxidizin~ nHllt'rials to th!' (it'struetioll or damagin~ 11.111\ aluminum mixturt').
of ait·(·raft strul'turt's is tht' dil'Pl't real'tion of an Ora ph itt" ill a runge of ilartieie sizes, has been
oxodizillg' agl'lIt with tltt' LIt'I ('ontainrd in the USI'l\ Slll'l't'AAfully as a lubri('ant to prevent the
air(·I'Hi't. Tltt· it jell is Il}lllt'alillg' ht'('IlUs!' of tIlt' stit'king of pl'll!'ting Illld compression pllllch~ duro
I'utt'ntial ('itt'lIIi('ull'lH'rgy ft'Il'llst' situ'!' only oxygen ing tht' loatlillg of inci.·ndiary ammunitioIl. This
01' all oxidizing' Hg'('n! is plat'l'd in tilt· projectilt' lubricant is normally added in amounts ranging
anti no SPII('" is r"quir!'(} f(;r ftlt'l. :\[allr rather from O.:!f> pt>re!'nt to 2.0 ~lt'r(·l'nt. Stearates of zinc
ditlh'ult pl'lIl'1i('al problt'lIIs lilt' ill\,ol\'t'd in adapI· and Hlulllilllllll hav!' bpell I'lIIployt'd in II. number of
illg this Ilrillt'ipl,' to realisti(· targl't conditiolls sll1all arms illl·t·/Itliary l'ompositions to prevent
\lsi ng sf "tHI"".! projt'ttilt' "0111 POIH'lIts lind fuzing IUllips fl'O":' for\llill~ ill th!' rnixtur!'s Illld to im·
IIlt·dtllnisllls. :-;O\ll(' pf tit,· oxidizing' cit!,lIlicals pro',"t' tltt' fkw (·harllett'risti(·s during the automatic
whidl lIIil-!'lit ht' wwful :11 this (·Olllll·(·tioli illclude loadill!! prOl't'S!;('S. TtI!'s!' inl!,Tfdi!'nts are of some
I}\. ('I F:1. Brl<\. II ('II )4. (IF". ()~ l<'~. ():,F~. ;...r( ):11<\ a.'isisfall('" ill forllling pt·llt-ts of ttlt' mix in additioJi
(·I()~F. alit! ':--:1<\. It) t h,·j r flow ·illt!tlt·illg t'haraderisties. Zine st('.arate

5-19
AMCP 706·185

TABLE 5·7
TYPICAL SMALL ARMS INCENDIARY MIXTURES

IM-ll -!!)'); Potassium Pen,hloratt'


;")W;; ~Iagll('siulll-Alulllilllllll AI/oy (;")0/50) 27c Calciulll Resinat!'
:jOy, Baril:m :-';itrat('
DI-139
IM-~lA lOll. Magut'sium-AlulIlinum Alloy (50/50)
-!tl ~i~ :\IaglH'si UI:I-Alur.lill!\IlI Alloy (50/50) -10 'It. Nt'll Phosphorus
-iHt,Ic Barium Xitrat(' 47;; Barium Xitratl'
:lJ~ CalciullI Resinatt' ;3~i(, AluminuJIl Stt'arate
1'1; Asphaltum
DI-H2
IM-23 -Hij; Magllt'sium-Alumilllllll Alloy (50/50)
:iWI. ~lagll('sium-All1Inillulll Alloy (50/:JO) 48 ~I. BltriuIII Xitratt'
,jO';' Potassiulll Perchlorate Asphaltulll
('/
1 /1 Graphite
1l\l-2tl
:iO'/~ :\lagllesillllh:\lumillum Alloy (50/50) lM-2H
-!Ot,~ Bl!rillJll Xitratt' ;")0'1< Zirconiulll (60jtlO) (lot 0)
10'/; PutassiulIl Per('hlorate 2;;j; )lagllt'siIlJll-AlumiuulIl Alloy
~j'!v Potassium Perchlorate (-250)
Dl-oH
:;0% ~,laglwsilllll-Alulllilllllll Alloy (;',()/;jO) IM-241
AUlIllOllill1lJ Xitl'att' :iO?, ZirconiullI (20/05)
~-!'A Bariulll Xitralt' :!;)'I< Magw'sillJll-AlumillullJ Alloy
1'·'
I' Zin(' Stearate :!5?" Potassium Perchlorate (-250)

1M-09 IM·:3H:J
,jOj,. :\Iagllesilllll-Alullliuulll Alloy (;)O/:iO) -l!)j\ )iagnt'siuJIl-AluruillulIl Alloy (;iOj30)
-W'/; Bariulll Xitl'att' . W~I. AmllloniuUl Perehloratt~
lO'i; 1rOil UXitll' (}<\'~03) 2% CalL'iuUI Resillatt'
DI-112 :'.10X-:!B (High gxplosi Vt' Illeendiary "'illers)
,-,:! ?, AlUlIlillUJll Powder
:'.iagllt'siulII.AlulllillulII Alloy (:iO/50)
- (
;, /1
!
Tung-stt'll Powder :It,?, AlIllllUlliuUl Pt'f(·hloratt'
,iW; BariulII Xitl'alt> ti'i, HI>X / Wax (!)7 la)
-! j; '1':-\'1' (Cuatt'd 011 tilt' AmmollillIll Perchlorate)
Dl-1 :W 2'/< ('al\~illlll Stt'uratt>
-!!l',( :'I\agll!'siulII-Alulllilllllll Alloy (;,O/[)() 1'/< Uraphite

III Iht' lll1lOllllts of 1'/ -:!~:; has b"t'l! lIlost widely 5·4.1.4 Typical Small Arms Incendiary Bullets
lh('t! fOl' this pUI'JiOSt>, AlulllillUIII slt'ul'lltt' hilS also 'I'y pi('lIl ill\'t'Jldiliry roullds Urt~ sbowll ill J.'iKUrt'S
ht't'll t"llployt'd fur this "tll'pOSt', ;,-7 through ;,-10. llirlstratt'd art' II. l'ali\H'r .;)tJ
ill('('lldiliry hllllt,:. Fig-urt> :J-7. Illlll Ii ('alib!'r .:,0
5·4,1.3.4 Typical Compositions 1I1'111Or-pit'ft'lIIg' illl'\'lIdiury, }<'if,('llft' ;,-H. A ~O :.lI11l
'I'lI(' ,'oIlI(H,sil inlls of 1-1 sIllall !lrlllS ill('Plltlial'Y 1I1"II1OI, .. pit"rl'ill~ illt't'lldilll'), build. i~ shown ill }<'ig--

Illixtllrt'S, ('ollsitit'I't'd to h,' lypi('III, al't' ~dvt'll ill IIrt' ;,-!! /llld 1\ :!() 111111 high (·xplosivp illt'Plldillry
Tablt' :,-7. projt'd ilt' is showll ill FIgurl> ;)-10.
AMCP 706-185

I NCENDIARY MIX TURE

GILDING METAL JACKET

GILDING METAL CLAD STEEL CONTAINER

LEAD-ANTIMONY SLUG

TOTAL WEIGHT: 512 GRAINS

Figure 5-7, Typical Caliber ,50 Incendiary Bullet

5-4.2 INCENDIARIES FOR GROUND hallds of t'olllbat troops. Littlt', if any. ri'fort was
APPLICA TION dil't'dl'd toward st\ldyin~ thost' fadors eoncerul'd
UrOllllll illl"'IHliarips ilH'itHII' that ('Ias:; of mUlli- with tht, initiatioll of '\rstrudiw fil'PS ill various
tiolls IIsl'd fol' dlllllllg'(', maillly by ('olllhIlStioll, to targt'ts. As a ('OIlSl'qll\'IH'P, !f,ss is known about
gl't,Hlld tllr~,'ts IIlld III'" ('ollsidl'rllhly la'!!t'r thall tilt' tlrt' fal'lors whit'h mif.!'ht illerp/ls\, til<' ei'frctivelH'ss
;';lIlall arms illl'l'lldiari,·s PI'l'\'illllSly dis(,lIs;';,'(l. Ill- of illt't'lldillry Illunitiolls against groulld targets
("'Ildiary bUlIlbs, for "XllIllpll', Ill'" III 0 I'!' I'ffl'(,tiw I hllll is knowll abollt tl\(' I'ffl'(·tivl'lIt'ss of illcendi-
1Ig'lIillst I'itit's thall hi~.dl "xpiosin's, ,·sp.· .. ially wht'll Hri('s Ilgaillst lIir(,l'Iift tllrgt'ts.
IIlltip('I'S()IlIlt'1 1'1'111111'(';'; HI',' illl,/tld('d to dday fir"
figilting' OP'·I'lItioIlS. Tilt, dt'llI,\" ill fir,· fighting' 0Iwra. 5-4,2.1 Ignition and Combustion of Ground Targets
tioll;'; ullows till' sllIallt·1' lin's to grow Ilwl I1l1iu> to 11\('l'lltlial'Y alll\ ot ht'r flalllt·· producing weapons,
fOl'lll It I'Olltial!ratioll w/ridl is allllost illlpo~'liLle to likt' 1Il{)~t Wt'apOllS wwd agllillst ground target .. , are
(·olltrul. III IlIlIll,\" ('I\...,,·S, tllxi(' t'tf,'l'ts l'l'sllitillg' frolll " sOllr('t' of t'Ilt'I·t!Y whi(·h, wht'll IIbsorbt'd by the
th(· liS.' of ill('('lldiari,'" or tlUIII(' W('/lPOllS (high cllt'· largt't. will ('allst' dUlIIltgl'. 'flrl' amollnt of t'ut'rgy
bOil IllOlIllXid,' ('olltt'llt-iow OX)'''''11 ('OIlIl'llt) ,'allSt' IIhsorlwd from tilt' illt't'lltiiary sour('(' by tht' target
mUll,\" ('IISlIIIIti,·s. III ""lilt' ('liSt'S, th" pS,\l'holog'i,'al is llot IIslIlIlIy :mffil'il'llt tll prodlll't' Ilpprt'('iablc
f"ar PI','\"'llts ,'ff,'l'Ii\'" tir,· til!lrtillg' OP('I'llti!>I1S lUll! dlllllllt!" hut s('I'\",S ollly to illitialt' ('ombustioll nf
11111)' ('t'sllIt ill tlr,' loss III' t''1UiPIHt'llt t:ll'lIlWh ahan- tht' tul!!"t ill tht, ()XYt!.'1l (,f til., Ilil'. Small firt's
t\OIlIlIt'llt. stlll't"'1 ill thi~ ; "lllllt'r st'l'\,,· as iJ!;llitioll ;;our('('s
H""HIIS" pl'lIgl't'ss ill lilt' dt'\'"lo!lIl1('llt of jll('\'lidi· for tli;, rt'lllllilldl'r til' tlrl' tal'gd Illlltt>rial. resulting
Ilry !llId t!alllt' W""POllS fllr Uh" 1t~lIillst grolllld tar. ill tht! ,;pl't'lId (If tlll' Iii'". Tit, i~uiti()1l pl'()('ess and
j!t't,.; hilS ht"'1\ 11111.1,· lIluillIy dllrillj! lilll"~ tlf strt's,>;, ,'uI'I,\: j!r()\\lit of th,' lir,' art' tht' t·ritil·1I.1 s~es in
"lllphasis hilS b""ll di/'t'l'It,d toward tilt' .i'·\'t'I()Plllt'llt t h,' o\P\','IIIPlIlt'lIt of II dallllll!"-proc!u('lU!! tirt'.
of Wt'lq)(IIlS whi"1i "()1I1d b,· rapidly put into tlr!' To illiliut" hurnillg of a targl't ill air, thrf'l'

5-21
AIICP 706-185

INCENDIARY MIXTURE 1M-II

GILDING METAL JACKET


TUNGSTEN-CHROMIUM STEEL CORE
LEAD BASE FILLER

TOTAL WEIGHT: 662 GRAINS

Figure 5·8. Typical Caliber .50 Armor·Piercing Incendiary Bu'Ie,

1'S8('ntilils must be provided, lHillll'ly: (1) Ii source of /lnd a combinlltion of thesp two. Fillings CM .lJ.lso
heat to initilltp tht' firt', (2) combustible material bt' elassitit'd int.o those which owe their incendiary
whir.h servt's as kindling, and (!!) the fueL All effect to a self.supporting exothermic reaction and
in('endiary munitions, except those whic!l art' spon· thuse which dt'pend on atmosphprie oxygen for
taneously combnstible. must ('olltHin all initiator. their combustion.
Th(' ml:ljor part of I:In illcf'ndiary filling serves as
the kindling and HIl' targ?t supplit's tilt' fuel. The 5-4.2.2.1 Metal·Based Ground Incendiaries
t'fficit'll('Y of lUI illt't'lHlillry dt'pt'IIIIs Oll thi~ total Iuct'ndiaries containing metallic components a't'e
heat output and thl' ratt' of tr/lnsft'r of tht' energy of two t:'pes: those which utilize thp oxygen of the
to tht' targ!'t so as to initiat!' 1\ s!'qUf'nc(> of events air in ttll'il" eomhnstioll, and those in which lI,n
which will rt'suIt in thl' hurning of Ow targct, oxidizing agPllt furnishes thp oxygen,
80lid matt'rials. such as wood. must hI' h('ated to a Magnesium-aluminum alloy used both ItS the
suffil'it'nt\y high teJll,wrat urt' ill Iml(,1" to form the l'ast' and ill the composition of Ii four-pound in-
gllSt'<)\)S intl'rllll'diat!'s to rt'ad wit h thp oxygen of cendiary homb is an t'ffectiY(' incendiary and W8S
tht' air. Liquid fuels. as dist"llSSl'd ill detllil in widely used ill World War I I in raids against
Paral~'rl\"h fi·4.:!.:!.:!.1, also IUllst hI' vaporizt'd bt'- German al!d ,JllpalH'st' citips. Reaction with oxygen
fort' 1'llJllbllstion is init iutt,(i. of Iht' air produces more hl'at with all incendiary
me!!tl thall with solid oxidizing compounds. The
5·4.2.2 Incendiary Compositions Ill'll' of thest' ('ompollllds, th('rt'fore, must be justi-
Most of t ht, l't'SI'llfCh Oil ill' ~ ~ltiiarie!l has betH fied by an inl'rt'ase in eil'eetivem'ss due to the high-
('uueel"lH'd wit h qualltity IIlId ty. ,e of combUistibl1' Pr ratt' of ht'at rl'kase.
Ulwd I:IS all illct'IHlial"Y fill(':,. llH,t'lldialY filll'rs I'l:In Thel'mitl'-ty!)e incendiary mixtures are com-
bt' hasil~l!.lIy e1assifi('(1 in to til I"l'(' (,Il: t'gol"it's: IU('tal· post'd of approximat(' oxygt'll-balalll'ed mixtures
ba!iI'd illcf'ntiiuril's, liquid fu,'I·based ilH'l'n(liaries, of red!win~ and oxidizing agents. While there are

5-22
AMCP 706·185

OTATING BAND, COPPER OR GILDING METAL

STARTER MIXTURE
STEEL ADAPTER IM-136

ALUMINUM ALLOY ANVIL

ALUMINUM ALLOY

RMOR- PIERCING STEEL BODY

TOTAL WEIGHT: 1700 GRAINS

Figure 5-9. Typical 20 mm Armor-Piercing Incendiary Bullet

a largf' number of possible combinatiuns which 2AI + 3FeO - Al 2 0 a + 3Fe + ~H


('ontain olle or more rf'ducing agents with one or
and givps the stoichiometrical rati.o of one part of
more oxidizing agents; aluminum (,rable 5-1) and,
aluminum to four parts of ferrous oxide. Since
to a lesser e1l:tent, magnesium (Table 5-8) have iron oxide scalp (hammer scale) is a mi1l:ture of
bf'en the only reduemg agf'nts used in thermite- ferrous and fprric oxide in various proportioIU!, the
type incendiary mixtures. stoichiometric amount of aluminum required to
Military thermite for incendiary purposes is rpact with the available oxygen present will also
t'omposf'd of 2.75 parts of iron oxidp scale and one vary.
part of granular aluminum. 20 Thp reaction: Tht' ferrous oxide, FeO, content of the hammer
8AI + 3I<'ea04 - 4AbOa + 9Fe + ~H sealp has Iittlf' f't!pct on either the burning time or
thp pPJwtration of the moltpn iron produced by the
r,ivrs tht' stoiehiometrical ratio of one part of alu-
thermitp rClwtion. A lower ferrous oxide ~ontent
minum to 3.2 parts of iron oxide, 1. . esO.. Ferric
producf's a considerably better flame and better
oxidr, Fe203, reacts as foliows:
propagation of burning; howrver, for values below
2AI + Fe20a - Al 2 0 3 + 2Fr-/- ~H 22 prrernt fprrous oxil1e, the improvement is slight.
and gives thr stoichiometrical ratio of one part of Thinllrr !iakr sealrs, such f.~ pipe scalf' and rod
aluminum to 2.96 parts of f",rrie oxior. I<"'errous seal(', have brPIl found to be more satisfactory than
oxidp, F('O, rpaets as follows: ('oarSt'r seales; however, thp use of a slight excess

5-23
Al4CP 706·185

GILDING METAL ROTATING BAND

$TEEL BASE COVER

SHELL
INCENDIARY CHARGE
(lM- II)
(lM-142)

TOTAL WEIGHT I 1600 GRAINS (APPROX,)

Figure 5·10. Typical 20mm High Explosive Incendiary Projectile

of aluminum minimizes ttl{' effect of particle shape haw been tried without appreciable success. The
of the hamuH'T scale. cl)mpositions uf some of the incendiary mixtures
The nse of low-purity aluminum (H2.5 per- tried are /liven in Table 5-9.
('ent) requires a higher ratio of aluminum to ham-
mer scale (1 to 2.7 -2.H) to obtain optimum burning
(·haractt'ristics. The ust' of filll'-Illesb granular 5·4.2.2.2 J,iquid Fuel·Based Incendiaries
aluminum results in decreased burning timt's ap- Liquid fuel incendiaries depend entirely upon
proaching a mir.imUl'1 limit with decreas(! in par- the oxygen of the air for their combustion. The
ticle size. If the aluminum is too coarse, poor organie substance with the highest beat of com-
propagation. pOOl' flame, and a longt'r burning time bustion on a volume basis is anthracene with 11,900
I·esult. calories per milliliter. A wide variety of natu • .:: l
During World War I, binders such as sodium oils and waxes fall in the range of 8,500 to 9,200
silicatt', sulfur or celluloid wert' added in order to calories !WI' milliliter. For hydrocarbons, there is
rt'duce segregation of the thermite after loading; a definite relationship between the heats of comhllil-
however, til est' techni(IUeS Wf're only partially suc- tion and the hydrogen-carbon ratio as sht~wn in
ct·ssful. Therllli tt' has not bef'1I lIsed since World Table 5·10. The order of heat on a unit-volume
War [ for illcendiary applications. While the heat basis ill the inverse' of the' order of the hydrogen-
rf'il'ased by a thprmitl' mixture is sufficient to heat ear bon ratios, whilt' the position is rever'3ed on a
t!w products of reaction to arOl!IJd :moo°c, the unit-weight basis. While the hent evolutioli per
incendiary action is confined to a relatively small unit-volumt' of n-octane is comparatively low, its
arpa. In order to improvp tllf' illcC'IHiiary effective- h{'at evolution per unit-weight is wry high (11,-
Iiess, several other incendiary tom positions, in- 500 ealories per gram), being exceedeu only by
eluding sew'ral modifif'd thf'rmitp compositions, boron and bt'rylliura on this basis.

5-24
AMCP 706·185

TABLE 5·S wa»tt', but thi» rnetho(l was only fairly satisfactory.
HEAT OF REACTION OF THERMITE-TYPE llul'illg' World War II thi .. idt'a wa~; revived and,
MIXTURES CONTAINING MAGNESIUM uasl'd on d('vl'lopment work, 14 percent cotton
--------,- -,--- waste Haturated with H6 percent of a [iO/flO mixture
.11 ixtllrf II eat of reaction,
of I!lisolillt' alHi fuel oil wus tried as a por:sible fill-
cally
ing for in!'endiary bombs, but was diseontinued R:'1
Mg + Bb S 2 3 •.••••••••.••..•••••••• 507 nlO1'l' erfedi'\ t' fill('rs lk t~aIlH' a \I/liiable.
;)Mg + Ba(NOah ................. . 1,636
4Mg + BaSU 4 •.•••.•.•..••.••••••• 1,046 5·4.2.2.2.2 Solidified LiqUid Incendiaries
4Mg + CaS04 .................... . 1,529
Bpcaus(' of the high d('g~ee of dispersion and
:UI'Ig + F1'2()a ..................... . 1,O;W
flash burning of liquid ;nc'!udiaries,
COIISt'qlIPllt
4Mg -+- Fe30, ................ ' .... . 956
many substam'es hav!' been propose,l for solidify-
2l\Ig + }<'eS:! ...................... . 764
ing liquid ilwt'}l(iiaries. 'rhf's(' include :~1
Mg -+- PbO ....................... . 378
2Mg -+- PbO:! ..................... . 789 a. }<'atty aeid (h-rivatives
4Mg + Pb 3 0 4 . • . • • • . • • • • • • • . . . . • • • • 736 (1) Aluminum, sodium, zinc, and ammo-
5Mg + PbSl)" .................... . 1,054 nium salts
4Mg-+- MgS04 .................... . 1,661 (2) I ,('ad salts of hydroxy adds
2Mg -+- MIlO:! ..................... . 1,248 (:3) Sulfonated products
;)Mg+ 2KNOa .................... . 798 (-!) AmitIes
4Mg + KeIO" .................... . 2,442 (3) Fatty Reids per se
!)Mg + K2~hOH .................... . 1,870 «(j) Natural waxes
-!~rg -+- K 2 S0 4 . • . . • • . . . • • • • • • • • • • • • 1,916 (a) Nitrated
DIg -+- Na2S04 ................... . 1,060 ( b) Sulfonated
(e) Per s(!
(7) Anilidts
5·4.2.2.2.1 Liquid Incendiaries h. Polyhydroxy d('rivatives
I;iqui<i incendiaries sllch a» petroleum oils, ( 1) Glycol compounds: }<jsters of fatty acids
('arbon disulfide, wood-distillation product», and (2) Ethanolamine compounds
OtlH'f flammable liquids, weI''' tested during World (a) Esters of fatty acids
War I. Tht'sr matt-rial» all had the drawback of (b) ('ompounds of mono-. di-, and trio
('x('('ssi\'(' dispersion; to overeomp this, the liquids ethunolamine
\\'('1'1' absorb('() in SOIllP rnatrrial sueh as cotton (a) Glyerrol compounds

TABLE 5·9
MODIFIED THERMITE COMPOSITIONS
Constituents Composition, Percent

Calcium Sulfate
Therm-& Thl'rlil H-2 Therm 6·j-c Barytcs Thcrmifc Thermitc
._----
Iroll Oxide ~calt' 61 55.2 44 69.2
Aluminulll 22.8 25 25 25.3 40.9
Barium ~itrah' 15 19.5 29
Sulfur 0.90 2 1.0
Castor ()il 0,30 0.30 0.3
Barium Hulfat(' 15.3
Cal('iulll Hulfatl' 57,8

5·25
AMCP 706-185

TABLE 5-10
HEATS OF COMBUSTION AN'D HYDROGEN-CARBON
RA TIOS OF SELECTED FUELS

Hydrogen-
f{ ydrucarbon Carbon CaLories Calm'ies Dl3nsity,
Rati.o per ml per g g/u
,AntlllaCelH' 0.72 11,900 9,500 1.25
~aphthalen{' (J.HO 11,000 9,600 1.15
Toluene 1.14 il,800 10,200 0.866
~Iethy I('y(~ lolwXllllt' 2.00 H,600 11,100 0.769
1I-0dane 2.2:) H,lOO 11,500 0.706

(ll) Saponifil'd wg-rlable oil mixes a. Rubber (natural and synthetic)


(b) :'\itrated wgetable oils b. Aluminum salts of mil.:ed fatty acids and
(e) Vegetable oi Is per Sf' naphthenic acid
( -l) Polysaccbarid(, compounds (~. Polyacrylates
(II) LhC~OSt' anhydride
( h) Dextrins 5-4.2.2.2.2.1 Ruhber Thickeners
((.) Pectins
Tht' addition of thickners-'-e.g., smoked rub-
(5) (\'lIulose ('!-:it'rs
I)('r, cr!'pf' rubber, and latex-to gasoline produces
(a) Ethyl (·eIlulosf' (7 to 10 Iwrcent)
all incendiary filling resembling sticky rubber ce-
(1,1 Pulp
ment. I<'illings of this type are reasonably satis-
('. Hesillolls 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
eV<'r, rubber was in critically short supply and
(e) Damar
other thickf'ners had to be developed. Satisfactory
(d) East India fossil
thickent'rs ('an also be made with somt' synthetic
((') African fossil
rubbers.
(f) New Zealand fossil
(2) Synthetic: Saponified polyacrylates
5-4.2.2.2.2.2 Napalm Thickeners
d. I!ydroearboll derivative"
(1) Paraffin The napalm thickener finally adoptf'd consisted
(2) Synthetic rubber of a granular ba!'e aluminum soap of naphthenic,
(a) Natural rubber ol!'ie, and coconut fatty acids. The sodium soap
( 4) Salts of sulfonated pt'troleum fractions used for the pr!'~ipitatioll of the aluminum soap
(;}) Salts of naphthenie lH'id (~olltained 0.10 to 0.15 percent alpha-naphthol. Tht

!'. IlIor!{anic dpri;tatives recoml!l!'nded formula of thp organie aeids ufied in


(1) Orgallo-si\i('on compounds: Esters making till' napalm thiekeIler was:
(2) Bentonite Parts by weight
(3) Oil shale COCOIlut fatty acids f)O
Naphtht'nic add 25
()f thesp, only a f?w were eyer found praeti('al for
()It'ie acid 25
lIS(' in tliick('llillg iu('endiary liquids. The most SUl'-
('pssflll sllbstan('ps wt'rt': 'I'hp alumimun ('Ol1tellt of the finish(;d thickener

5-26
AMCP 706-185

TABLE 5-11
COMPOSITION OF 1M-TYPE INCENDIARY GELS
Code 1M 1M 1M
Type 1 Type ;] Type 3 F-1416 F-142,9 F-1431 F'-1457

Constituent Composition, Percent

Isobutyl methacrylate
polymer AE (1M) 5,0 5,0 2.0 3.0 3.0 3.0 3.0
Ste3rie aeid 3.0 1.0 4.0 3.0 4.5
(Fatty acids) 2.5 3.0
Naphthenia acid 2.5 3.0 3.0 1.0 0.5
Calcium oxiJe 2.0 3.1 4.0 3.5
Caustic soda (40% solution) 3.0 4.5
A.mmonium hydl.'oxide (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.R prrcent and the moisture napalm thickrner which may cause partial or com-
content from 0.4 to 0.8 percent. Varying the eom- plete breakdown of gels formed with gasoline or
position of napalm from the standard to 2 :1 :1 ratio oxidation of thr thickener, include excess water,
of COC0nut to oleic to naphthenic a~id indieated that lime, caustic soda; soaps of sodium, copper, lead,
the viscosity of the gel increased primarily with iron, manganese, and eobalt; powdered or sheet zinc
increm,ed oleic aeids and, to a lesser extent, with and lead; lead nitrate; rust preventatives contain-
increasrd eoconut al'id above normal composition. ing amines, al('ohols, and all acids. Tetraethyllead,
'rhe acid number of the coconut acid was found im- on the other hand, has no injurious effects.
portant. TrOll was an undesirahle impurity when The fundamental reactions may be expressed
found in the alum but not in the acid. Impurities in as follows (IIR denotes the mixture of fatty and
naphthenic acid) :

6NaOH + 4HR + AI 2 (S04la-", 2Al(OH) R2 + 3Na S04 + 4H 0


2 2

6NaOH + 2lIR + AI 2 (S04h -'" 2Al(0II)2R + 3Na2S04 + 2H 0 2

The soaps may hydrolyze:


Becausp of hydrolysis, AIR3 does not form, and
Al(OH) R~ + H~O -'" Al(On hR + HR fatty acid in t'xcess of that required remains as
Al(OH)2R + H~O --,> Al(OII)a + JIR such:

Three processes have becn used ~ucCf~ssful!y for


th!· mallufadllf{' of napalm. All art' hased 011 tlw 5-4.2.2.2.2.3 Methacrylate Thickeners
above t'<llIations, but the mechanical details for :-;atisfac1ory thickelH'd gasolille could be made
('ombining' tht' matl'rials differ. wht'll li>-20 prr<·t'nt isobutyl methacrylatp polymer
Napalm. while a satisfal'tory thickeller, is sus- (Dl) was addt'd. Some saiisfadory 1M gels are
ceptibh· tu oxidation by the atmosp:lert· and is slIlIImarized in Table 5-11.
hygrosl'opic, rt'sulting' ill a thickenl'd gasoline with IJOW tpllljlt'.·aturl' stability is favored by a low
poor characteristics. polymer eonte-lIt, tilt' liSP of polymer of low meth-

5-27
AMCP 706-185

TABLE 5-12
COMPOSITION OF PT INCENJHARY MIXTURES
Code PT-l PT-2 PT-3

Constituent Composition, Percent

Goop 49.0 30.0


Isobutyl methacrylate
polymer AE 3.0
Magnesium (coarse) 10.0 10.0 30.0
(50 riO Mg-AI alloy) 10.0
Sodium Nitrate 5.0 H.O 6.5
Gasoline ;30.0 44.0 37.5
Petroleum Oil Extract a.o
(Bright stock) 10.0
GH·S (Buna-S
synthetic rubber) 8.0 6.0
Sulfur monochloride (S2Cb) 0.2 (add) 0.2 (add)

Iwrylic acid coutent, a high soap (~ontent, a high troops. Becausr wilite phosphorus has a low com-
concentration of gelling agent, a low watf'r con- bustion trmperature, it is relatively ineffective
tent, and tht' liSP of gasoline which has a low ag-ainst any bnt thr most rasily ignitible targets.
aniline point. With a reasonably stable basic 'rhr alkali metals, esprcially sodium, have been
formula, the most important factors appear to be nsrd as ill(,(,lldillries but the results have not been
the nature of the gasoline and the strength and con- satisfactory.
('entl'ation of the gelling agent. High temperature
stability is favored by a high polymer content, a
5-4.2.3 Typical Incendiary Devit:es
high stearic acid content, and the use of con-
l'entrated solutions of the gelling agent, i.e, a low nit' prindpal military eharacteristic of an in-
water content. The presence of oxygenated solv('nts (,t'l\(liary d('vice is its ability to initiate combustion
destroys high temperature stability. of matt' rill I with which it comes in contact, and to
In order to increase the effectiVfmess of the in- provid(' the l'lIergy to maintain th~ (~ombustion
('('ndiary filling in starting fires in targets more pro{'{'SS anti assist in l'nlarging the area over which
difficult to ignite, a (~omplex filling wa.., develop(·d ('ombustioll takrs plaet'. This charaeteristic is
having as its main constituent "goop", a mixtu:~e l'allt'd firt' raising power. Oth('r military character-
of magnesium parti('lcs and asphalt. To this was isti('s covt'fing tat'tical uS(', provision of fire-fight-
addt'd gasoline, thiC'kened with 1M oxidizing agents ing dpterrents, and d('sign drtails are also speci-
and magnesium seraps. PT-1 composition, and the fied.
substitutt's PT-~ and PT-3, used syntheti(' rubber Tht' fOIll'-pound magllrsiulIl alloy bomb, shown
instl'ad of 1M and an alumimllll-lIIagnl'sium alloy in Figure 5-] 1, was tlst'd during World War II in
ill plael' of "goop' '. (Rep Tabll' 5-12.) trt'mt'ndolls quantitil's. Its hrxagonal !lhape adapted
it to ass('mbl, I dusters for shipping and loading
5·4.2.2.3 Other Incendiaries on phUlPS. A1"'r dropping from thl' planes tilt'
Phosphorus and its compounds havr bern lCled bombs wprt' st'parlltt'd from tht' (·lusters and widely
as an incrndiary against personnr) ancl readily- (lispl'rst'd ill ralldom mallllpr. The pxplosivt' charge
ignitible materials. Burning phosphorus produces ill thl' bast' w!.s t'xplodt'd by thr heat, providing It
sprious skill burns and tends to dpmoralize attlieked clt·t!·rrt'nt to fightinl!, th(' fire. Only a portion of

5-28
AlICP 706-185

'the bombs had the high explosive charge; the others


wt're constructed as shown in !t'igure 5-12.
A "fire bomb" using napalm-thickened gaso-
liIll' as the incendiary filling is illm.trated in Figure
5-13. An incendiary grenade, suitable either for
combat use or for destru(ltion of materiel, is
illustrated in Figure 5-14. It is loaded with a
ilHEET STEEL
thermate, &ond iH provided with an igniting charge, 'TAIL SFCTlON
sp('cified as first fire mixture. FIRING PIN - - - , ; "

FIRING PIN
5-5 DELAY COMPOSITIONS AND HEAT
POWDERS
Gasless pyrotechnic mixtures are used for pro-
ducing a controlled amount of heat and for time
delays in a Dumber of military applications. These
eompositions, which arc physical mixtures of cer-
tain metals with olle or more powdered oxidizing
agents, react at a predetermined rate when ignited
FIRST FIRE _ _./
by the application of heat or flame. 'I'heir com- MIXTURE
bustion is charae1erized by high reaction tempera- MAGNESIUM
ALLOY 80DY
tures and the formation of ll}ainly solid products,
Both the burning rate and calorific output can be
varied nver fairly wide ranges by controlling the
'"properties and proportions of the ingredients. THERMA.E
:·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
influencl>d by pressure; "gasless" compositions
are particularly valuable for use in armament,
e.g., in short delay bomb fuzes. IRON NOSE

5-5.1 PYROTECHNIC DELAYS


Some ordnance items are more effective if
functioning is delayed for an interval of ;,ime after
the initiatil!~ stimulus. While a variety of me· Figure 5-11. Four-Pound Magnesium Alloy Incendiary
80mb
chanical and electrical drvices 29 have been em-
ployed for this purpose, a time delay can be
obtained by incorporating a pyrote~hnic delay device consisting of an initiator, delay column,
rlement into an explosivr train. The time delay, and an output terminl\.l charge or relay; all as-
in this casp, deprnds on the length and rate of sembled into a specially designed inert housing.
hurnin~ of thr drlay (·omposition. Time delays
In some designs, one or mere of these components
('an also be obtained by controlling the rate of heat may be omitted. In some cases, depending on the
flow throllg'h a thermal barrier,30 or by the rupture application and delay composition, thr delay ele-
of a barrirr by the build-up of ~as pressure. 11l ment may also include baffies, a housing, and pro-
vision for an intern",l free volume. Based on their
5-5.1.1 Delay Elements l'onstnlction, pyrote,?hnic delays cali be subdivided
A delay plement is a self-contained pyrotechnic into two general types, obturated or vented.2e

5-29
AHCP 7OO·1SS

5-5.1.1.2 Vented DeIlY ElementrG,82


Ven ted delay elements have opwing!j through
which the gases procuced by the fUllctioning may
escape. Venit,;d delays arp used when large quau-
tities of gas ai.·€: produced by the burning of the
SHEET STEEL
delay powder and may even be necessary for" gas-
FIRING PIN - - . - - - - " " TAil SECTION less" mixtures when long delay times are required
in order to t'liminate pressure bn~ldup within the
delay elem(>nt. Venting exposes the burnin~ delay
composition to ambient, pressure. All a conse-
quence, the burning rate of the delay mixture is sen-
SAFETY
PLUNGER sitive to ('hanges in altitude. In addition, these
PRIMER-----'
vents requirf' sealing up to the time of functioning'
in order to protect the delay composition from
humidity. Two methods for sealing vented delays
are iIlustratf'd in Figure 5-16.
~_MAGNESIUM Another vented debty is the time ring which
ALLOY BODY
consists, as shown in Figure 5-17, of a column of
fuze powder which is pressed into the fuze cavity.
Because of its ('onstruction, the ring delay occu-
lHERMATE----"
pies a large part of the total fuze volume. With a
ring delay the deIay timt: ean he set to any desired
DELAY ==-__-" value within its time i'angt' by rotating a calibratJd
DETONATOR
ring which vades the lengt.h of the delay train that
must bt' bllrllpd bpfor~ th~ terminal charge func-
tions.

IRON NOSE
5-5.1.2 Delay CompoSl'D.ons
The delay componitious, being a critical part
of the delay element, should ideally have certain
Figure 5-12. Four-PoL.nd Thermite Incendiary Bomb charaett'ristics which may be summarized a.."! fol-
lows:
5-5.1.1.1 Obturated Delay Elements a. The ingredients should he &table and non-
An obturated delay element, as shown in Figure hygroscopic; shoultl 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 of the initiator and delay able and inexpensive; and should be rompatible
composition before the functioning of the terminal with each other.
eharge. Delays ill which the gases pruduced are b. Thf' compositions should be capable of being
internally vented into a closed chamber ill the eX- blended, loaded, and assembled into an item with
plosive device arf' considel'ed to bt> obturated. minimum risk from impact, friction, moisture, heat,
Becaust· they are st>alt·d, obturated delays are Bot and pleetrical dis(·harge.
influenced by the effeets of tht' ambient pressure t'. ThpY should be readily ignitible, Ilnd should
Of humidity. Th ... eombustion products art' (~OJl­ I'hang'r litt 1(' in Jlrrformanee eharactC'risties wit.h
tained which prcvents possible harm to othH com- small l'hallg('f; iu pt'rt'entages of ingrpdients. Their
por mts of the deviee. Short time dplays 11ft' o"ten burning ratp" shoulli be rt'produl'ible within each
obturatt·c IlS obturation tpBds to iucrellse tht' avel'· bateh Ilntl from hatch to blltl'h with It minimum
age burning rate of th!' dl'IIlY ('ompositioll. of variation.

5-30
,--------------------------------------------------------------------- -------------------------------------~

AMCP 706·185

This page is reproduced at the


back of the report by a different
reproduction method to prOVide
better detail.
Figure 5-13. Typical Napaim 80rrb

d. Tht'y shouid bl' cnmpatibll' with their eOI1- \lted largely to its good dry surveillance character-
tainl'r as wl'll as with other contading composi- istics, its ('ase of ignition, its wide availability in
tions. Performatl{'(' characteristics should not reprocitwible quality and granulation, its e8.&e of
chang(' appr('ciably with long term storage. loading, and its versatility from the standpoint of
P. They should be !"platively insensitivE' to delay times obtair..able.
changes ill pressurt' and t('mperature. As already indicated, black powder produces
f. They should bp l'apabl(' of withstanding thl' gases on burning, and the burning rate is affected
\'ihratioll and shot·k of transportation, setback, ro- by pressure. Hf'nce, the disposition of the gases is
tation, and impad, aud should be r('sistant to a primllry cOllsidrration in design; delay elements
physieul ahus!' illlwrPllt in tht' loadin~. and firing IIsing bla('k powder are g('Il('rally vented. The
of aml!llluitioll. hurnil1~ ratt' of black powner is affected by the ro-
ta tional spped of the projectile and by the ambient
5-5.1.2.1 Black Powder Delays PI'I'SSlirt'. A major shorteoming of black pow de!"

Blaek powder has bpI'1! 101l1{ and widely used has b{,PI1 and still is its marked hygroscopicity.
as Ii delay Ill/ttt'rial in Hpit!' of t hI' fad that it dot·s As has bet'n in<iil'att'd t'arl;t'r, bt>eaust' of these un-
not IIH'l't !lUlU), of tht' idt'al ('haructt'ristil's for a df''iir1tbles, I!llsh>ss ti('lay l'ompositiollS wert' de-
dplay ('om positioll. This pOJlularity may bl' uttrih- ,"!'Iopt'd.

5-31
AMCP 706·185

Y.X:<>6I~ PRIMER HOI..D£R

Figure 5·J5. Obturated Delay Element


Figure 5·J4. Typic," Incendiary Grenade
5-5.1.3 Factors Affecting P"rformanceB8
5·5.1.2.2 Typical Gasless Compositions Thp pl'opagative burning of a pressed column
Th" gasless pyroteehdc mixtures which have of a gaslpss delay composition is a combustion re-
been rp8sonably satisfu('!'Jry for delays aI"f~ given action in which the fuel and oxidizer react to give
in Tabl!' ;)-13. Different buruing rates can be ob· psst'ntially solid products. 'I'hp gases formed con-
tainNi by 'wlpcting a sppeific composition or by sist mainly of hydrogen, watpr, nitrogen, carbon
yarying thp proportions of illflrpdients in a com- mOl1oxidp, carbon dioxide, and traces of organic
position. matt'rials.=17 These gaseous products are produced
TllP burning ratps obtaillPd with these COIll- as a result of thp presence of impurities or for
positions art' given in Tablr 5-14. lTlHlpr eontrolled othpr rt'asons not directly related to the primary
laboratory ('onditiolls, the eOt'ffieirnt of variatiou reuetion. The observed vplocities of thp reaction
of most of the ('~mpositioJls listed is thrt'(' percpnt haw bpt'JI justifipd; however, quantitative agree-
or h·ss. Lot-to-lot variability may bp compensated ment was plirply on tht' basis of thennal flow. B8 •Be
by adjusting the length of thp dplay culumn for QlIl'Stiow; have beel' raised concerning the de-
eaeh upw lot of dt'lay composition or by adding tails of burning of gil..'!lpss delay compositions.
appropriait' ingrpdipnts and rpmixing to speed up I<'or SOUle ('ompositions, there is evidence that t.he
'Jr slow down tht' mixtllrp. Variation may be con- formatioll of a gaseous phase plays un important
trollt'd by ust' of standardiz('d raw materials and part ill tht' o\'t'rall rpal'tioll mechanism while con-
prt'paratioll pro~,pdures. (}('lISt,d phast' rpactions arp important in th(' pre-

5-32
- - - - - - - - - - - - --------------
AMCP 706-185

PRIMER

SOLDER
G
'~~r~~~_METAL
~ SPOOL SOLDERED
IN PLACE

OUNTER-
BORE

METHOD A METHOD B
Figure 5-16, Seflling of Vented Delay Element

ignition rearti()ns,:lil.40.41.4~.43 DT A and TO A 5·5.1.3.1 Composition


studies of the ingredients in bariuIIl t'hromate- Theri' arr a large number of exothermal reac-
boron delay cOIllpositions do not, however, indicate tions betwl'en inorganic solids which yield little or
th~ formation of a gaseous phase bdore ignition no gaseous product~. However, most of the reac-
of tIl(' composition,H and that a gaseous phase may tions art' not satisfactory for one or more of the
nut bE' important, at h'ast in thifl particular rE'ac- following rt'asons:
iioll. a. Erratic burning rates
In some rast's thl' effectiveness< of an explosive b. La:cge ('olumn diameter required for reliable
traill depends gl'patly on the accuracy of t.hf; time propagation
delay prorluprd by thr burning of a dE'lay column, ('. Largp temprrature co~ffi.cicnt of burning rate
W}-,ih' it is possible under controlled laboratory d. Failure at low trmperatures
l'ollditions to obtain coeffieients of variation (Para- p. Hygroscopicity

graph 5-S. 1.2.2). less than three prrcent for many f. Hapid dpterioratioll
df'lay mixturrs, thE' effect of ambient condition;; g. Unavailability of reproducible supply of raw
and llHmufllrturing variation in many casE'S is materials
sOlllrwhat Ips+; than drsirablr. l<"'acto1'S whieh may h. LargE' pressure coefficient of burning rate
infllH'Ill'p thl' al'curacy I)f a gaslE'fls pyrotrchnil' I. Failure at low pressure

ilJl'lude: Rl'a(,tions which wert' studied are summarized


a. CompositiolJ alld Quantity of Charge in Tabh· G-15.~4 !Tnder the standardized conditions
/). Ex tprnal Prpssnre for tlirse t('stl-., it wafl found that for each oxidiz-
l'. Extl'rnal Tt'llll)('ratur(' ing agent uSt'd, vcry fast burninr, times were ob-
d. Tl'rminal Chargl' tain('d with magllt'sium, aluminum, zirconium, and
t' Partielt' Sizt' titanilll,l. Slower burning times wt're obtained with
f. Ignition silicon, mangallPSP, and chromiulll; while still slow-
~. ( 'olumn l>iamt·trr ('1' ones oeenrrl'd with iron, tungsten, and Gthers.
h. I,oadillg Pressure ~1('tltls whil'h gaY!' fast hurning times with silver
I. Housing' :\1atrria I oxi<l". sil\'er ('hromate. barium pE'roxide, and lead
.1. Acet'lt'ra I ion l'hromate ga\'(' slow('r burning timcs with cuprous
k ~tol'a~-rl' ()xi<l(" har'iulIl ('hromatt" and iron oxide.
I. Prol'pssi Ilg' Thl' variation ill burning' rate for thl' barium

5-33
AMCP 706-185

TABLE 5-13
GASLESS DELAY COMPOSITIONS IN CURRENT USE33,34,35,M,Gl

Fuel, % Oxidants, % Inert, %

Mangan!:'se Barium Chromate Lead Chromate None


:30 to 45 o 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-Zirconiu Barium Chromate Potassium Pprehlorate None


Alloy 26 60 14

N ickel-Zirconi urn Barium Chromate Potas~ium Perchlorate None


Mix
5/31 22 42
5/17 70 8

Tungsten Barium Chromat!:' Potassium Perchlorate Diatolilaceous !:'arth


27 to 39 59 to 46 !Uj 5 to 12
;j9 to 87 46 to 5 4.8 :{ to 10
20 to 50 70 to 4U 10

Molybd!:,lIum Barium Chromate Potassium Pt'rchloratt'


20 to 30 70 to 60 10

Silicon Diatomaceous t'arth


20 Max R parts
by weight
Zirc'oniulll Lead Dioxide
28 72

l'hromatp-boroll system as the p!:'rct'utage of boron ;)·1 H,S:l illtlit'atps that t'ompositiOl!" with less than
in the composition was increased to 50 percent is 11 J)!:'rt"~llt boron burn slower than those contain-
summarized in TablE' 5_16.:\3 As indicl',ted by thl' iug lIIort' than 13 perct'nt boron when the amount
,lata prt'M'ntt'd in this tablt" a sharp drop in hurn· of ht'at ('v(I!Vt'd is Ow samt' ,
iug' timt' is nbtained initially as the percentage of
boron is in('rt'as('tl. At approximu tely 1 () percellt 5-5.1.3.2 External Pressure
boron, tllP burning' rat<' It,\'t'ls nff and remains Jj{'ar-
As shown ill }o'igllrt' [i-I!l for a 95.4% barium
Iy ('tlIlstant to a;lproxilllatt'1y 2fi Ilt'J'('t'!It boroll.
l'hrOlllat.'··tu~'{, borun ('olllpositioll, an iIlt'rease in
wht'n it bpg'ills to tit'('rpast' qllite rapidl)', 'l'ht,
tht' "Xlt'I'Jlal Prt'SSIlI't' rt'stlited ill H dt'cl'ellse ill
Iwat of r('a('t iOIl reat' ht's Il lIlax i III UIIl II t ap pruxi,
bllrllillf! tilllt·s (an illl'rt'aSI' in burning ratt·). 'I'hl'
lIlatp\y 13 pt'rl','nt buron, wllieh is a sOlllt'what \owi'r
pl'rt't'lIta~t' thalJ that l'olJlpositioll (In pefl'l'ntl
rt'l,ltiollship is hypt'l'bolil' and ':!l1l ue rt'pl'i'St'ntN!
by Ull t'q Ililt iOIl "I' t)ll' form:
produl'illg' the m!lXilllllU; hurniJl~ rll!t', A plot of
total heat p\'ol\'l'd against bumiu!! timcj;, l"igun' (5.11 )
AKCP 706-185

TABLE 5-14
BURNING RATES OF GASLESS DELAY COMPOSITIONS83-36.Cil.112

InverF'! Burning Rate,


Composition sec/in.

BaCrO./B (amorphous) u.5-3.5


95/5 1.5
90/10 0.6
BaCrO./B (crystalline) 9-12.5
BaCrO~!KCI04/Zr-Ni(70-30) /Zr-Ni (30-70) 3-11
60/14/9 (70-30) /17 (30-70) 6
60/14/3(70-30) /23(30-70) 11
BaCrO./PbCrO./Mn 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
Zr /Ni/BaCrO./KC10 4
5/31/42/22 6.5
5/17/70/8 17.5
BaO:?/Se/Talc
84/16/0.5 added 2.3 (approx)
PbO:?/Zr
28/72 < 0.5
ilaCrO:!/ Cr 2 03/ B 4.5-8.5
44/41/15 4.5 (approx)
44/42/14 6.5 (approx)
BaCr04/KCIO./ W
40/10/50 12.5 (approx)
tiOi 10 j30 31 (approx)
32/5/5H 1
41/5/49 10
58/10/27 40

\\'it"I"" t is Iii,· bllt'lliut-{ tilllP ill s,·,·ollds. !I is pn's- slig'htly with ill('I'('asitl': pn'sslIrl' abovl' atmosplH'r-
stII·" ill pOllllds ""!" sqUIlI'I' illl·}I. and It /lnd /I urt' i('. H"slt!ts with mixtur,·s whidl ('ontl1illl'd mall-
'·Oll~taills. ':',.0' lIUI/II·t·i"1I1 \'llilh'S of tlI,· t'()lIstllllis g'allt's,·, I.. obalt allt! /I lli"k"I-zir"onillJll lIlixturt' as
an' II O.I:l alit! (/ ~.;I:.! for Ih,' !l;).-I '-I.li bariulll tilt' fllt'l illdit'at!'d that /I ,·hung'!' in ('ompositioll
..iII"Olila t I·-ItO 1"0 II i 'll! Jllltlsi I io II. It!' liJ,· atmosph"!"t· did 1I0t ha\'(' a sig'llifh'lIlIt I'fi'rct
:\iI si),!llitkHIlI dllillt-{'· :1,; fOUlld, s,·,· l<'ig-ure 1111 tilt' bUl"lIinl-! ,.at,·,~~
:'-l~l, ill tilt' hurlling lilllt'" 101" /I !I0I10 Hllil AIIl!1
h/l I'i\l III ,·ht·O!iJllti·-IHII"OIl i'illllposil iOIl for I'r"ssllrt's 5-5.1.3..3 External Temperature
'''~:i thllll IItllw"ph'·l"ii·. .\" slww/I ill Fit-{ul" 'i-:!{), tht' humin!! times for
H,'sld!" "htain!'d with uth"1" d,·III." lJIixtlll",'S IIlso di·lay "ollll'osilioIlS W,'\"i' fOJllld til d",·rt·lIs,· with
illtllt"atl'ti that thi' bUrJlillg 1"111,' wO\lld illi'rt'lIs,' illl'J't"I~illg' t'·llIpi·ratlll',·. !·'Ol' ~'0I10 hariuIlI ,·hro
• 2 rOI,ludK !tot ijCoited. lIIall,-bol"lIn, a 1'101 of hllrnillt-{ I'att· IIgainst thp
AMCP 706·185

TABLE 5·15
HEATS OF REACTION OF INORGANIC MIXTURES
CONSIDERED FOR DELAYS

Mdalo
I Silter (lride Si:", Chromllte Barium Peroride Lead Chromate Cur;ou. O.id. Barium CAl'OIIIGle Iron O:tid.
-t;.H' -t;.W/n -t;.UO -t;.W/n -t;.H" -t;.H'/n -6.H' -t;.I1'/n -t;. , -t;.8"/n -t;.H' -t;.Wh -t;.H' -t;.I1'/
-~-----. -6Fo.5
- - 68.9(1)
.-- ---~~~-.
- - - - - - - - - - - - - - - - - - ----
MAG:'>ESIUM 139.1 69.6(1) 126.7 63.4(1) 660.7 56.1(1) 103.6 51.8(~) :192.9 48.81~ 239.8 40.0
AL UMINUM 378.0 6~.0 1869.0 62.3 340.8 56.8(1) 148&.6 49.5 271.5 45.3 253.6 42.3 ) 200.5 33.4
ZIRCONIUM 244.1 61.0 1206.5 60.3 219.7 M.9(1) 950.9 47.5 173.1 43.3 481.5 40.3 377.3 31.4
fITANIUM 211.0 52.S 1(:'41.0 52.1 186.2 46.6(1) 785.4 39.3(5) 140.0 3S.a 384.2 32.0 278.0 23.2
S ILCON 187.0 46.8 921 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)
M ANGANESE 89.5 44.S 440.5 44.1 77.1 38.6(4) 312.7 31.3 54.0 21.0(10) lH.1 24.0(23) 91.0 lA.2(N)
C HROMIUM 262 42.0(N) 1239 41.3(N) 214.8 35.8(5) 855.6 28.5 145.5 24.3 63.8 21.3 14.5 12.4
ZINC 76.5 383 374.5 37.5 63.9 ~2.0 247.7 24.S 41.0 20.5 104.6 17.4 52.0 8.7
T IN 124.1 31.0 606.5 30.3 99.3 24.8 350.9 17.5 53.1 13.3 123.6 10.3 17.3 1.4
I RON 177.5 29.6(8) 865.5 28.9(8) 140.3 23.4 483.1 16.1(11) 71.0 11.8(N) 53.1 8.9(N) 0 0
CADMIUM 58.2 29.1 284 28.4 45.8 22.9 1116.2 15.6 22.7 11.4 50.2 8.4 -2.9 -ll.5
T UNGSTEN i74.7 29.1 852.5 .8.4 137.5 22.9 469.1 15.6 68.2 11.4 50.3 8.4
M
.OLYBDENUM 155.5 25.9 759 25.2 118.3 19.7 313.1 12.4(17) 49.0 3.2 31.1 5.2
N ICKEL 50.5 25.3 250.0 25.0 39.0 19.5 122.2 12.2 15.9 8.0 29.d 5.0
COBALT 51.4 25.7 245.5 24.e 38.1 19.1 117.7 11.8 15.0 7.5 27.1 4.5
ANTIMONY 145 2t.2 704.0 23.5(10) 107.8 18.0(6) 320.6 10.7 38.5 6.4 20.6 3.4
8 ISMUTH 116.1 19.4 544.0 18.1 78.9 13.2 176.1 6.9 d.6 1.6 -8.3 -1.4
COPPER 3\.5 15.8 150.5 15.1 10.4 8.2 22.7 2.3 -29.9 -5.0
N ONMETALS
PHOSPHORUS 195 39(1) 192.4 38.5(1) 487 ~ 48.8(1) 128.4 25.7(2) 21a 21.3 552.8 18.4(6) 35.3 ,.1(15)
S ULFUR 142.1 23.7 682.5 22.8(4) 158.2 26.4(4) 101.2 16.9(9) 95.9 4.8 28.5 4.8 -15.1 -ll.5
S ELENIUM 67.9 11.3 311.5 10.4
I
80.6 14.4 31.3 5.2
I -6.2 -ll.3

-t;.H" HEAT OF RUCTION.


-.6.H'/o EQUIVALENT m;AT OF REACTION (HEAT OF REACTION PER ELECTRON CHARGE).
(N) NO REACTION OBSERVED.
(I) VERY F~.sT BURNING RATE.
() BURNING TIME, SECONDS

IOA'arithm of the absolutr tempel'aturp results in a The magnitude of this reduction iTI burning time
straig'ht linf'. For tht' Hii.4 / 4.6 compositions, thi.s for several· barium chromate-boron compositions
is also trur for most of tht' temperature range; is a function of the burning rate of the eomposi-
howeW'l', for SOIllf' 9:),4/4.6 compositions, thert' is tion. (~ee Table 5-17.) As shown in Table 5-18 th~
a departure from this type of relationship at the reduction ill burnmg rate is less for the more
low<:'r temperaturrs. Over the narrower tempera- rapid burning t'omposit:ons. Obt.uration of the
turt' range (_600~' to 160°F), the burning rate is delay column substantially increases the magni-
('s~,~nti&lIy it lin('ar fll11ction of th(' 10glO tempera- tude of the anticiDatory effect. The anticipatory
ture. effed is reduced by barriers, between t.he delay
column and the thermally-sensitive terminal
5·5.1.3.4 Terminal Charge, Anticipatory Effect46 ehargp, which wo,11d reduce the flow of gases. The
The burning eharacteristics of pressed delay importance of gas permeation in the burning of
cOIn positions are different wheH loaded above a pressf'd delay eOJr.positions is indicated.
thermally-sensitive terminal charge. The overall
burning' time and the reprodllcibilit.;}' are buth de- 5-5.1.3.5 Particle Size
erea."ed under these conditions. This anticipatory 'l'he effect of particle size on the inverse burn-
pfl'ect has been observed with a variety of thermal- ing rates of delay compositions follow a nearly
ly-sensitiw terminal ('harge;; fOJ> both gaseous and direet proportionality. In addition to increasing
IlIl11gaSf'OllS cit'lay ('ompositiolls. Th(' ~ft\~ct. has also tht' burning rate, reduction of the particle sizE'
been observrd for typical end item delay ('lp~.lents tE'nds to reduee the effect.s of temper.ature and
hn "ing a Ipad styphnatt'-l('aci azidl' rrlay. pressurE'. This effect is shown to a marked degree
Til(> ('xtellt uf the reduction in bUnJin~ timf' by tungsten dE'lay ('ompositions, as is shown in
that O('('UI'S with dt'lay elements having thermally- Table 5-HI. Although th,> pereentage compositiollA
"ipnsitiw Terminal (.'harges, t'omparerl WIth ·.imilarly art' not idrnti('al. th<,y are close enough that little
IH'esfwd <ida)' eollImlls without a terminal (~harg'e, diffprE'l1l't> ill burning time would bp observed if t.he
&pproa<'llt'!> a l'onS~allt "alue aE the length of tilt' tUJl~st(,1l fUt·1 harl th£' Slunt' surfa/'e area. The
dpiay eolu:illl 'ibov!' th('('l'rminal charge illereases. w('ight, avt'ragE' diamE'tt'r, and thE' surface area

5·36
---------------- ------------------------

AMCP 706·185

TABLE 5·16
EFFECT OF PERCENT COMPOSITION ON BURNING TIME,
HEAT OF REACTION, AND IMPACT VALUES
OF THE BARIUM CHROMATE·BORON SYSTEM

No. I I Heat <1 Reaction I


I
1

Charge
WI,
Results
Allg and
Range I
Avg
Burning
Tim~,
II Range,
R.....
sec/sec
- - - - - - Total
Volume Cal in
gas Loaded
Impact
Test
PA,
% Boron mg Based on sec
Cal/sec inches 1 sec B.T. Cal/(J ml/g Fuze
----. --------1----1---·- -----1----1----- ---. -.--1---1-----
3.0c;; 2130 5 7.56 0.469 0.620 Incomplete reaction 40+
3.5%
4.0%
2150
2140
4
4
3.04
1. 72
0.070
0.031
0.020
0.018
278
354
5.0
5.0
I· 597
768
161l
446
40+
40+
4.5% 2125 5 1.44 0.040 0.028 400 4.0 850 590 39
5.0%
6.0%
2130
2110 I,
5 1.09
0.767
0.653
0.035
0.021
0.010
0.032
0.027
420
231
8.0
8.4
895
909
821
1186
1387
40+
37
38
7.0% 2000 4 0.016 453 6.4 906
8.0% 2000 4 0.560 0.001 0.002 462 7.9 924 1650 28
9.0% 2000 4 0.539 0.002 0.004 474 7.5 948 1758 29
10.0% 1975 <1 0.465 0.01.') 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% 19()Q 4 0.397 0.006 0.015 1)56 8.9 1056 2661 20
15.0% 1875 4 0.382 0.027 0,(171 551 7.0 103a 2704 16
17.0% 1800 4 0.375 1 0.027 0.072 043 11.6 977 2606 13
19.0% 1750 4 0.366 0.021 0.057 535 8.8 936 2558 16
21.0% 1685 4 0.376 0.007 0.019 526 8.6 881) 2363 34
23.0% 1650 4 0.407 0.0?.3 0.057 503 4.2 830 2703 40
25.0% 1625 4 0.433 0.025 0.058 497 10.2 808 1865 40+
30.0% 1611 4 0 . .')7<1 0.025 0.044 473 lOA 762 1328 40+
35.0% 1500 4 0.965 0.115 0.119 446 12.7 669 693 40+
40.0% 1430 4 2 19 0.110 0.050 399 14.1 571 261 40+
'15.0% 1360 3 5.25· 0.210 0.040 364 15.0 495 94 40+
5O.0o/~
I 1290 2 14.5* I 1.000 0.069 Incomplete reaction 40+

·2 rouads no~ ignited

were determined on thp micromerograph. Under ehal'ge of an igniter composition on top of 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 bu.-ning ablr, in minimum quantities, of igniting the delay
time of about one-fifth oi the former. column. The ('omplex interactions between initiat-
For the 90/10 barium chromate-boron composi- ing source and igniter and, in turn, igniter and
tion, thr use of boron of 1, 13.5, and 53 micron main (~harge are yet to be determined. For the
average Jlar~i('le size resulted in an increase ill the most part, igniters have been and still are selected
inverse burning rate of 0.45, 6.61 and 9.53 sc-!onds on an arbitrary basis. Compositions of some of
per inch, respectively. Similar rrsuits werp ob· the ignition powders which have proved relatively
served for manganese delays.35 satisfactory are given in Table 5··20. These mix-
In addition to the ave"'I.ge partide size, t.he tures are also gasless
particle sizr distribution and blrnding or deiay
mixturrs is important if rrpt'oducible butl,iug 5·5.1.3.7 Column D~meter
fatrs arp to bp obtaine rl,f7 r'o)' the barium cltro- Radial 10sS€fl of heat can retard or extlllguish
mate-boron eomposition, the-e a)1nears to be little thr reaction in a delay eoluffin. Such losses be-
diift'rcncc [)rtween delay mixture~ produce() by eOllle more serious as thr column diameter, bunl-
wrt and dry blendiHg methodF. Wet ble'lding is ing rate, and flmhient tprnperature are reduced.
prerl'rrl'd for safety reasons. Thrt-Op effpcts com biLe to result in a failure diam·
t'ter associated with a giWll celllY mix for a given
5·5.1.3.6 Ignition Compositions lUllbiellt eonditioll. J<'or mangauesl' delay compo-
ROIIIP gasless ()play eompositions arf' diffit'ult sitions Ht -C!'°F tl. ... fnilm·c diHnH't('r for a three-
til igl•. te. It is th' usual pr ..ctice tc pn'ss a small st'('ond )h'f ilH'h composition if.; less than 0.109 illl'h;

5-37
AMCP 706·185

TABLE 5·17
EXTENT OF ANTICIPATORY EFFECT AS A FUNCTION OF
BURNING RATE OF VARIOUS BARIUM CHROll(ATE-BORON

Average Burning Time, msec


95/5 90/10 86/14

Delay composition alone 464 167 132


Delay composition above terminally
pressed IOO-mg incrernent of 81-98 ~ 158 124 116
Burning' time reduction, msec :~06 43 16

81·98 squibs were empolycd for initiation of columns. Oomposition loaded in M112 fuze
housings at 36,000 psi.
81·98 Composition:
MoOs-26%
KCl0 4-21%
Zr-53%

II COMPOSITIC'-N CON1A1NING 11% 8 AND BELDW.


6.4 • COMPOSITION CONTAINING "'II. aAND OVER.

VENT -~;ff::,F''$>~~~:----- VENT


1... STAB PRIIIIIER AND
9L"-CK POWDER
'"z
0
0
<> 4.8
'.6

'"
N
STARTING CHARG£:
'"
II>

.,; 4.0
2
;:: 3.2

'"iiz 2.4

~ELT WASHERS
'"
:::>
III 1.6

0.8
ILACiC I'OWIlf:R
~,,*~-~t--IOOSTER (LOOSE
LOADED)
1000 900 800 100
CALDRIES

Figure 5-18. Total Heat Evolved Versus Burning Time of


Binary Barium Chromate-Boron Compositions Loaded to a
Height of 0.79 Inch in ,4.11 _ Fuzl.. .lousing at 36,000 psi

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


and 0.156 inch, whilp for II. 12.5-sccond per inch
compositiolJ, tllP failure diameter is between 0.156
and 0.203 inch. As shown in Table 5-21, the effect
of columll diameter was found to be significant for
all fJ5/5 barium chromate-boron delay systems and
for obtmated 90/10 barium (·hromate-boron de-
lays.4~
SfCTICN ".-x

Delay Type Rllt10r T,out; V.nt.d, W"lao\J' BalO•. 5-5.1.3.8 Loading Pressure
Tllrt,: S.'.eI;"•. r 10 21 »C'01l0 •.
Loading'
Upper R,.,,·-1.18S G/O"",
Burtling' ratt'S of delay mixtures will decrease
Low., R,n, - 3.6"0 G,O"'5. as thc ('onsolidation pressure increases. The rather
A-l Blae" Powd.', Lo",rJ.(/ '" Piau ,,, S,n,l. Incr.m.n, of 68.000 pli.
~lIlaIl and systematic (·hanges with loading pres-

Figure 5-1'. Time Delay Ring or Train, Vented sun' for bariulll dlromate-borou composition are

5·38
--- ----- -- -----------------------------~------------
-------------------------

AMCP 706·185

TABLE 5·18
EXTENT OF ANTICIPATORY EFFECT AS A I<'UNCTION OF
COLUMN LENGTH 55/35/10 TUNGSTEN·BARIUM CHROMATE·
POTASSIUM CHROMATE COMPOSITION.

Average B'urn,i,ng
B1trning T~'me Length of
Time,··· RanJe, Percent ~ Burning ~/v Oolumn Oolman
mseo msec Range Time By-passed By-passed, 1:n.

One 1000-mg increment


Without terminal charge 2348 411 18
With terminal charge" 1473 462 ~n 875 37 0.07

Two IOOO-mg increments


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

Three lOOO-mg increments


Without terminal charge 6082 328 5 15
With terminal charge 5192 ]042 2u 890 O.OS-

Four S60-mg increments


Without terminal charge 6914 33'7 5
With terminal charge 6173 990 16 741 11 0.08

• Sl-98 squibs were employed for initiation of columns. The cOll1poMitioJ\~ was leaded i.n
M1l2 fuze hO'lsings at 36,000 psi.
** Sl·98 terminal charges were used .
•• * Average burning time values have been reduced by 6 Illsce in order to take into ac·
coun~ the burning time of the terminal eharge itself.

summarized in 'rable 5_22.40 These effects mi~ht


be used to !~')mpensate for the differences in burn-
ing rate from lot to lot. However, this metho~L has
not been uspd dul' to the established praetiee of
120
loadlu/r delays at pressures iJetween 30,000 and
-10,000 psi ill order to withst;'lnd the forces to
100 --~-------,-~ whieh it is subjected in use. Yielding of the delay
0.80
• 954% BaC''lo-4t% 6" DP· 4U6 plemeut while pressing tht' delay cOnlp().§ition will
.. 954% BaC,Q,~' 4 6;1" 8 - OP'-409
• 9!t .• "., BoCtO,,-4.6'4 8- DP-480 eaust' erratic delay time!1.
• 90% 80C,04- 10% B - D?-419
060 .. 81 % BaC"lo- 19'11. 8 .. OP-602

040~==========~============-c-:=-=-- 5-5.1.3.9 Housinl~ Material


ro •
ozo The body intu whi~'h It delay composition is
.J....-..--J,..._.~ ____ _l_~~ ___ ~~ _____ ••• _ _ .
loadl'd sent's u:; a h('ut sink, as mt't.als in general
000
10 20 '0 40 ~o 60 70 80 ar(' mW'h better conductors of heat than delny
em.
(~ompositiohs, ) .>ela)· eoJulUlls clost' to their low-
PAESSURl. MERCURY

tellJ[wrature fad\ll'c diameters t(,lll1 to have larger


tf'lIlpt'ral un' ('OPfticients as t.he surrounding wall
Figure 5-19. Burning Time uf M112 fuze Ver.us External
Pressure tltiekness i.~ iUJreased. For material!:. well above

5·39
,------------- --- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,

AMCP 706,,185

TABLE 5·19
EFFECT OF SPECIFIC SURFACE ON BURNING
TIME OF TUNGSTEN DELAY COMPOSITIONS

Type oj'
Ta flusten Composition M10 ND 34.99

Surface Area
em2 /g 1377 709
Fuel
( ;haracteristics

f Weight Average
Diametp.r, microlls 2.3 4.9

))elay Tungsten 40 33.0


( ;omposition,
% BaCr04 51.8 52.0

KClO., 4.8 4.8

Diatomaceous> Earth 8.4 5.2

Burning Time,
see/inch 4.17 21.5

TABLE 5·20
IGNITION POWDERS FOR GASLESS DELAY ELEMENTS

Pllcl, 'lo Oxidants, % Inert, %


----------- " - - - -
~irl~(}nillm l"rrri'~ Oxide Diatomaceous Earth
()5 25 10

Boron iJarium ChrOMate


10 90

Zirl'Olliul1J F'erric Oxide


a:i 50
Titanium
17

Zireoninm I<\'rril~ Oxide Dia.wmaceous Earth


G1 all 10

Boron l~l'ad Peroxide


:W 70

5-40
TABLE 5-21
EFFECT OF FUZE HOUSING MATERIAL AND DIMENSIONS ON BURNING TIME
OF BARIUM CHROMATE-BORON COMPOSITIONS

Parameters Effect

1. Metal H01t5-ings
a. Aluminum. Brass and Stainl~s.<; Step.l a. No effect on burning times over test temperatures, internal
diameter, wall thickness and for either vented or obturated
columns.
b. No interaction between metal and cOfuposition.
'2. Internal Diameter, inch
a. 0.25095/5 ve!lted vs obturated a. Results for vented columns significantly different at 95% con-
fidence level.
b. 0.37:3 95/5 vented vs obturated b. Results for obturated column:. significantly different at 95%
confidence level.
c. 0.250 90/10 vented vs obturated c. No significant difference for either column at this diameter.
d. 0.37(; 90/10 vented vs obturated d. Results foJ:' obturated column significantly different at 95%
confidence level.
3. Temperature, "'C
a. - 54, Room Temperature, and 76 a. The effect of temperature was signifieantly different at the
95% confidence level for all metals, internal diameters, wall
thickness and for vented and obturated columns.
4. Wall Thickness, inch (U.05, 0.15, 0.30, 0.50,
0.75, and 1.00)
a. 95/5 Yfnted and obturated columns a. Rei;ults 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 of column. :..
~
("l
."
~

01 ~
.-
.;..
.... fX
c..' >-
~ II:
(')
~
~

-
~
~

TABLE 5·22
EFFECT OF LOA!>ING PRESSURE ON BARIUM CHROMATE-BORON COMPOSITIONS

95/5 BaCrO.-B
Loading Pressure (loa psi) 36 18 9 S.6 1.3 0.5
Mean BR, sec/inch- 1.69 1.60 1.49 1.39 1.29 1.21
Mean BR, secigram 0.643 0.655 0.645 0.642 0.646 0.693
% Coefficient of Variation 1.2 0.6 0.7 0.7 0.8 0.8

90/10 BaCrO.-B
n
Mean BR, sec/inch 0.670 0.653 0.619 0,586 0.558 v.~
f!!!AA

Mean BR, sec/gram 0.272 0.276 0.280 0.287 0.297 2.309


% Coefficient of Variation 1.5 0.9 1.1 1.6 2.0 1.8

• BR = burning ra.te.
,------------------------------------------------------------------------------------------------

AIICP 706-185

tion or a subsequent eharge and extinguish the


220 300 12~
reaction. Quantitative data regarding the resis-
tanc", of dela.y compositions to this type of failure
II)
are not available. "Slag retention," i.e., the
~ 0.5 t. -0.40 LOG,O T -} 1.37 fraction of the weight of the original charge reo
o
o
W
." 0.4
maining in an open ended delay column after
w functioning, has been used as a possible qualitative
~ 0.3 indication of the resistance of a delay element
to acceleration forces: Slag r-etention for S\)me
i'" 02
delay compositions is ~ follows: manganese,
'"::>
!l) 0.1 > 95%; red lead, 90%.95%; tungsten, > 95%;
0.0 L _ _-.J...._ _ _...1.....:_ _~_:_:__-_::=:__-__::_::~...J
niekel-zirconium, 80%-90% ; huron, 59%.90%.84
2.34C 2.440 2.541) 2.640 2.740 2.840 Intrvduction of a binder will improve perfor-
mance nllder high aeceleration conditions; how·
Figure 6-20. Burning Time of MJJ2 Fuze Containing 90% rver, binders telHl to produce sufficiently large
Barium t=hromate.JO% Boron Composition Versus I.og· amounts of gaseous products so that the system
arithm of Absolute Temperature could no longer be considered gaseless_ Mechanical
support of 1;he delay column at both ends t.ends
their failure diameters, the effect of wall thick· to reduce variati{)Il in burning times by minimizing
ness becomes less important. 32 As shown in Table 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
differrners observed werr small and had no ap- 'rhe effectiveness of an item of ammunition
parent trend. No l-Vignificant difi'errllce due to may dt'}wlIcl greatly on accuracy of the delay. Be·
wall thickness was noted for thc 90/10 barium caust' it is necessary to store ammunition for a
chromate·boron compositions. 48 IOllg time, it is important to know the effect of
storage on thc hurning times of delay composjtions.
As also shown in Table 5-21, the material uscd
for the housing did not appreciably affcct the In gereral, dry storage for relatively long periods
burning ratp of barium chromate-boron composi- of 1imp rl'suits in little change in burning time.
tions. 48 For l'xample, barium chromate·boron composi-
Dplay eompositions havc bern loadrd and con- tions loaded and stored over a desiccant show little
l'hangl' afta time intervals up to two years, as il.
solidatrd into ll'ad tubing by a swaging technique.
The aeeUl'aey of delays prepared by thr lead-tube Itlstrah'u ill Table 5-23. For loose powders stored
up to two ypars ill unheat<'d magazines and then
method depends on many factors associated with
loadrd, a slight illerea..'!e in hurning time has been
thr composition, applieation, pte. However, it
ohs(·r\'l'd. Storage under dry conditions prevents
may hI' said that ill SOlllp appliratiOl:s it is more
furthrr ilH'reh'ip in bUl'nillg time and may reverse
aceuratt' and in others lrss accurate than the
j he trl'lId as shu-.vlI in 'fable 5-24.
l'onvelltional method of tilling. 49
\VIJeu manganese delay mixtures are kept dry,
thl'ir hurning times will not increase more than five
IWf('rnt during pight weeks' storage at +165°}4'.
5-5.1 .3.10 Acceleration
Roml' mixtures containing manganese did not
l>rlay ell'IIlt'llts ar!' oftl'n sul)ject!'d to wry high l·hallg"l' their burning times when stored without
accelerations while tltl' delay t"ompositioll is buru- sealing" at 100 Jll'rcl'nt relative humidity and
ing, as in skip bombing. If thl' structllrl' of thl' + WfjoF'. Othl'r llJallgalH~~ mixtures deteriorate
matl'rial at or bphilld tIll' rpadion front is too rapidly umll'r thl' S/UIII' conditions. This wide
weak, the aecelerations may cause the hot products \'uriat ion in :.;tora~(' stahility is due to differences
to lost' l'Olllad with thl' IlJlhllrJIl'(1 tIday (·omposi- ill t ht' manga:ll'SP powdrr used in preparing them,

5-43
AMCP 706-185

TABLE 5-23
EFFECT OF STORAGE ON FUZES LOADED WITH
BARIUM CHROMATE-BORON COMPOSITIONS

Zero Time Stored 19 months


Mean }!fean
Comp., B. T.,· % Coe}'. B. T.,· % Coef.
%B flee. Std. Dev. Var. Sec. Std. Dev. Var-.
------
10.0 0.514 0.013 ~.5 0.515 0.025 4.9
10.0 0.590 0.012 2.0 0.579 0.012 2.2
10.0 0.519 0.015 3.0 0.476 0.010 2.2
10.0 0.574 0.004 0.8 0.522 0.012 2.2
5.0 1.590 0.015 0.9 1.587 0.020 1.3
5.0 1.075 0.016 1.5 1.059 0.015 1.4
5.0 1.294 0.026 2.0 1.264 0.019 1.5
5.0 0.818 0.016 2.0 0.785 0.016 2.0
5.0 1.192 0.036 itO 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
* E. T. = burning time.
TABLE 5-24
BURNING TIMES OF FUZES LOADED WITH 93/7 BARIUM
CHROMATE-BORON COMPOSITIONS STORED LOOSE
UNDER V A.RIOUS CONDITIONS

Init'ial Oonditions Storage Oonditions


l',[ea,n B. T.,· % Coe/. Mean B. 1'.,· % Coe/.
Sec. Var. l'emp. Time Sec. Var.

150°C 4
hours 0.707 1.1
8
hoUl's 0.722 1.0
0.694 2.7 105°C week1 0.723 1.8
50% RH week1 0.720 1.5
Desiccated week1 0.685 1.7
0.647 2.3 150°C 4 hourfl 0.685 2.5
Composition!1 loaded in M1l2 Puze Housings at 36,000 psi.
* B.T. = burning time.

and, apparently, is associated with the manga.nese Por zirconium-nickel delays, four weeks' dry
crystllIJite size aIHl surface oxidatiou. Protective sUl'Vt'illunce illereases burning times up to 16 per-
treatment of tht' manganese fUt>l ug-ainst l'orrOSiuIl I.~ent. \Vet >;ul'veillance f()r four weeks results in
~xjda.tion of surface by dichromat-ioll and coat· llnrpliabl" pf'rformanc(>. Delay composition!1 of
iug with a thill film of stearic acill--tlid not im- !'\liCOl1 and rt'd lead exhibited ilH~reased burning
prOVl' the dry >;urveillallet' properti(>s of llHlTlg-uneSf: tiIll'>S of up to 1() pim.·('Ilt after ~our weeks' dry
dt'lay puwdt>rs but did improvt' tllt> wPt surveil· "u rveijJanee and were unreliable after four weeks'
lanre eharuetcristics. wet Hurveillll.llee.

5··44
A.M:CP 7()6..185

In general, results of 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 "ther ex-
burning times after four weeks of dry surveillance. plosively loaded items is used to produce the ig-
'Vet surveillance appreciably affects performance nition stimulus required to initiate the main pyro-
of most delay mixtures, in some cases sufficiently to technic composition. Sucll a train can be con-
makf' the mixture unreliable. sidered as divided into three parts. The first
part contains a sensitive initil!ting composition
5-5.2 HEAT POWDERS30 that can be initiated by a relatively small, me-
ehanical, electrical, or chemical stimulus. This
The majority of pyrotechnic heat powders have
initiatir.g composition, on burning, produces saffi-
been dewloped for thermal battery applications
cient heat to initiate intermediate explosive or
to melt the solid electrolyte and activate the electro-
pyrotechnic compositilln(s) in the second part
chemical sYfltem. In general, the heat powder-
of tIll' explosive train. The uutput of this second
which ~enerates between 850 and 500 calories per
part will initiate the main charge in the third part
gram-is mixed with inorganic fibers and made
of the explosive train.29.31.32 In many eases, a de-
into heat paper using cOllventional paper making
lay train (see Paragraph 5-5.1) can be included
techniques. 'l'he heat paper can be stamped into
in the second part of an explosive train. Emphasis
r'~quired shapf's and easily assembled with the other
in the f0110wing paragraphs will be on initiator,
battery components. Other uses include warming
first fire, and starter compositions used in pyro-
of battery plect r olytes, melting of 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 awl gl'.sless delay compositions can be
dieabd that ignition is a complex phenomenon.
used interehangeably; however, th(, electrical con-
Ignition failurps of pyrotechnic items emphasized
ductivity of the products formed during burning
the need for more research ami the need for more
is important in thf' ability of heat powders to satis-
understanding of the ignition and combustion
factorily perform their function.
processes. The availahle compositions, with de-
'l'he heat entput d a he,lt powder is of prime
seriptions of their applit~atiJns, 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 mixturf'. Other important characteristics in-
clude: 5-6.1 PRIME IGNITIONIIO
a. Heat of reaction. Basically determines the Primc ignition is the starting of a fire without
heat output per unit weight of heat powder. the use of another fire and ineludes methods based
b. Gas e\'olutioll. The gases evolved must be on friction, percussion, coneentratioll of the sun'~
eontroHed bf'cause it is possible they will afIeet ra:'s by mirrors or lenses, and lin electric impulse.
the behavior of thl' heat battery. Many matprial", and mixt.ures of materials
e. Barning raip. Basieully determines the rate have been found which produce heat as a result
of heat releasf' by til!' heat mixture powder. (The of chl'llIical reaetion and which require relatively
burning rah' of hl'at paper has been suggested as litth· physi :,al pifort for initiation. Chemicals, such
a ITlt'llI1S of obtaining II controllpd delay time.) as whit(· phosphorus and phosphorus-eontaining
compounds, burst into flame on exposure to air.
Othpr matprials, induding many metal~ which eODl-
5-6 INITIATORS, FIRST FIRES, AND mOllly will Hot ig-nite iii air, become pyro}Jhoric
STARTERS whplI finely ~roulld; while other matt'riais are acti-
'flit' illitiatiul1 of t'ombuptioll of a pyrotel!hnic \'a,p(} by ('xposurl' to wllt('r or UCi(l, t.o a spark
l'ollJpositioll fequin·s tilat Ii pl)rtiol1 of till' l'OIllIlOsi- with II small {'flI'rgy l'Olltent, (Ir to very slight im·
lioll Ill' l'uis('d tt, its illHitioll teml)('ratnre. (Sl'l' pad. Still llt\wr mixtures requirf' only a small lind
fdso Pnl"lll!mph :J·:l.ti.l', Sill(~p SOllll' pyrotechnic pl't'dit'tablP amount of f'llt'rg-y to ht' initiated. This

5-45
AMCP 706-185

last group, which includes matcheu, is of im- airplane flare contains 14 parts potaBsium chlorate
portance as initiators for ordnance items. and 1.6 parts charcoal ht'l.rdened 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 of the l~omposition.tSl Modi.
animal glue. The striking strip is composed of red fied scrat~h sensitive mixtures containing some
phosphorus in Ii similar binder. Use 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 easHy when It tt' starter. 8
rubbed on the striking surface. The friction and In addition to matches aud other scratch sensi-
contact of potassium chlorate crystals with red tive materials, prime ignition of pyrotechnic muni-
phosphorus results ill the ignition of the match tions. Jike other munitions, is accomplished with:
head which, in turn, causes the ignition of paraffin a. Pert·usskn (or stab) primer which contains
impregnated in the match "plint. A typical match a mixture that is relatively sensitivf' to impact and
head formula, and that for the ~triker, are given friction, or
ill Tables 5-2;; and 5_26. 50 b. Electrically ignited primer (or squib) in
which the heat produced by the flow of electric
TARLE 5·25 current in a bridgewirc ignites a heat sensitive
COMMERCIAL explosive. For ('ortain applications, especially
SAFETY M~TCH COMPOSITION those involving' initiatiOl of high cxplosives, a
brid~ewire may Iw exploded by application of a
Ingredient Percent-
hi~h current pulse causing direct initiation of some
----------------------------- less-sensitive explosives. 29 ,31,32.52
Animal (Hide) Glue ..... . 9-11
Extpnder (~tarch. Dextrin) ........... . 2-3 C!'rtain chemical reactions have been used for
Sulfur (Hos-in) ....................... . 3-5 ignitioll of explosive trains. As has been indicated
Potassium Chloratt:.................... 45-55 ('arlier, sOllie materials burn when exposed to air.
Ncutralizer (Zinc Oxidc, All example is white phosphorus. It has been used
Calcium Carbonatc) ............... . 45-55 ill burst!'r" for jelled gasoline incendiaries where
Infusorial (Diatomaceous) Earth .... , .. 5-6 it serV<'s the dual purpose of igniting the incendi-
Other Hilie('olls Ii'ill!'r ................. . 15-32 ary. aud the reigniting jelled gasoline which has
bl'E'n extinguished. Diethyl zinc, or triethyl alu-
• lI'ractional percl'utages of It soluble burning rate minum, contained in a glass vial, has bcen used
patalyst, sudl aH potassium dichromate, arp added, also
soluble tly~ ~tuffs. Lpad thiosulfate or zine f('rrocyanidt' to ignitf' a mateh mix in a silent igniter. Some
ean hI' uaed if thp match head is to he white. matrrials, notably the alkali metals, reaet very
vigol'ously with water, liberating hydrogen which
Presfmt "strike-anywherc" (SAW) matchcs
is ignitrd by the hrat of reaction. Bursters fillrd
have a fHnaB, easily ignitibh' tip l'olllposed of
with sodiulIl have bcpn (~ollsidered for igniting oil
tdraphosphorlls t risulfidt' (phosphorus sesquisuI-
"li<'ks 011 watpr.s Th(; vigorous chemical reaction
fide) aflixt'd to a lal'g!'l' bulb \'ompme(l of a rather
rrsultillg' from bringing iron pOWder, potassium
ins('w,it ivp lIlodifit'd, saft'ty mateh lwad \'omposi-
IH',"mflIlganate, and sulfuric acid togethcr is an·
tion. 'I'alll,· 5-:n givps th(' formulation for two sud;
(~OInpositiulls. f.ll
othel" method of prim!' ignition.
Tltt' mat"h mixtures lIse(; in lIlunition>.; are gen·
"rally IIllIl'h )t'SH (·omplieat!·d in eorupositio1J and 5·6.2 CHAR ACTERISTICS OF IDEAL
IllallUfal'tllrt' thun tit" commercial match mixtures IGNITER, FIRST FIRE, AND
whi, h rt'ljllirt' a spt'('ial striking- sllrfa(~t'. Com- STARTER COMPOSITIONS
positions whi('h haw be('n widl'ly ased in friction The !·oltlpo>.;itions llsl'd to ignit(> any burning.
pl'illlt'rs for artill('ry art' g-ivell ill Tahlt' ;1·2R. A tyP(' Jlyrotl'C'hni(' should haw thl' following <'har-
eOlllposit io" us('d ill tht' frietioll prim!': for an adl'risties ;~3

5-46
AMCP 706-185

TABLE 5-26
SAFETY MATCH STRIKER COM~OSITION

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


I"Igred-ient % % %
Binder " 20 16
R€d Phosphorus 53 50 50
Antimony Sulfide 42
Charcoal 5
Carbon Black 4
Neutralizer (ZnO, CaeO s ) -5
Sand 30
Powdered Glass 25

* In NC laquer, Dextrin, Casein, Animal Glue, plus hardener of U.S. Pat. 2,722,434 129.
t Formulas 1 and 2 are "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 of a neutralizer and preservative for red
phospho?us.

TABLE 5-27
SAW ("STRIKE-ANYWHERE") MATCH COMPOSITION

F'ormula 1,· Formula 2,·


Ingredient % %
-----
Animal Glue 11 12
Extender 4 5
Paraffin 2
Potassium Chlorate 32 37
Phosphorus Sesquisulfide (P4 S a) 10 3
Sulfur 6
Rosin 4 6
Dammar Gum 3
Infusorial Earth 3
Powdered Glass al1<l Otlwr Filler 33 21%
Potassium Dichromate 1%
Zinc Oxide 6 1

• Formula 1 repreJl'nts the tip formula whi~h ignites on any hard surface. Pormula 2 is
the match cOlllpositioll'8 bas". lou,led with combustibles for strong billowing flame but Ilf low
frictioll sensitivity.

a. Be igniteu by the prim('r, fuze, or match 'rhe speeifie lIutllr!' of tht' ignition (~()mpositioJl
employ('(l i:l tlll' munition. is primarily determined by the partieular ignition
h. IgTite tll(' main pyrotedlllie ('ompositioll. pl'oblt'HI sille!' it involv(,ll tlw n!ltur(~ of the filling
('. Hl' suml'iently ins("lsitiVt' for safe handling to h(· ig'lIitl'd and th!' lllt'thod by whieh the ignition
III manufaduring and loading operations. l'olllpositiolJ i~ ignited. The wi/it' 'Variety of fillings
d. Be resistant to tbt· effect of moisture. liNN} in burning-type munitions mak('s it impossible

5-47
AMCP 706·185

TABLE 5·28 be ignited appears to be the most practical basis


FP.ICTION PRIMER COMPOSITIONS for diffrrl'ntiation of the various compositions.
Ignition compositions may be classified as those:
a. For munitions containing thermite-type fill-
Ingrcdient Parts by Weight
ings or illuminating compositions, the reaction
Potassium Chlorate ............. , 56.2 44.6 should be very hot yet (wolve little gas.
Antimony Sulfide............... 24.6 44.6 h. For munitions containing He smoke fillings,
Sulfur ........................ 9.0 3.6 the rraction should be hot. and preferably produce
Meal Powder. . . . . . . . . . . . . . . . . . . . 3.6 some slag; some cvolution of gas is acceptable,
Ground Glass .................. , 10.2 3.6 e. For munitions containing eolored smoke mix-
tures and toxie smoke mixtures, the reaction prod-
uct may vary from gaseous slag to highly gaseous
to dew lor one composition for all purposes. A
with no sla.g.
t'ompositioll prol' acing a slag and a high tempera-
Ignition compositions which are used as rocket
turl' would \)(' dt'sirabll' for ignition of a thermite-
neotor igniters arr usually ignited by the output
typt' i]\epndial'~' or most illuminating" compositions,
of a black powilf'r which was commonly used for
but would be ullsatifofactory for ignition of a
this purpose, has bern rrplacea by ignitrf eom-
('olorl'd smok(' siuer the high trmperatur(' would
positions composl'd of a powdered metal and in-
('ause flaming of tht' dye.
organie oxidizrr.
Rl'quil'l'ments for ig"lIitioll eompositions, there-
fore, must lw Yaril'd dplwndiug on their use. Ig-
nition mixtures call he elassified as slag-producing 5-6.3 TYPICAL COMPOSITIONS
or gas-produl'ing mixturl's. As SOIl1l' l'ompositions 1'he eompositiolls of typical igniter, first firc,
pro(hlt,(, hoth sb/r alld gas, tIll' 1ypt' of filling to and star1t'J' mixtures art' ~ivell in 1'ablr fi-29.

REFERENCES
1. 'I'llI' l'lIl'rmoclll'lHistry of Tnrclldiaric:;, NDRe Ii. n. II. (~l1stard, G. Praneis, W. Sehnackenberg,
lTIIIlUlllhl'I'<'d, ~ Aug. 1943, Available at Tech- Small Arm,~ /lIC1'ndiary AJlltnunition, A Re-
nieal Library, Edgl'w()od Arsenal, as NDRC I'il'll' of Ihl' lTistory and J)cvclopmc1It, Frank-
Mi:·;('. Puh. :lOH, Hl']wrt of Division 11, Na- fortl Arsl'nal H{'port H-1407-3, DecemberW56.
tiollal I h'f('nSl' Hf'seareh ('olllJnittee, Office of 7. L. Finkl·!stl·ilJ, A. E. Gaul, IrIC('ndiaries, Vol.
Scielltilil' HeSl'HI'l'1I alld l)('vl'lopment, Wash- 18, Pari n of Ilisto"!1 of HfSl'llrch atlli Devel-
ing'toll, D. C. Optlll'lIt of Ihl' Ohemical Wm'/lIrf Service in
,)
"\. T. Wil~oll, J)1'l!e/oplllcllf of MOX Explo- World I\' (II' n, E(lgc\'/ootl ArSl'nal, Maryland.
Sil'IS: VII1'iOIiS ,Oxidants in MOX, NFOC.6, H. :-1, .J. ;\llll~r/llll. Sfltrtas, Vol. 16' of History of
National \'nrtht'r11 Corporation, 'Wcst Hall· Hl'sl'a/"eh and DC1,I'l0Plllfllt of thl' Chemical
OWl', :'IIass., Dt·('l'IIlI.II:'r 1!l:i2. War/an Sl'rl'iCf ill World War n, Edgp.wood
:1. H. W. E\'IIIlS, R.cpl'rim( IIlal /nvt'sti[lat1'o-n of Arsl'llItl, MaryJlllld.
infral"l'd Ha~li{/Iin!l ROIII'Ct'S, TN-9, Dt'llver R(·- !I. \v ..Jost. Rxplosiln' lind ('lImbuslioll Processes
SI':ll'dl Illstituft', Dl"Il\'('I', ('(Jlorado, .July 196] ill OUSI'S, l\1l'Ol'lIw-lIill Book (~o,' 1m., N. Y.,
(DllC-A]) :l:.!-t H07). 1~l-t(J.
4. S. G'lI'dllll, ('. Campilt'll, ., nitrf'reutilll Ther- 10. B. I'I'wis lIud O. VOIl glb!', ('olltbusfioll Plat/lCs
11 lit I Allulysi!' of t IlOIg-uui(' ('ompounds," Au- IIIIt! r:./'p/osi!JlIs IIf (iasls, :!ud Ed., Al'adrmic
alyt Il'al ('hl'mistry 27, llO~ (1955). Prt'SS, 1111'., ~ y" 1961.
f). A. \I. PI'l'lltiss, (,hl'tnicais in lVar, Ml'Grllw- 11. II. V ('oWlll'd Hud (; W ..JIlIlt'i:i, j,imits of
Bill Bllok (~I)., 111('., N. Y., 19:n F/a7lllll(lliilit)l of nasI's (m.i Vupors, Bulletin
AMCP 706·185

TABLE 5·29
SOME FIRST FIRE, STARTER, AND IGNITER COMPOSITIONS

Composition (Percent by weight)

Aluminum 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 (FeIlO,,) 25
Iron Oxide (li'e2 0 a) 25
Iron Oxide (Scale) 22
Lead Oxide (Pb0 2) 80
Lead Oxide (Pb S0 4 ) 35
Potassium Nitrate
Tetranitracarbizole 5
Laminae Binder s· .~
•• •• .... ••
* Laminae hinuer: Laminae 99'/<; Lupl'r~oi l'le.
U Most of thpse compositioJls "1\11 be used as 11 ioos(' powder mixture or with biJl<1er~ Ruch
a~ ('elluloiu, nitrocellulose or NC lacquer.

REFERENCES (cont'd)
;)O:!, BIII't'1t1i of ;\1 illes, Washingtull, D. C., 16. Glillfirl' Tl'sts to Ddl'rminl' thl' Vulnerabilit11
1!15~. of Jd·j't'opelll'd Aircraft Pucis, Repurt F-27-1,
I:!. A. O. Whitt', .. Lilllits fur til(' l'ropllgatioll of Navul 1'1'1IVl!l~ Oroillld, Bureau of Ns;~'aJ
\<'1!1Il11' ill IllllulIllllublt' Limits," .Journal of W,'allol\s, \VashillgtOll, D. ('., Decl'lllber 1.945.
tit,' Alllt'ril'llll Chl'lllil'al Soeiety 127 (19~5). 17. A. Htt'ill, M.•1. Torseh, Efll'ctivl'nfSS of In-
1:1. U. \'Oll Elbl', B. Ll'wis, l'Hpt'r,; prl's£'nted at t'l'udiary Ammunition Ayainst Aircraft Fuel
'J'hird I:-'YIlIJ)()siulll 011 Combustion lIud l<'luult' 'l'unks, BRL Mt'1ll01'llntllllIl Rt'port o4H4, Aber-
IIIltI ~~xpl(lsioll Phl'I10lllt'IlIl, Ilt'ld at Ilnivl'rsity tlp,'11 PI'(lvillt! OrOlllltl, Md., 194H (DDC-ATI
of WiS('IlIlSill, H('pt. 7-11, 19047, with Bureau of ·l~ :IH:l).
~lill('S, Pit tsburgh, i'll. IH. A.• 1. !\1dzlt'r, Jlillimllm ,""park Ignitio1~ E1~ef'­
1·1. (: W. ,lollt's, HI smrch 011 Plammahility C'har- !lilS lif 1:: "lIrl' PudlO at Atmosphl'nc and Re-
at:/I'ristics (if Aircraft Pllt'/S, Prof.{ress Report eI'I('ld l'rls.wrl, NACA-HMB5:UI:n, National
~u. f), Burt'ull uf !\lillt':", l'it1sbllr~h, Pa., Advisory ('oll1lllitt"t' for At'rolluuties, Wash-
l\1llrt'h 1%1. il1!!toll, n. C., l!lfi:l.
1:" Selillcr of I'drult'lwI, IV, Uxford 11llvit'rsity 1~1. u. \V BaUSt'l'lll!lIl, J II I1lstrllmt'Tlt fot' Dc-
l'rt,~", 19:1~. ffrlllina::lill of 1',.all~·i/'llt Plaml' 1'(mperatuf'CS,

5-4!J
AMCP 706·185

REFERENCES (cont'd)
Phase Report No.4, Denver Research Insti- :1:3. B. W(lrbe~, S. I.-opatin, Develop'mcnt of J)elay
tute, Denver, Colorado, 1952. Puwders, Picatinny Arsenal Technical Report
20. 'l'hermite, Pluin, Incendiary, CWS l"ormula :H77, Picatinny Ar~enal, Doyer, N. J., 1958.
No. 0-1-1, 19 A;lgust 1944 (CW~ Formulary, a4. M. F. Murphy, A Comparative Study of Five
T('chllical Command, EdgewooJ Arsenai, 1 Pyrotechnic Delay Composit£.ons, NA VaRD-
September 1945). Edgewood Arsenal, Mary- 5671, Naval Ordnance I~aboratory, Bureau of
land. Naval Weapons, Washington, D. C., 1958.
21. A Solidified lhl Incendiary, b"[P-182-1, Massa- :1;,). M. F. Murphy, Current Topics in Gasless Heat
chusctts Institu[(> of Technology, Cambridge, Powder Work at NOL, Spee~h before NOL
Massach usetts. Pyrotrchnie Symposium, Naval Ordmmce Lab-
2:? D. Hart, Gasless Pou,ders for Delay Elements oratory, Bureau of Naval "Weapons, WaShing-
of Fuzes, Picatiliny Arsl'lIal Technical Report ton, D. C., 1959.
1239, PicatinllY Arsellul, Dover, N. J., 1943. :16. R. 11. (~omYIl, Pyrotechnic Research at DOFL.
2:{. s. Sag'e, Manufactllrl' of Bari1tm Chr'Jrnate I'a,rt II. Pyrotechnic Delays, 'rn-10l5, Harry
Delay Powder on a Semi-Flant Scale, Pica- Diamond 'Jaboratories, INashington, D. C.
tinny Arsenul Technical Report 1432, Pica- :17. P. Hochlill, Mass SpectrometriL~ Analysis of
tinny Arsenal, Dover, N..1"., 1944. Gas('olls Combustion Products from Delay
24. D. Hart, Dday Compositi:ms, Research and P(lu'cicrs, Pieatillny Arsenal Technical Report
DeveJoplllt'llt Lecture 27, PicatinllY Arsenal, :'006, Picatinny Arsenal, Dover, N. J., 1954.
Dover, N. J., 1956. :~8. R. A W. Hill, T. 1.-. Cottrell, "Studies of
2;"). (~. A. PoppcJldieck, Resrarch on Ileal-Pro- Combustion Waves ill eolids," Fourth Sym-
d1lcing ComjJo.~itions, l<~irst Quarterly Report, posium (Intrrnat-ional) o'n Combust·ion, The
('ontra\!t; D~\-:W-039-SC-7fi071, Catalyst Re- Williams and Wilkins Company, Baltimore,
search Corporation, Baltimore, Md., 1958. Md., 1963.
26. 1.-. Apostolos, Powder Plate Development, Cat- :19, .1. R Spi~e, h A. K. Staveley, "'rhe Propaga-
alyst Resear('h Corporation, Baltimore, Md., tion of Exothermie Reactions in Solid Systems,
1953. Part I. Pr'";gnition Reactions. Part II. Hc&.ts
27. Apparatus for Testing Pulp and Paper, Bulle- of Rraetioll and Rates of Burning," J Duena!
till VII, Williams Apparatus Comnltny, Wa- of the Soeiety of Chemical Induiltry 68, 313-
tertown, N. Y. HI, 348-55 (1949).
2B. H. II. ComYll, i'yrotlchll'ic Research at DOFL. .to. s. Nakahara, "Stu.i.es on Delay Powd~rs, I.
Part I. Heat Source MaterWls, Teehnical Re- Measun'lllrnt of Temp{·rature of Combustion
port 8M, 11arry Diamond LaiJoratories, Wash- of Dela~- Powders," {llallstrial Explosives So-
ington, D. C., 1960 (DDC-AD iJ21 045). cil'fJJ .101l7"1!fll, 1958.
2H. AM <'P 7()fj-21O, E'lgilleerillg' Design Hand- 41. S. ~likahara, T. ILki;a, "Studies on Delay
book, /i'I/Zl'S, Gt'n('ral and Mechanical. Powclt l'8, II. The (~olllbustjon Pressure of De-
:w. H. H. ('omyn, The Usc of Gasl('ss Mixtures for lay Pl)wtii'l's," Industrial Explosives Socict!!
Producing Controiled Time Delays in Ord- Journal, 195H.
nance DcviCl'··. DOFIj Rrport 22-576, Harry 42. S. ~akllhara, T. Hikita, "Studies on Delay
Diall"'Jld Ijabol'lltorirs, \Vashillgton, D. ('., PO'A{!t'rs, III. Oa l\frl'hanisllI of Delay Pow-
J 957. dt'rs," hldllstr'ial E.rvlosivl's Society Journal,
:n. Ordnance Erplosive Train D('sigth?rS lIand. 19l1H.
book, R-ll11, Naval Ortillan(,t' Ijaboratory, ·n. S. Xakaham, "Studi"s Oil Dl'lay Powders,
Bureau of Nllval W('apOIlS, Washillgton, D. C., IV. Th('o!'y of t 'ombustioll Propagation Ve
1952. loeity of J)f>!ay Powders," l-ndNslrial Explo-
:12. AM('I' 70fi-17!I, Engillt·t'ring' Dt'sigJl Hand Sil"'S Nor;"d" JOllrl/al, 1958.
book, E.r plosill(, Truins. 44. S. GOldoll, l'~. D. ('!'aile, (.'ompilati'nl m1<1

5-50
AMCP 706-185

REFERENCES (cont'd)
Evaluation or the Ignition 1'ernperature Pa· Sands ~.lrovbg Ground, November 17, 1959,
mmete,-s a,nd Differenf'::1l Thermal, -in('lysis Pie'ltiluy Arsenal, Dover, N. J.
[:Jr Pyrotechn£c Systems. 1. Barium Chromate- -±9. '1'h.~ App!ication of Lead Tubir:.g to tit') Fillin!/
Boron, Picatinny Arsenal rrechnical N"te 24, of Pyrotechnic Delays, Branch Memo X4/3/58,
Picatinny Arsenal, Dover, ~. J. Armame~lt Research and Developm;ont. Estab-
45. R. Comyn, R. Skeltor;, Effect of Pressure on lishment, Mini:;try of Sunply, Great Britain.
the Burn 1;ng Rate of Ga..~l!JSS Delays, NAVOHD- 50, H. Ellern. Modern Pyrotechnics, Uhemip.al
1787, Naval Ordn:l>lCeLaboratory, Bureau of Put-~ishing' Co" 1961.
Naval Weapons, Washington D. C. 51. K. L. Davis, Chemistry of Powdp~' and Ex-
-lo. 1\1. Gilford, B. Werbel. G. W,lllgart{,Jl, iI. Key, plos'ives, .loilll \Viley ~;, SO;U', N. Yo, 1943.
The Anticipating Effect. A St1ldy of the Burn- R. ('. Mallinger, Bc.ckgro1l'nd of Exptad1;ng
ing Mcchtwisril 0/ Delay-Relay Coiumns, Pica- BridgcUJirc. and C . Jnventiond Systems, Pre-
tinny ArlSemd Technical Report 3047 T)ica- sented at Amerir'an Ordnance Association
tinny Arsenal, Dover, N, J., 1964. ,Jnint Tecl.ni<?al Meetin~ on Exploding Bridge-
47. R. E. McIntyre, Factors Affecting the Blend- wire Systems, Los Allgeles, Ca:ifornia., Febru-
ing of (iasless 1Il-ixt1U'es, TI1-648, Harry DIa- ary 10-11, 1964.
mond Ijaboratories, \Vashington, D. C., 1959. S. .J. Ma~raIll, A S1;rvey of Stm·ters for Burn-
B. \Verhel, Recent Advances 1:'" PYI'atechnic ing Type iliunitions, TDMR-655, Edgewood
Delny Compositions, Speech presented at White Arsenal, Maryland,

5-5]
AMCP 706·185

CHAPTER 6

PRODUCTION OF LIGHT

6-1 RISTORlCAL SUMMARY prepared in 1786 and first mentioned I!S an in-
Miiitary pyroteehmc items useJ for illumina- gredient in a pyrotechnic composition in 1823.6
tion aud signaling by the military share a com- By 1830 several formulas containing P()ta.'l:JiU\ll
mon origin with the spectarular white and colored chlorate had been developed for firewerk disp!ay,
flames pr<lduced by fireworks. Tracing the de- military ~ignaling and signaling at sea. While
velopr.:J.ent of these compositions is relatively easy most colol's could be produced in a more or less
since there was little progress made ill the develop- satisfactory manner by 1850, it was sever~l years
ment of flame producing compositions untii the later before a s:;.tisfactory blue flame was pro-
introdaci"ion 04' potassium chlor&.te pyrotechnic duced. This was accomplished ty addhg copper
mixtures near the end of the 18th century.1 salts to compositions cont,,'1inin~ pota..~dum '.lhlorate.
The color was enriched by the us~ of calomel,
6-1.1 CONSOLIDATED ILLUMINANTS Hg2 Cl 2 . During this period colored flames pro-
duced by adding color-emitting salts to potas-
6-1.1.1 Fh.res 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 divided into two types, those designed to pro- quality, these \.lompositions were abandoned be-
duce force and sparks, and those producing a cause of their sensitivity to imPf.ct and friction.
flame,l·:! Early effort,. were directed toward the Sulfur was replaced first by powdered Ehellae and
developmellt of spark and force producing COlli- later by other gums and resins.
pc..sitions. At that time, there was no known way MagneGium was first produced on a com.mercial
of impal."tir.g color to a flame. As a result, there scale in 1860 ar.d WdS used by European pyroteeh-
was little difference to the twe between a flame nicians several yeart; litter. In the United States,
produced by a pyrotechnic mixture and one result- possibly beca.use of its cost, magnesium was not
ing from the burning of pitch, petroleum, (r used in military PYl"otcchnic mixtures unti! .I.L":,,ocnd
resinous wood. Sparks could be varied in form and 1926.•\lumin 11m was not used appreciably in pyro-
brightness, although not in color, so that spark tellhnic compositions until near the end of the 19th
compositions becam£:, and remained for ceuturic";, century when it bt'cflme commercially available.
the main eon&ideration of the fireworks maker. Illuminating compositions for military appli-
The fe" flame compositions available in the eations were, basically, the same as those used in
17th century usually included a flammable liquid firework disl/lays over two h~n~red years earlier.
in order to ensure combustion of the rest of th'l A primitive type of light producing item- ·whose
mixture consisting of gunpowder, antimony sul- . composition consisteu of saltpeter, sulfur, resin,
fide, and arsenie sulfide. Appier1,2 was far in aud linseed oil--was included in British military
advance of his time when he suggested the use of store<; until at least 1870. ~~ost important of the
acetate of copper to give a green tin~ t(' a flame. few iuventwns i1' military pyrotechnics during the
By the early part of the 19th centu~y, a pyro- latter part of the l!Hh century was the parachute
technist, Claude-~'ortune Ruggieri,3.4,5 sugg~sted light whieh &ppe.)!"s to have originated about 182G
the USe of metal salts and ammoniulll chloride in in Denmark mu(;h in adva~ce of its widespread m;e
the production of a colored flame. in the WO!·~':l Wars of the 20th century. Another
The modern era in pyrotechnics l;egan with the invention, the VelY Pistol which was patented in
introduction of potassium chlorate which was fil'st 1878, originated as It '.livil s;gnaling d~vice. Ini-

6-]
AllCP 706-1M5

tially, the pistol had a one-inch bore; this was ':-he range or the crude gnns ir.troduc!:'u after
later increased to one arId one-half inches during the inwiJtion of r,ulJPowder was sO ~hnrt that the
World War I. Improved illuminating and Rig- point of impact of the pojectile '!ould h~ noted
naling devices were developed in the 1914-1918 by the eye. However, this was no longer possihle
period becau,!ji, they wele requii'ed ir the trench after the .introdlletion of wcapons which firl"d
warfare of World War I to a much greater extent small-cnliber, high-ve~ocity buliets over ranges of
thnu in prior wars. The growing import.ance of more than a thousllnd yards. During World War I,
air warfare ')pcned a wil~le new field. f(lr the use the need for tracers was intensified by the wide us~
of ilIuminants ann signals. Simulators and del~oys of ma('hine guns. The need for tracers berame
were developed for the purpose of mislea,~ing enemy eeute, coincident with t!1C enormous expenditure
(,bservers. of ammunition by infantry anrl air strvice. At
Most of the illuminating and sig'f.aling devices long range. in the air and Oll the grouIld, it was
produced in the l'er~od between W orId IN ars were almos: impo.~siblr to ~stimate range and correct
developed by empirical medlods. Tlw limited
Itim by observing the point of impact of bullets
amount of work perfnrmed in this period necessi.
which did not incorporate tracers.
tated a hurried attempt to put the pyrotechnic
During W orId War I, the air services of both
field on a scientific basis at the start of World War
the Allied and Central Powers urgeD-tty demanqed
II. Thi& attempt "'~s halllprlr~d by the necE'ssity
an efficient, accurate tracer bullet and, as the re-
ot producing itilms fur im!l1ediate use on the baW",-
sult, tracer ammunition was S~0n developed by all
field. Most of the research and devE'lopruent con-
of the be'ligerentr.;. A German tracer cOl.lpositicn
tinued to rely upon empiricism. However, a lim-
-containing a mixture (I! magnes;um, strontium
ited amount of basic and applied research: much
nitrate, calcium hydroxide and rosin·- was 110t
of it directed toward the developr~,ellt of better
very satisfhctory be~ause it was difficult to ignIte
light producing compositions, was started at sev-
and produced. a very d:m and t!dlGtillct~race.
eral nf the Government installations amI cnntinued
The French tried ~everal tl'ac"r mixtures which
after the war. Results of the work done after the
eontaimll a small amount of linseed C'il as a
war were extremely rewarding. At the e:ld of
lJinarr. These tracers were auite brilliant. and de-
'World War II some Opinion was expressed that
pendable but were unstable in storage and became
little improvement could he made in flare and
practically useless soon after manufacture. As a
photoflash eompositions. 7 Contrary to this opinion,
rpsult, ]:<'re,ch tracers were made immediately be-
major improvements were made, some of them in
hind the lines Sf) that the ammunition could be
time to be of great serviee in the Korean Conflict.8
placed in the hands of the troops as promptly as
Current research and developme'lt cffort is
possible. If the ammunition could not be used
being directed toward the development of advf'1ced
within two or thrj'e weeks, it was scrapped and
flare compositions, for both illuminating ane sig.
relJlaced.
naling purpos{'s, to function at altitudes where
After the United States entered the War, a pro-
little or no atmospheric oxygen is available.
gram of drveloping bette!' tra~ci' ammunition for
the American Expeditionary Forces was activrted.
6·1.1.2 Tracers The rtsult of thi£ work was the development of
Before the invention of gunpowder and the use M:1917 tracer ammunition, which consisted of a
of bullets, there was no need for tracers. The jacket pi ('upronie!c('\ surrounding a container of
projectiles used, namely !Spears and arrows, were gilding lIlt'tal Ilnd a It'ad shot. The tracer composi-
large in size, and traveled at a low velocity, so that tioll wa.'; a lllixture of barium tleroxide and mag-
their line of flight eoulrl be readily foI:owed. Ar- nesium in grain alCOhol, which was dried and
rows tipped with burning g'ril'3S roigU be con- prt.'ssi'd into the container at 48,000 pounds pel'
sidered the first trd.Cerf;. ThongI' the prjm~ I eaoon squarr ineh. This tracer was quite satisfactory
for nsing these burning :lrrows was to start fires, and pro<.~ueed a trace-;\'hich was not c[;pecially
the ,,'Oursc of }he arro\V c::mld be followed at night. brilliant-for aLout 500 yards. Another traccr

6·2
AMCP 706-185

was developed in cooperati01l with the British, v('stigated as a means of improving color of the
using Ii mi.<ture of barium nitrate, barium pe"fOX- flame and buring. During this period, calcium
ide, ;IllU magnesium loadpd ill a hollow brass bul- rl'sinate was introduced as an improved composi-
Jpt. All ignitpl' mix of bariulI1 peroxide and mag- tion binder. By 1929, there was concern as to the
nesium was rpquired with thi" tracer mixture. t'ffects of ineorporuting mercury compounds such
The using services werp not satisfied with the as ('alompl in, tracer buHets ~cause, under certain
status of tracer ammunition at the end of the War, conditions, it was observed that the jacke'l:s split
and again studies directed toward the production in storagt', probably due to the liberation of the
of It bl'ttpr tracer Lullet were rel-:un:ed. Many mercnry from the calomel. Investigatian proved
mixtures wpr!' tl"ip<1 during this period and. it was that the ('racking of the jacket was due to the pres-
found that calomel wou)(} increase the brilliance ('nce of fr!'e me:cury, and elimination of tracer
allr} luminosity of ehe trace r,roduecd; this result~d ('ompos~tlons followed..

ill the intl'oduction of tlw M1928 tracer bullet, IE addition to this work, a limited amount of
(~aliber .:m, and tllP design of an Ml924 prototypP. I'l'seareh and dpvelopment effort directed toward
During this ppriod. tnl('ers were dpveloped fo:- thp develoPllll'llt. of red tracer compositions for
caliber .50 ann also f9r ('aliber .45 weapons; thesp ammunition larger than caiiher .50 was iuitiated.
we!'(' llspd primarily as red, green, and white sig- During- this same period, the Navy had de7eloped
lIal rounds. It is also intpresting to note that tht and adoptprl !mtidactory compm:itions for red,
MHl28 tra(~er was evaluatt'd as a small arms in- whitf, grp('\J, and orange tracero.
('elldiary bullpt and found to bi' superior to thp About 19:~4, study of hst records showed that
thpll-availabll' small arms incendiary ammunition; Army tra(~l'rs beeame unsatisfactory after five
for somc tinw thereafter this trl:1cer also served as Yl'ars' st()ra~t', 'fhe tracer composition had been
a RJIlall arIlIR incPlldiary. By Dpecmb('r 1926, mili- wet-pro(:<'ssed to obtain good storage :Jtability; i.e.,
tary requirements brought about Rtandaldization th!' ('alt-inm f('sinllte was dissolveJ in carbon tetra-
of the rl'd traeer as th8 onl~' ont' appro ved for l'hloritip, mixl'(l to a paste with the other ingred-
~('neral military use. 'fhe designation was "Bul- iPllts, bakt'd dry, and pulverized to a powder to
let, Traccr. Calibl'r .ao, 1\11." The tracer composi- r!'nder all ingredientq moisture-repellent. Poor
tion contailled strontium peroxide made by the storage stability was apparently due, not to the
dry process and a highrr-dpl1sity calomel. tracer composition, but rather to the dry-blended
Th(, igniter composition eomained barium per- barium }Y'roxidp-magnesium-red lead igniter com-
oxide and fill(, magnesium. Tracer M1 was 11lso position. Red jpad, although aiding bonding and
!oadl'd with it sHbignitt·r consisting of three parts i(lPlltifieation of the igniter composition, was found
ignitpr and Ollt' part tracPI (:omposition to influre to b(' ehemieally illP.ompatible with barium per-
i~llitioll (,f thl' tracer l'omposition. 'fhese changes oxide and, thereforp, was removed from trle formu-
I'P;.;u\tt'd ill Hll iJl(~n'ased Ipl1gth of trace to 1aOO la. The magn('siuIU was pre-treated with water to
yards for ('aliber '::JO trae('l's, and to 2200 yards fDrm a Pl'otpctivp oxide coating and one percent
for ealibl'!' .:i() trae('rs. Rt'st'Rn'h awl t!t'velopment ZllW Rtparatp was added as a water repellent. This

('oIJe('l'llpd with sma II arms anllJlunition (~olltinued ignitrI' blpnd pro\'Pd to be more stable under high-
at a very limited rare rp~\llting in ehanges such as hnmidity testing and was adopted for use in 1937.
H\(' df'v('lopJl1t'ut of it gilding metal bullet jaeket Durillg' thp period from 1935 to 1941, develop-
to rppla('(' tlH' (:upronickpl jacket. 'rtw bullet de- 1Ilf'llt work 011 delay action and ~.im igniters for
sign of thp caliiwr .:30 Ml tra('PI' Will: st ClnclaI'dizrd smail al'lllS tra(,I'I's was acthe. D• 10 'fwo composi-
il] 1929. bas('d ulwil thp ,'n!)2~ prototype round; tions wl'rp dpwloppd which were st.andardized.
how!'ver, tht· pyrotechnic compositions wer~ 'fhrse ('ompositiolls furm the basis for all delay
changed signifi('antly during the Iwrio0 between al'tioJi and dim ignit.ers used ill small arms am-
World ,YetI' [ and 1929. For f>xarnpl", many IIl1lnitioll. '1'11<' basi{'. composition is designated 1-
stl'OiltiUlll l'ompollllds SHch as strontium pl'l"oxide. 1:lH Dt'lay A('tion and is composed of 90 percent
stl'ontiulll oX.llatp. and stl'olltinlfl nitrlltl' wt're in- strolltil'm IWl'oxide and HI percent ealciUl:1 resi-

6-3
AMCP 706·185

natt>. Dim initial trace is controlled by the quan- metal particlps of H8 percent metal content. Dur-
tity of magnesium addpd to I-l:J6 composition. ing the war, magnesium powder was used whieh
Standard 1-194 Dim Igniter contains 6 percent ranged from dark gray to almost black with a
magnesium. Compositions incorporating "delay metal content as low as 80 percent.
action" fUllction so as to produce no visible trace Another pxample wai'> the immediate change
up to some prescribed distanep along the trajec- from wet-processing of tracer compositiollS to dry-
tory; then thp trarer composition is ignited. This procf'ssing, or simple blending of the dry in-
action is desirable to avoid revealing gun positions. gredipnts. This was a faster and less hazardous
Dim ignition provides a dim h'ace and has the method but it producpd eompositions that were
advantage of providing fire control directly from more difficult to load, less uniform in ignition and
thp gUll muzzle for somf prps('ribed distance, at burning, and more susct'ptibl!' to attack by mois-
which distancp thl' bright trac!'r composition is ture. ~'or several years the te(~hnieal effort ex-
ignitpd. This type of ignition is particulady de- pelld('d in both the Government and industry-
sirl!.ble for firing at planes and other fast-moving when conducting ehemieal, engineering, and func-
otjPcts at night since the dark-adapted eyes of the tional tests-had the purpose of assuring a con-
glib ncr would be seriously affected by the stand- tinuous supply of ammunition which was intended
anI, lJright igniter ('OIJlposition used for daylight for almost immediatp expenditure by the troops.
eondit~ons. To i!lsnre propiOr functioning and As the war proceeded, it became apparent that
storage "tability 0: delay and dim igniters, it was much of this war production would not be used
lI!'eessary to develop a high assay, wet-processpd immediately aud would probably nmain for rela-
(or precipi.tated) strontium peroxide. Unconverted tiwly long ppriods in storage depots.
strolltium hydroxide (always present in this com-
A I'Pview of the overall situation aimed at
pound) had to be reacted with t hp free abietic
improving' quality of pyrotechnic ammunition was
acid of til(> calciulIl resinate which had prpviously
thrn initiated, and research programs for this
b!'('11 dis~olved in carbon tetrachloride. This wet-
purpose rei'>ulted. In addition, the continuous de-
proel'ssill~ techniqll(' provided Ii ('omposition more
wloprnent of many new types of tracer ammuni-
spllsitiv(' to ignition and lpss affret('d by moisture.
tion ('ontinued. These developments ineluded col-
During' tht' ]!)3G-]!Nl period, the Navy again
orpd sllIokp tracers, tracers for caliber .30 Ml;
beeault· interpi'>ted in the devplopment of dim and
('alibt'r .30 cal'binl'; caliber .45; caliber .50; ealiber
dark types of tru('('rs for use with th(· 40 mm gun
bf'ealls(' of th(' self-d!'stI'l1et rl'quil'<'ments for its .()(); ~O mm; and the larger artillery rounds (most
amllluJlitioll. of which ineludpd the combination types, i.e., arm-
Tmllll'diutdy prior t <Ind during \Vorld \Var or-pit'ccing trat'er, and armor-piercing incendiary
II, dt'llumds \\,prt' suddpnly iliadI' on UB. industry tracer) .
to supply hUl!t~ qllf1rltitips of pyrotpchnie chemicals TIlt' surge of effort for improved tracer pyro-
whieh had JlI'E~vionsly be(,11 supplied in very lim- tp('hni('s, hpgull during ·World 'Val' II, included
itl'd q llaJltitics by olily a ft'w manufacturers. These rpsf'al'ch and dt'wlopment programs to investigate
d"mands resu lted ill largf' proeuetion of such higher plll'ity chemicals, effect of chemical im-
thelllieals as the alkalilw (>arth p<'roxitles, per- purities Oil flllH'tioning and stability, critical mois-
l'hloratl's, nitratps, awl magnesi'Im powdpr uy es- ture ('ontpnt p<'rmissible for long term storage, de-
tablishJll('nts with relativf'ly litde l'xperience in yplopnH'nt of Hll'tal and plastic types of base
tlwir manufa<'ture. Bp('ullst' of tll(' urgf'lH'y of ('losllrl' seals to pI'pvent moisturp putry, alld water
Illaintailling ppak produ<'tion sehedules, Spt·eitica- pre-oxidation and dichromat!' trpatmellt of mag··
tinns tl,·fining the quality of raw materials were Il('sium powder for improv(,(j stauility. Tn addi-
oftpll waivptl 10 th!' detriment of overall ammuni- tion, mally IIPW kinds of materials were drveloped
I ion fll!wtion and stability during ~torag(·. A not- for liSP in pyrot('('huit! l'ompositions. These include
ablt· pxample was maglwsiuTlI powder, which had up\\, ~radps of' alkalint'-t'arth peroxides, atomized
hl'pn 1'1'0<111('('<1 during pt'll<'etinlP as ell'an, bright (('ollsistiJlg' of spheril'ul particl!'s) magnesium,

6-4
AJrlCP 706·185

magnesium-aluminum alloys, and titanium and States after World War I, when commercial flash-
boron powders. light powder was exploded in 25-, 60- and 100-
More basic studies have included inv~stiga­ pound containers with only partially satisfactory
tions of threshold visibility and its relationship to results. In 1925, the Air Corps tested commerClial
background, distance, candlepower, and color val- photoflash powder, carried in towed gliders, as a
ues; the relationship between impact sensitivity light source. About this time, attempts to pro-
of the composition and reliability of tracer igni- duce a suitable photoflash powder followed two
tion, and the effect of cavity geometry and high general lines of investigation. The first was to
speed bullet rotation on the candlepower and burn- develop a fast burning flashlight composition and
ing time; and particle-size measurement and the the second involved the development of illuminat-
effect of particle size on burning characteristics. ing materials which could be detonated. Essen-
Recent studies have been concerned with the de- tially, all photoflash mixtures used during the
termmation of the reaction kinetics of pyrotechnic period through World War II were of the first
compositions by such methods as differential type. Development of an illuminating mixture
thermal analysis and differential gravimetric anal- which could be detonated was not completed until
ysis. Use of pyrotechnics at very high altitudes after World War II.
pres!'nts new problems. 'l'hese problems have re- The hazardous and unsatisfactory system using
sulted in studies of the mechanisms of reaction at the towed glider, which limited a mission to one
low pressure and/or in the absence of an oxygen photograph, was abandoned in favor of a para-
atmosphere and the development of pyrotechnic chute-suspended cylindrical bomb. While other
compositions designed from the data thus obtained. shapes were tried later, this shape, in general,
proved to be most efficient. An important require-
6-1.2 NON CONSOLIDATED ILLUMINANTS
ment was for a flash powder that would produce
Nonconsolidated illuminants are comprised peak light output during the time the camera
mainly of various types of photoflash devices in- shutter was open. This resulted in the develop-
cluding photoflash bombs and cartridges, and spot- ment, by 1930, of a photoflash mixture consisting
ting devices. They consist of loose-loaded pyro-
of 84 percent magnesium, 26 percent aluminum,
technic compositions which react rapidly to pro- and 40 percent potassium perchlorate. This was
duce a brilliant flash of light, when confined, established as the Standard Type I photoflash
similar to that produced by the common photoflash powder.
bulb. In the early part of the 1930 's, two photoflash
bomb designs were in use: one, a rectangular ply-
6-1.2.1 Photoflash Devices
wood box designed to be carried on external racks;
The use of photoflash powder to provide arti-
the other, a paper t'lbe se\"en inches in diameter
ficial illumination for photographic purposes was
and 32 inches long, which coatained about 25
fairly common long before the military use of air-
pounds of flash powder. This latter type became
(,raft for reconnaissance purposes. Toward the end
the first standard photoflash bomb and was later
of W orId War I, when the importance of aerial
known as the Tl or M12 Photoflash BombP It
photographic reconnaissance during the day hai
was rarried within the fuselage of the airplane;
been widely recognized, the military advantages
used a parachute to retard its drop; and was satis-
of night aerial photography also became apparent
faetory for use with aircraft operating at 200
and attempts to provide devices for this purpose
miles per hour at !1ltitudes up to 5000 feet. The
were made by both Allied lind Central Powers.
final modification of this bomb produced a peak
6-1.2.1.1 Photoflash Bombs intensity of 325 million candlepower and an aver-
age total radiation of 22 million candlepower-
6-1.2.1.1.1 Compi)sition TYl',e seconds. The M12 Photoflash Bomb was used for
The study of artificial light sources for night trainiug purposes only.
aerial photography was cvntinued in the United The M23 Photoflash Bomb 12 was devdoped in

6-5
AMCP 706·185

()r<it'r to increast' the number of photographs ob- the "P!Juirrnlpllt that it should be 110 more sPllsitive
tainablt' on a mission. It contained about seven to projretill' fragmrl1ts and bullet impact than a
pounds of flash powder in a cylindrical paper- gPIH'ral Jlurpose bomb.
board case. tJater it was placed in a strt'amlined Work on photoflash compositions continued
steel outer case to improvt' its operational char- with considprabh· rmphasis directed toward the
acteristics. Dt'velopment of the M46 Photoflash deve!opmt'nt of flash mixtures containing calcium,
Bomb was started just bt'fof(' the United States whirh wert' more effective at highf'r altitudes than
enterrd World War I I. This bomb contained up oth,'r photoflash mixtures.
to 25 pounds of photoflash mixture in a stream-
lined metal case and was widely used in 'Vorld
6·1.2.1.1.2 Dust Type 14
War II for photography from intermediate alti-
'}'he need for night illuminant safer than the
tudf's.
standard flash powder bomb (which was easily
In an attempt to increase the intensity of the
uetonatpd by bullpt impact) led to a requirement
light from pyrotechnics, scientists under National
for a Ipss-sPJI<.;itive powder composition. 'fhis ap-
Drf!'lIse Ht'st'areh Committee auspicps at Wesleyan
proach was considered to be preferable to armor-
University and at the California Institute of Tech-
iug th!~ bomb. By 1943, British reports of the de-
nology conducted a more fundamental study of
wlopment of a safe metal dust bomb, using either
photoflash powdpr. Both groups reached the con-
aluminum or magnesium powder detonated hy a
dusion that 110 real improvem('nt in flash output
tetryl burster, had been rpcpiwd. Initial tests
could bt' gained by changing the standard mag-
lI,ad!' in this country of the metal dust type were
IlPsiuJE-aluminllm-potassiulll perchloratr mixture
1I0t ('lIcouragiIl~. It was found that the "safe"
tlWIl in liSP. ('onsidpratioll was then given to pos-
powder produc!'d only about 20 per('ent as much
sibil' methods of obtaining a mort' pffirient dis-
light as the staJldard photoflash bomb. Further
tribution of thr light from thp flash. I<~urther
work r('sulted ill the T8 bomb, which was a cOIn-
study, howpvpr, indicated that a largpr homb was
plete failurp. Instead of dispprsiug" as a dust to
an easipr way to obtain highpr lewis of illumina- ('xplout' in a short bright flash, thp milled mag-
tion. Because of 'IOrtages of aluminum lind mag- IH'Silllll powder used in till' bomh apparently com-
nt'sillln powdprs at tht' starr of \Vorld War II, a pacted into largp adhering mas,~es which burned
mixturp using a magnesium-aluminum alloy as a progrpssively.
fllPI illstrad of Ii mixturp of llIagnpsiulll and Tlw 'rHE1 bomb, containing 70 pounds of flake
aluminuJll, known a..., Typl' I I, ('lass A, photoflash aluminum and wl'ighing over 200 pounds, reaehl'd
powdt'r was dev!'lopP!l. !'atp!" barium nitrate wa." Ii pt'ak illtf'lIsity of one billion candlepower in
adoptt'd as th(' ()xidiz('!'. This mixtUl'p was knowlI about 12 milJist'eonds. This was little more than
as Type 1I, Class B, photoflash powder. I,ater, till' lwak calldlppowpr of tht' 50-poul1d M46 bomb.
it IIt'W staildard photoflash powdpr, Typf' r I I. ('la.'>s A rillg-shappd flash wilh a characteristic n:m-
A, !'om;istill/! of -W IWr(~t'llt alumillum, :W percf'llt IUllIillOIlS ('or!' ,"as prOdUl~p(i, pr!'sumably caused
hariulll lIitnlte, and :30 pP!"('l'nt pota"siulII 1)er- by gaSt'Olls ,lel'ollllJ\)sit;on of till' high explosive
ehlorait' was adoptf'dyl It was found that thp lat- burst!'r. Th!' sa III I' dark rcnter was also noted m
t!'r mixture, whl'lI l'ollfilwd ill II /rt'llvy-wnlIl'd cas .. tht· British dust bombs, Mark 111 and Mark IV.
ing, would pl"OdlH~P lltort' light output from a By th!' ('1\(1 of th(' War, .;;ulal! seal!' tests of a
smallt'r alld safer phototiash bomb. Thl's!' results \'lIril'ty of ltH'tHi dllsts, burst!',..,. and !'asings showed
led to th!' l'!Ull'('lIatioll of fllrthl'l" work Oil thin- (hat a !'o/lil'al burst,'r plimillatt'(} till' dark core.
Intlled plwtojJasit iWlubs 1'01' high altitud!', Hight (·olltiIlUill;.(' n'sl'iln'h on hldal dust bombs
<It'l"illl pltotogmplty. and It'd to till' dl'v,'loPIllt'llt sh()\\,pd that a sat isfal'tory bomb was unattainahle
of the :.;al'l'l" hl'av.\'-wall"d bOlllhs. Tltpsp bombs with Illagllt'sillll1 dust. 'rlw smaJlt r thp bUl'stpr, in
W('!"t' ill produl'fioll in latt' 1!1:;1 ami \\'prl' US( d ill proportioll to \\(·ight of dllst, th!' ,'{realt'r the dli-
tll(' l\.or!';U1 COllflid ill 1!1;)~. Whill' lilliI'll saf('" !'it'Il('Y ill t<'nlls of !'aIHlh'po\\,pr-st'l'0I1ds per grall',
than til!' AI-Hi, this typt' of bomh stiJl did 1I0t 1I1l'\'t but 1}j(' slowt'r thl' Hash. ~ll satisfa!'tory poillt of

6·6
AMCP 706-185

compromis~ could be found. 'I'he use of atomizeu 6-1.1.2.2 Photoflash Cartridgesl6


magnesium-aluminum alloy was then suggcsted While 1I10S: of the night aerial photographs
because of its llonhygroscopic nature. It provided during' th~ parly phases of World ·War II were
twicc tht' peak ('andlepower of magnesium dW'It ob1"cdned at relatively high altit.udes, the need
aceompani{'d by relatively little change in total for low lpvel night aerial photographs during the
light output. lattE'r ph asps of the war '" as anticipated. There-
A separate development project was started in fore, devplopment of smtable photoflash mixtures,
19J8 and led to the standardization of the M122 RS well as cart.ridges and ejectors for this purpose,
(lust bomb in 1952. 15 Thc M122 was cight inches was started hut the work prcgressed slowly because
in diameter by ')4 inches in length, with a total of low priority.
weigLt of 110 pcunds. The bomb achieved a P(;ak In 194:) when the need became acute, the
of 0.82 bHEon candlepower, although the average IT Ilited Statt's' designs were not complete and a
of several tests was about 0.70, and in the best 40 photoflash t'artridge flesiglled ~nd developed by the
millisecond period it produ~ed au) million candle- British was used. This cartridge was based on
power·seconds. It was ~low to peak, requiring t lw ca~f' used for the Very parar;::lute flare. By
about 4~ milliseconds. 'I'he flash was so long in
1945, the first low altitudp photoflash cartridge
duration that on one occa:,ioll two photographs
developed in the United States was based on a
were taken with a single camf'ra using th,> light
sta,ldar<l signal flare casi' and contained about
of a sin~::lf' bomb. Under idt'al ('onditions of clear
five ounct's of TYP3 II, C~ass B f!.ash powder.
atmosphf'r? and nigh reflectance terrain, it was
Its lig-ht outlJllt characteristics were poor and,
possible to obtaiu usable photo~raphs at altitudes
heIH~.(" it was not standardized or USed dllril1g
of 16,000 to 20,000 feet. Good photos under normal
eonditions were possible at altitudes of 5000 to \\lorld War II.
12,00 f{'pt. The l){)mb was stable from an airspeed The first ('llih·d 3tates startdardized photoflash
of IH;i to 400 miles per hour. The RB·26 aircraft ('artridge was developed by hJ49. It contained the
earried a load of ten M122 bombs; the RB-45C then lIew Type rI[ photoflash powder and could be
parried twenty-five; and the RB·50 carried fifty- used to obtain satisfactory acr;al photographs up
two. Procurement was initiatf'd too lftte for US{> to an altitude of 400C feet. These cartriue-es were
ill tllt' Korean action. used extensively in the Kor~all COl,llict for low
altitude night rr('onnaissance photogrhphy. As the
taetical situati.on in Korea oftpn :equired night
6-1.2.1.1.3 Segregated Oxidant Type photographs at higher altituues, the M45 bomb
In 1!l50, tht> development of a segre~ated oxi. was also widely used. Howewr, due to the greater
(\ant t.nIP photoflash bumh was begun in an at· weight of the 1\146 bomb, fewer units could be
tellipt to obtain both the safety frolll impact eal'ril'd, r(,sllltill~ ill a demand for smaller unihl
illitiatiod assueiatt'd with tli(' dust typP bomb and haviJl~ adt'yuatp candlepowe:·. 'rhis requircmep-t
the high Iwak light intensity assoeiated with thl' had bl'PlI unticipatt'd and tests using the Type HI,
photoftaKh powdl'r type bomb. In addition, this ;1O/40/aO formula (potassium perchlorate 30%,
typ!' iJomlJ--ill whieh tIlt' burster, oxidant, and allllninmn 40%, and barium nitrate 30%) had been
IllPtal dust an' louci!'d spparately ill eoaxial cylin. mad(~ as parly as 1947, using chargt's ranging in
dt'rs--ah;o should bl' I'l'lal iwly ills!'nsiti, '. to alti. size from 1.7 to 7 ponnds. Thf' 1.7-pouud charge
tHell' as l'olllpal'l'd to dw dust whil'h dep"nd ('n- was fouwl to Iw t'nt.irely ,hlequate up to 8000 feet
tin'I~' on atlllosphel'ie oXy;~(,ll. Cl)llsidprablp e/fort and \\'w; loaded as till> 1~n2:l eurtridge with an ob-
was llirpl'lpt! towarll th<, d<,\·t'\opment of a bomb tllratl'd delay fuze of two, four, or six seeonds.
of this tyP('; howl'wr, tli(' results cbtaincd did uot \\,fork 01\ photoflash eartridgps eontinued after
pro\,t' to bt' lllarkt'dly superior to those obtained til!' KOI'PHll ('onftict.
with thp IIPW('l' nOlls<,:,rl'l'gatt,d typ<,s. As a result, III IHiil all att'lIIpt was made to obtain an in-
tilt· sl'gl't'gatt'd oxidant photoflash bomb was Hot t'l'('(ts('d light output tOg'pthpr with sat'\' \'harae-
dt'\'('IOl't'd illtu a standardizl'll itl'l!l. tprist i(·s f(lr U'iP in photoflash <.:artrillges. A high

6·7
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 t.ra-
with massive bursters of RDX. This mixture ga.ve jeetcl'Y of the missile. Flash signals also have been
twice the total light of the Type III 30/4.0/30 developed to evaluate the functioning of the mis-
formula and was I elatively insensitive to both fric- sile warhead frequency system.
tion and flame initiation. Since that time, a limited Purther information and references on non-
amount of work has been continued 01'. photoflash con<.;olidated illuminants may be foltnd in compre-
cartridges and associated high rate ejection :.;;ystems hensive reports :wailable.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 BEHAVIOR OF LIGHT


For many years, the flash and smokr. produced In a strict physieal sense, light is that electro-
by the functioning of a small explosive charge, nlllglleti(~ radiatioll which affects thp eye and pro-
usnally black powder, was used as an aid in spot- (Inces vision. TJIP wavelength range of visible
ting the point of impact of practiceammnnition. radiation extends from approximately 3800A to
Oeeasio>wll;', these eharges were also uSdd in con- 7000A; the ang'strom unit, A, is equal to 10- 8 centi-
nection with ('crtain items of service ammunition. mpters. Other units used for indicating the wave-
During and after World War II, the develop- Ipng"th of elE'dromagn£'tie radiation include the
ment of large (~aliber weapons for use in tanks mi('ron, fl., which is equal to 10 4 angstrom units.
erea(ed a need for simple and l'21iable target ac- TII a less striet sensE', the term light is also applied
quisition for these weapons. One of the more satis- to I'lpctromagnetie radiation whose waveJ p l1gths
factory systems developed employed Ii subcaliber art' longer (infrared) or shorter (ultraviolet)
spotting rifle aligned with the major weapon. This thall thosc for visible light.
rifle fired a I)rojectile having a trajectory closely A II forms of t'I('etromagnetie radiation, in-
matching. in the eritical range, that of the major ('lndiJlg lip:ht, are absorbpd and emitted as iniegral
w!'apon so the lowtion of the flash and smoke pro- I!umbers of I'llergy quanta and are tramlmitted by
dnccd by the pyrotechnic ctarge in the subcaliber partirlps known as photons. The amonnt of energy,
round indicated where the major round would hit. E. a8s(wiated with each photon is:
High precision tl'aeking datE! is necessary in
thl' develojlllH'nt of ilitprmediate- and long-range E=hv (6-1)
lllis~;jlp systems. To obtain this data, brilliant !ight whcr(' v is the frequency of the radiation, and It
flashes must bp produced of sufficient intensity to is Plal1!'k's (·oll.'ltant. This equation is often ex-
be r('('ordcrl hy .1 tl'lH'king ('amera and also be of pr(,8)';('(1 in other ways, such as:
a short ellough duration to provid,~ ac('urate posi-
he h -
tion information. Early sources 'If light used E =T = eli (6.2)
[or this purpose wer" of the gas difwharge type.
wherp c is the \"~loeity of light in centimetprs per
'1'0 obtain sufficipnt light intenl-lity without the
sceond; ). is tht., wawlength in centimeters; v is
weight. JWllalty ass()('iatpd with electronic flash
the wave number, the re(~iprocal of the wavelength
s,Vst(,JlI~, PYI'Otpphni,' light som'cps wpre dcyeloped
ill ('plltimptl'!'s; allel h is PlaJlek's consta~lt.
for this (IlIr!>osl'. Whih' th(· tirst pyrutel'lmie sys-
All "I"d romagllt'til' radiations, inclUding light,
t(1Il dp\'('lopl'd, tIl!' Dais,Y Photoflash Cartridgt', was
haV!' I'oth partil'ir alld WIlW properties. Thitl
a satisfador.\' :igllt ,,0111'('(' f(,r Ii tm/king' aid, it
(jllalisti(' Hature is also applirable to IIIdtter. Ac-
l'1'('atp(l oth('r problellls, tl)(> most SPI'iolls of which
('o;'ding to thp dl'Brogli .. "'Illation, thl' wavelength
was the prodlli·tion of Il11'LI fragmf'nts and at-
ass(wiated with it partide of lllass '/II. moving at a
tt'lluation of radio signals, whieh !'esnltpd 1'1'0111 tIll'
wlOl'ity u is given by:
flllletiollillg' of tlH' flash signal.
III addition to minimizing' tl)('s:' problems, It
}.".: '-- ( 6-3)
f:ll,theI' dp\,pfopIIH'nt. reslII tt'rI ill a s('rips of flash 1111'

6-8
,-------------- - - - - -------- ----- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - l

AKCP 706-185

Many of the effects of light may be simply sist, ~n the optical region, of colored lines, colored
explained by assuming that light, in a uniform bands, and colored regions on a dark backgr<Jund.
medium, will travel in straight lines at measurable Absorption spectra al'e 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 eases other light-absorbing materials on 'I. brightly col-
of interest in pyrotechnics. The direction, or path orrd backg..ound. Both types (>f spectra can be
of light, is often represented by a straight line observed ir: wavelength regions outside the visible
called a ray. Other effects, which canaot be ex- by special techniques.
p:ained by geometric optics, must be diecussed in Depending on the appearance of the spectra
terms of the wave nature of light, while still others produced in a given wavelength interval, bott-
must be expl".ined in terms of the particular nature emission and absorption spectra C'Ul be further
of light. classified "8
discrete or contbuous 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- pyrotel!hnic light Gources for both illumination
surements and instrumentation required for eval- and signb1ing is import!JUt; therefore emphasis in
uation, and to carry out the necessa~y research the following paragraphs will be Oil emission
aimed at improving light and color sources. Some spectra.
of these properties in(llude reflection, transmission,
absorption, ref:raction, and the optical character- 6-2.2.1 Discrete Spectra
istics associated with mirrors and lenses. These Luminous gases and vapors nndf'r moderate or
subjects will not be discussed in detail as standard low pressures J:'eld emission spectra which consist
physics texts cover them and may be consulted of dr finitely placed bright lines or closely placed
when required. 20 One of the most important char- groups of bright lines called bands. "'he energy,
acteristics associated with the electromagnet;c spec- E, associated with Ii. quantum of light having the
trum of radiation is spectral distribution; analysis sam£' frequpncy, '1--i.e., a spectral line--is:
of this distribution provides an excellent tool for
determining the emitting species in flames and E=hv=E2-E. (6-4)
other light sources. For this reason, several of where h is Planck '8 constant. This energy is the
the subsequent paragraphs are devoted to this area. diff~rence betwee!l two liuantized energy level~ in
the atom or molecule, designated above as El and
6-2.2 SPECTRAL DISTRIBUTION E',!, so that. the wavelengths of the spectral lines
are characteristic of the radiat.ing source. The
If a narrow beam of white light is passed
number of lines ana their relative intensities in
through a prism, each wavelength is deviated in
an emission spectra also depend on the n!ethod of
direction by a dif:'erent amount and the light beam
exeitation.
is spread uut into all array of colors. The array
A line observed in an emission spectrum re-
of colors is ealled the visiLle spectrum, and extends
sults from the transition of the atom or molecule
from about OA-micron to about 0.7 -micron. This
from a higher, E 2 • to lower, El, energy level ;21 i.e.,
visible portioll of the spectrum represents a very
the transfer of quanta of energy is e~'olved. If
small fraction of the pleetromagnetic radiation
the line is observed in an aborptioJl spectrum, the
cl)mmonly t'lUitted by radiatioll sources, and lies
Ittom or molecule is raised from a lower to higher
between tht' longer wavelrngth (infrared) and the
<jllantizpd pI:erf.,'Y level hy the absorption of a light
shorter wavl'lellgth (ultraviolet) port.ions of the
quantum of thp propt'r frequency.
t'le<!irumagnetic radiation spectrum to which the
eye is insensitive.
Rpeetra of two ~~ent'lal types <ire observed, 6·2.2.1.1 Line Spectra22
(·missioll spectra and absorption STK'ctra. Emission Line speetrll-consist.ing of II. series of sharp,
spedra arl' pro(luct'll by light which is emitted brightl,v colored lines on a dark background-are
from IUlllin()lI~ and iUl'Il11Uf'SCent bodies and con- produced by single or chemically uncombined

6-9
AMCP 706-185

!!
.. -
~
n
~N 8of ~ g.: Al constant; and kl and k2 are integers. The Lyman
series found in the ultraviolet, and for ,vhich
tnF:·.--'rnwlllll~!~,_~l~-rll k, = 1 and k2 = 2, 3, 4, ---, is caused by transi-
ij~1 III i
111'11 IIIII
I TIt
I 11111
lIonilGtion!
\ Ilv.1
tions from excited atomic states to the ground state
00 312 •
7
:1111 I '11'
~
c+-
1

~-r
'!III 50G •
i E or lowest atomic energy state, ItS is also illustrated
6 ~
• I
I
I
;
I
i
304 -:.f in Figure 6-1. The Balmer .;;eries found in the vis-
5 :, ~t-- -:~ 300-0 ~
eE
0

3
j : I
I
I
I
1
293

j
"j!
~ . ible spe~tra for which kl = 2 and k2 = 3, 4, 5, ---, is

...
278 li
1I I caused by transitions from excited atomic states
. I
- -
a ..
to the first ex.cited state. Other series-includ-
'T
235
> ';:
• a
~~
... .2
ing the Paschen series, Brackett series, and
L, o Pfund series-are found in the infrared. The
...i~ spectral lines for materials of higher atomic num-
Figure 6-1. Emission Spectrum and Energy (;!vel! of ber rapidly become so complex that they cannot
Hydrogen Atom he reprt'sented by a single simple equation.

atomr ~nd, therefore, are often called atomic spec-


tra to disting1lish them from the band spectra char- 6-2.2.1.2 Band Spectra23
acteristic of molecules- (Paragraph 6-2.2.1.2). The The emission spectra in the visible or ultra-
complexity of the line spectra prod.uced by emis- yiolrt region, dut' to molecules, consist of a rela-
sion depends on the particular atom involved and tively large number of regularly arranged, but
the method of rxcitatior. Normally, more lines eomplicated, groups of lines called bands. These
appear in a spl',d:: spectrum than in an arc spec- line sequences are called bands because they ap-
trum and both exhi0it more lines than a spectrum pear as structurelffis bands in low dispersion
produced by thermal excitati{lll in a flame. spectrographs. Each band spectrum shows, in gen-
'r.J.e term "lint;, spectra" can also be con- eral, a threefold strueture. It consist,;; of a nUDl-
sidered a coll,'ctivc 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
produeed only by neutral atoms while ionic spec- made up of ;( number of banJs, sometimes ar-
tra refers to spectra produced by ionized atoms. l'anged in seqta"nc!', consisting of a number of
Lc~ss energy is required to excite an atomic line than regularlv arranged lines.
is required to ionize an atom and excite an ionic 'fhi" thrt'efold structure is due to the partition-
line. In general, therefore, only atomic lines are ing of til!' total internal energy of the molecule into
found in the spectra excited by arcs alld flames. three parts resulting' from: the electron configura-
Linrs due to ionized atoms are fOllnd in spark- tion, thp vibration of the atoms in the molecule
excited spectra where excitation is due to high with respe('t to t'at·ll other, and the rotation of the
velocit.\r electrons and the !mergy is sufficient to molecule. Therf,fore, tht' location of the band sys-
t'xcite spectra corresponding to lar/le differences telll in tht' visible or ultraviolet region of the spec-
in energy. trum is dt'tt'I'mined by the magnitude of the energy
Because the !'nergy levels in an atom are re- dIlUl),rt's assoeiated with these transitions. All
lated. to the configuration of the extra-nuclear bunds of a bund system are associated with the
electrons, the simplest line sJwetra are produced ('hang'(' in t'lt'ctron l~ollfigurati()ll. The position of
by atomie hydrogcll (not!' that the spl'ctra for balld h a band syst!'1Il is associatt'd with It change
ionizt'd helium will be similar) wl}('re thl' observed in vibrational t'lll'rgy; ehanges ill the rotational
sI)('('tra (!<'igurt' 6-1) call be represented by: t'lIt'rgy dl'tl'rmill!.' the l()('atioll of the different lines.
Changes in ('nerb"Y of 11 1lI0iecule due to a
(6-5 ) chang!' ill rotational '!llel'gy Ilrt, UII ordpr of mag-
lJitutlp SIllllller thall thos!' dm' to vibrational
where v is the WIlVt' Ilumbt':, th!' recipr()cal of t'hallg'('s wllil'll, ill tllrll, urt' all ord!'l' of magni-
the wav!'I!'llgth ill ,~elltilllett~rH; R is titl' Rydbeqr t ud!' smallt'!' than th!' t'Jll'r,:), !'hllllg'f'S dlle to a

6-10
,-----------------------------------------------------------------------

AMCP 706·185

6·2.3 RADIATION SOURCES


KJnotic Radiation sonrces can be classified in terms of
the spectral distributions of their radiation and
in terms of the manner in which this radiation is

~:o 0:0 0:0 o*fo --


0:0
excited, Continuous radiation is generally pro-
duced by hot sol~ds (Paragraph 6-2.2.2), Although
light produced by certain lasers is very nearly
monochromatic, there is no source of strictly mono-
Figure 6-2. Various Types of Spectra and Corresponding l'hromatic radiation. A narrow range of wave-
Electronic, Vibrational and Rotational Motion
lengths can be obtained by isolating, with a
monochromator or filters, one of the bright lines
change iF electronic configuration of the molecule
produt'ed in emission by certain elements. A wider
(Figure 6-2), The relatively small amounts of
range of wavelencths (however manifest in the
energ-J cOl"responding to emission or absorption in
"isible spectrum to give the sensation of a color)
the far i'1frared and microwave regions are due
('all be isolated by similar methods from sources
to changrs in rOTational energy of the molecule.
producing band or continuous spectra,27
The spectrum associated with these changes is
called the rotation spectrum. 'fhc energy changes
corl'l'sponding to thr 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 rnergy, 'I'hr superimposition of the effects part, on the pmission from a material heated to a
tItl!' to rotation, on those due to changes in vibra- high temperaturl'. The radiation produced is con-
tional lewl, result in the morc eomplex viblation- tillllOUS in nature, resembling that of a blackbody.
rotation siwetrum, As aL'eady indicated, the band
systelt\ fOllnd in the visible and ultraviolet is due 6-2.3.1.1 Blackbody
to thl' sUJwrimposition of pnergy changes due to A "blackbody" is an idealized body which will
('hang(>s in eleetron and eonfiguration in vibration absorb all thr radiant t'nergy falling upon it, A
and rotation. blackbody can bc approximated experimentally by
all enelosure haying a very small opening in one
6·2.2.2 ContinuGus Spectra21.24.2~ wall through whi(·h radilition may enter or leave.
A eontinllOUs emission spectrum in the visible AI'('onlillg to the Stefan-Boltzmaun Law, the total
region is a eontinllous brightly colored blUld ex- radiation E emitted by It blackbody at an abso-
tending from eolor to color. Incandescent solids, Illte tt'nllWrature 7' is:
liquids, and gases, under high pressures, produce
(6-6)
a mort' or Il'ss t~ontinuous spectrum which may
('xtend without interruption from the extr~me wh!'r!' a is It ('Ollstaut cqual to 7.5(j X 10- 0
erg
lIItruviolt't thnHlgh tht' extrem(' infran>d, Thl' ('m- a dt'f.('--4, 'l'h,' intensity of radiation from a
I'IH'rgy in any range, A to (A + dA), of wavelengths blltt'kbotly at a giwll temTH'rature varies with the
of a l'OlltillllOIlS spt'l'trum is a continuous function WIIVt'lt'lIg'th Il('('or(lillg to Plltllek's li:quation:
of tilt' wuw\t'llgth so that tilt' radiation is char-
II!·tt'rizt'd by II ('()J\tinlluJIl of wa\'t'lpngths.
(6-7~
WhilP t'ontillUOIIS spt'..tra art' gt'llerally pro-
!lu('t'd "r il','alldt'sl'('llt solids, liquids, and gases;
I't'gions of ('olltilllllH1S t·mission or aL",ol'ptioll lllay \Vh('r .. r: A is tht' radiaJH't' of wa\"elen~th A, c is the
l'I'slllt in gasps at low Ill't'SSUl'l' wlwll at I.. ast 01H' \'plo('ity of light, k is BoItzllllIllll'S ('onstltllt, and h
of thl' 1'lIt'I'!:Y statl'S ili\'II!"t't! ill tht' transition is i" I'lall('k's ('!Instant, This t'qulltioll; which it;
IIl1qUlIlttiz"t\, pO~M'ssillg' frt't' kilH,tit" t'/It·rf.('Y, 1'hl'8t' Il!uttl·d at variolls ('oll:-:tallt tt'lIlIH'rllturt's ill Figurl'
l'lIl1tilllll!, tlwrd'ol't', ('or!'t'spond to PI'O('t'SSt'S SIH'h as ti-:l, giws ('al('lIl1ltt'd "altH's whit·h Urt· in t'xtrellH'ly
ionizatioll, J't'I'ulIlLillatioll IIlId assu(·illtjoll.:.!~,:'!6 l!(lIl1j Ug'l'!·t'lllt'llt with tht· ilttt'llsity v/llues deter-

6-11
Al'4CP 706.. 185

""I
0
a:
(,) 300
::E
N
:a
u
II N 100
..... 250 :a
(.)
en .....
l- If)
I- .....
e .....
:.. 2CO ~
>- >
t: C) 10
VI It:
Z 150 UJ
.~
'"0 UJ

)( .....
:::I z
.J 100 ~~T' 3000·K ...t
lAo -.----- T· 2~OO-K 0
<:(
I- /T'2000-K cr:: 1.0
Z
e T' I!!,OO-K
DO
0
e
a:

WAVElENGTH,MICRONS 0.1 o!-......._=-!!':! "rL.,~--L""'-:-'="--::--::"'=-':---'::2-:}~OO'='--:3::-:0::'::0:-::0~-:350~0

Figure 6-3. Planck's law: Radiance as a Function of TEMPERATURE, OK


Wavelength for Various Temperatures Figure 6-4, Rad.iant Energy in Different Wava/ength
Bands as a ,I=unction of Temp<'lrature
mine(! t'xpl'rimelltally, The fUllction has a single-
for maximulll t,ffj!'it'lWY drt'rt'ases as does the value
valued maximullI, for eaeh tempt'ratun', which fOl' t ht' maximulIl {'ffj(~it'II('.y,~8
varies with tl'lllperat urI' along curve AB ill Fi~urt'
6-:~, Tht' Wit velt'ngth of the lIlaXimUIll is r.,viven by
6-2.3.1.2 Graybody
the t'q uu t ion:
A graybody, or 1l0nst'leetiVf radietol', radiates
. 28!17 at t'vt'ry wavelrngtn an arr:ount of t'\wrgy bearing'
Ama.r = -7-'- (6-8 )
/! l'ollstant ratio to 1111' amount radiated by I\. hlack-
h,)(lJ :it tlll' samt- ab80lute telllperatllrt·, This ratio
IIl1d tht' radiltllt't- at ~ma.r is giv('Jl by: is ('nl/,'d the t'1II1ssivity aud is less thun one for all
solid radiators, but way dosi'ly approach unity in
(6-9 )
SOIIi/' ellSt'S for IIll t'xtl'IHird wuve!t·ngth region.
As shuwlI ill I-'igurt' 6-4. tht' lunoUHt of fller!n' Thus, tIll' sped ra I distribut iOIl is t'X1H'tIy the !-laml'
radja!t-d ill allY giwJI WIt\'plt-lIgth rt·g-ioll by a l'(lll- liS lhat fol' /I bl!ll'~,bod'y but tilt' total t'lH'r;.,~ radi·
~tJlnt tt-III/lt'raturi' hlllt'khody radiator illl'reaH,-s atl't! i:- It'sli. St \'t'rlll mlid matt·rials<, ineluding'
t'(mtillllollsly but at <li/f.-n'lli raft's relativt' to tht' pilltiP11I1l, iroll. tllllJ.,-rstt'll, !Iud ('arill-n, are very
jllt·rt'IISt· ill tilt' total amount of radiation, with lit .tl'i~· llOllRt'lt'd iw radiators o\'t'r a fairly widr

:(,IIl11~I·atUI'('. 'I'1H'rt't'orl', as showll :11 }<'igil rt' 6.6, rll II g-t' of w!l\'~!t-lIgths.
tht' (-flj('if'llt''\ of ('ull\'l'rsioll of thernllil !'IIt'rgy into
radiatioll ill 1I purtil'lIlllr band varies wilh thl' 6-2,3.1.3 Incandescent Sources
tt- IIl llt-ratllrt' Hilt! .'xhibits Ii maximulU. As th" A.-tllul soli-! I'lIlii'ltllrs ar,' !let "blih'k" IlUJ.
wa\,{'!t'!Igth of tli., hlllld illl'rt'as.·s, thl- tt'IIII)('raturt' thl'il' total (-missioll is It,,;s thau thllt of n bbil'k-

6·12
AUCP '706-185

~
'-' IZOO
dOf)

~ 10QC
IL
<II
W
c! 800·

5
ef.
>-
U
2
IIJ 10
U
r:l
it:
CD

~ 2001
U.
LL.
:;; ~ .~.~- I , - ,--,---,
1800 1;)00 2200 2400 2800 1100 '000
IIJ
!S TEMPERATURE, DEGREES ABSOlUYE

F,gure 6-6. "Optical" Temperatures of a Tungsten Fiiament

cerium I)xides, 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. 'rhe efficiency of a Welsbach
malltle as a light source is also dne, in pp,rt, to
the catalytic activity of t.he oxides Sf) that thfl
chemical reactioIl is faster p,lld, th'lrefore, the heat
production greater near the mantle,
figure 6-5. 'soth6.mal Efficiencies: Fraction of Energy Trmperatnl'es of incandescent sources can be
Emitted by an I$nthermal Radiator in VariOU3 Wavelength ('stimated fl'om their total radiation by use of
Bandt as a Function of Temperatura
Stefan's Law, according to whit::h the total radia-
!xHly. III addition, their etl1issivit~ varies wit.h t.he tion = 5.67 X 10- 11 T4 ergs per se~ond per square
wavrh'ngth and adllal radiators are not gray- ct'ntimc+'pr. Tl'mp(,l.lltures determined in this way
bodies. The I'1H1 iation is thermal if Kirchoff's Law art' eallea radiation temperatures. If temperatures
applies, and the ratio of emissive to absorptiv,: arL' esf:imlited from the v,sible hrightnes:. at a par-
pOWl'rs is a constant for each wRvelrllgth and tern- ticular wa/elength, they are raIled brightness tem-
pprature. Application of thi~ law distinguiGhes lwratllres, If temperat,ures pre estimated on the
hctw(,t'll iueclndl'SCl'lIC(' 01' t Iwrmal radiation, and basis of the best fit of their emission curve to a
lumilll'SI'eIH:r ,)1' radiation exeitl'u by ot1:er blackbody in thp visible rt'gion, they are callen
lIIt,thods. 23 cohr tpmpt'raturps. While it is possible that tcm-
\Vhill' tilert' art' materials, such as tarbon, pt'raturl$ determined by these methods may differ
whosl' elllissivity is IH'arty ('Ollstant with wave- widr)y, ill extremr cases, from the true tempera-
I('ngth, tilt' t'missivity of I·t'rtain otlwr materiuls t urI', th(' difference is usualJy lesf' than a hundred
is strollgly wa \'(' Ieugth.·cirprnlit'nt. If t he ~mis­ dpgrp{,s for incannesc'ent solids such as furnaces
sivity is high in til(' visible regi,)JJ and relativdy and lamp filamenh. (Fi~ure 6-6).
low ill other sfwetral rt'giolls (t'specj~lly infrared),
a !lIfgl'r portion of til(' total radiatioll wiII be in 6·2.3.2 Luminescence
ihl' visib). and tht' heat -to-light ('oIlVt'rsioll effi- Lumiw'scelh'(' results whrn a process leads
eiellcy is improved. As Illl rxampJr, Welsbaeh dirt'l'f.ly to an atom or molecule in an ('xcitec. state,
lIlalltlt's, whil'h art' imprl'gllat.etl with thorium and from whil'h it can return to a low('r elldgy state

6-13
AMCP 7()6..185

a particula!" light source is not an easy task. Theo- 6-2.5.5 Color Value
retically, this can be accomplished for the Y value A commonly used designation for describing the
by multiplying the ordinate of the Y curve in color of a pyrvtechnic composition is the color
Figure 0-10 at each wavelength by the radiant value. This if defined as the ratio of the apparent.
:flux of the light source at the wavelength and sum- light intensity (through specific filters) to the total
minf;' over the visible spectrum. The X and Z (or unfiltered) intensity. This is usually accom-
values may be found by Ii like process and the plished through the use of two photocells, cae of
chromaticity coordinates tX, y and z can be eal- which is equipped with a glass filter. 'l'he ratio
cuiate,l. In practice, it is difficult to match ex- obtained is a measure of the vieual depth of color
actly the I.C.I. tristimulu9 curves; however, sev- of the flame.
eral methods have bAen suggestedSt which give
fairly good rEolnlts. 'rhe more widely used methods 6-2.6 ATMOSPHERIC EFFECTS
incorp 'rate barrier layer photocp.Us and oorrection Absorption and scattering can change the en-
filters. ergy distribution of light pasEing through the at-
mospher~. While the absorption in parts of the
6-2.5.4 Munsell Color SystemS! ultraviolet and infrared regions may be very
The Munsell color system specifies a surface large, th(' more important effects in the visible
color by giving, for usual viewing conditions, its region are due to scat.tering. A light beam passing
through a length x of the atmospht!re is attenuated
positio;l on a more or less arbitrary hue (Munsell
from the initial flux Fo, to a flux F', by an amount
hue), lightness (Munsell value), and saturation
which depends mainly on the scattering coefficient
(l\~unsell chroma) scales having nearly percep-
a, even though individual layers may absorb light.
i :<.tPy uniform steps. The Munsell value varies
from zero for an ideal black surface having a (6-13)
hminous reflectance equal to zero, to ten for iI.ll 1"0."p.articles wh(lse radii are less than approxi-
Ideal white diffusing surface having a luminous rlately Yio the w/tve);rlgth of the light A, the
refl(~ctance equal to one. Munsell chroma is ex- scattering coefficient a can be approximated by:
presned in arbi';;l'ary units intended to be percep-
tuall; , of the san' e size t·~gardless of value and hue. (6-14)
The :trongest known pigment colors have chroroas where A is effectively a constant. The theory for
of about 16 neutral grays; black and white have a sphprical partides comparable in size to the wave-
zero chroma value. Munsell hue is expressed on a length of light results in extremrly complicated ex-
scale intended to divide the hue circle (red, yellow, pl'esilions for the scattering coefficient.
grt'en, blue, purple, and black to red) into 100 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 of Color shorter wavelengths so that the color of the trans-
has been widely used as a color standard. It con- mitted light will ~hift toward the red. The pref-
sists of forty constant hue charts where all color erential sf!attering of the shorter wavelengths de-
Ran/pIes 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. At
stant Munsell value and the columns being value this time the t.ransmitted light appears blue or
scales at constant Munsell chroma. Comparison green. Tl ,en~ is little preferential sCI!.tte!"ing for
of an unknown color with these two faffiilies of particles whose radii arp greater than one to t.wo
sClllf'!; gives, by interpolation, the Munsell value microns. Little or no variaticIl in transmission
and Munsell chroma of thp ulJknown color, Inter- with wavelength is observed for fOb>'}; 0;'- thin clouds
polation between the constant hue charts gives the becal'se thl'ir drop size distribution is broad, If
Munsell hue. the scattering particlet are polydispersed but j

6-14
I\MCP 706·185, Cl

by tilt) l:llIlssiUIl of /·adiation. Und'H these circumstances, The radiatiilfi from any system in ~qmplctc
th~ ralliatilHI pru~ucl~d at certain w4velengths may be thermodynamic eqltHibrium wi!! be continuous anJ :.he
IlIll.:h t.\r<:ater than lht: amll~nt expt~cted :tuc tu Hlermal ~ilme as a blackbody ai tha t temperature; however, ,lame
rauiation. Brlla:Jly speaking. luminescence refers to the syst:ms do not fit in thiS category due to thei!
en:iSSllll\ lIf light for : ny rc:..son other than high n onequilibrium nature. In malt sroan flames, the
temperature. emission \.if rl'diation by the em!~ting molecules and
particles :s not balanct;d by the ab~orption of radiadon
1j·2.3.2, t Chemiluminescence resulting ir, a steady deactivation (,f excited molecules
It Ihe cxriTed atom or molecule :s forme(l dll ~ctly as and Tadiation cooling of st)lid particles. This e~ugy loss
the \\':,uitur a ~hemical reacti:)n, the phenomenon is must be made up by collision rl'Ocess('s in the f1clml; and,
kllLlwn as chemiluminescence. The emi~sion of if not efficie·\t enough, the di~j.rjblltior IJf enl rgy
fO[lllaIJL'h~l(h: bands from th,:, "cCj(~1 flame o" of ether between the exclted mole.:ules or solid parhcles may
aldc:hyd..:s and certain hydrocli~l:Ions, at tewpe(atures differ from equilibrium conditions. ill adJition, chemical
h~IW~C:ll 200ll and 400°C, are uue to equilibrium :nay not b~ obtained.
Chc"11ilumincsc..:n~l~. Radia';on frum the reaction lOne of The small particles that are fOimed in many' flalJles,
a [jUIl,"::; burner, tbe inner cone. is shont;l!r than can b( indudir.g most pyrotechnic flames, definitely influ-:;nce
"cCllulllc,l for thermally, and is duc to tile radiati'm produced by these flames. The continuous
t.:hc"liI1l111inesccil~c. The amo,lIlt of radia\it~n prodt.:ced background is empt>asized aId, in mar:j' l;ases, mo..t of
by .1 pyrotechnic flame which is due to the radiai.i:.':: produced is cont.inuous. This continuum
che milulllinesccnce is difficult to determi'l,;! and, under ;:>roduce<l by particles in (l flame cijffer~ from thl\t
I.crl:tin circumstances, the amoutlt may be ~ign;fi(.am. produced by a grayht'ay or blac\(bo~y be~ai.lse:
(I) The -emissiyj,y vf the material which makes up
6·2.L!.2 Phosp!lOrescence and Fluorescence the panicles varies with the wave!ength.
C,:rt~tlil ,ub .;(ances, including the ~F.lfides of calcium (2) The scattering of light by the particles change'S
anrl h;lIiul1I. when exposed to radiati,m, will cuntinue to with wavelength even if the mat"'ri~l making up the
gl nw a Tlef t fit' J adia [io'1 source is removed. This particle is black or gray.
ph'lllIllh'lllllt b known as pho~phorest'el1ce. In oil,cr While most cf the radiation produced by flames IS
11'.<tlc'tials. the !1)ow l)e!sists only for a fraclicll of a thcnr.·11 in origin, some of the radiation is Jue to
~~':()f1J. In the latter case, the phenomenon is known as chemilumint)sl.;fll1ce where the amount of light emhsion
till\! r"st.:~IlCC. I n general, the radia tion crli~ted by a i~ mu~h greater thlln that er.pected from ~ile\[oal
phosplwrcsccnt 01 tluor(;~cent materi..!! is of ,\ IUlIger emissiun. For prc'11!xed flames 0[ the "Bunsen" type,
w:tve!e'lgth ti\an the exciting ladii'tinn. In all these ca~cs. the emissi'JIl from iPtercan,i1 gases is the:Mal in origin.
abwlptlOfI Qr the C)[Cltlllg radiation causes rhe form.:lion FC)\, the reaction zone (the ihner cone) there ::J more

(If all eSi;i«~d molccule or atom. The IOllger w~velcngth mdiation than can be a~counted for thermally.
of the cmil!~ci light is attributed to the 'eturIl of the 'The d:aracteristicll of the radiation produced by all
('xci[,'d panide to the original llonexcitcd st:lte in two flames. whether they co:Jtain small particles or not, will
or rnore stcp~, rathcr than by a single tra'isition. '!lange as the flame size incre:tses. Self-absorption
~~com~s mme im}:-ortant and the radiation will a::,proach
6·2.3.3 Flame S{\urces2~,?6 more nearJy tru.t of a blackbody.
'nil;: dlJ"f distinction between combusuun anft other
chemical n;action~ is the :lppearan:cc of flame and the , ~HOTGMETRY
6,2.{
emission of light. Most flam~!> produce an emission : Photome~ry is the science of measuring light. Since
spectr<l of discrete band;; which may, (;..pecially for the eye if. very II<:nsitivc and nonlinear in its response to
lumillous flames c(lntaining solid particles, be tadiation, an arbitrary unit, the lumen, is used t·)
su~nmp')sed on a continuous baC'kground. e~'aluatc radiant electwmagnetic flux in

6·14 ' W
AM'CP 7()6·185

terms of its visual ~fte(~t. The h:men has the by eollision can bp utilized to inr~rease the nUMber
same dimensions as power. It has been found by of ('l'~ctrons rpllching the anodp for a given amount
t1xperiment thill, for be so-called normal observer, of illeident light. Still more sensitive photocells,
OIl(' lumen is l'quiv.1.1ent to 0.00.161 watt of mono- knowll BC;; photomultipliers, use the phenomenon of
('hromatic rrreen light of a wavelength correspond- secondary ('lectl'on emission to produce an internal
ing to the maximum in thevisibilit.y curve, 555 ampliachtiO!l of the order ()f one million. In all
millimicro~ls. Thc number of lumens produced eases, the reS1'('11se of the photocat.hode surfuec is
by Gne watt of radiant power is (JaIled the lumhous !oltH'ctrh1ly selective llnd is determined by the ba!<ie
efficiency of the source. 1<'01' a monochrvmatic matt-rial [\Ild its prepal'ation. Another t.ype of
source, the lumino~l.s effieieney is obtained l)y mul- lightosensitiv(' cells is the Dhotoc(ll.ld~l.ctive cell, in
tiplying the relati ve visibility for the wavelength :0 which the action ;)f light CSUS?S an increase in the
1!llpstiOJl by 680 lumens/watt. v ('lpetrica! eonductivity of the device. T~e selenium
eell is an t'xample. A third type of detection uti ..
lize:. the photo"oltaic effect in which a voltage is
6·2.4.1 Instrumems for Measuring Light Intensity rroduced across the interfa(Je separating a semi-
Instrllmen~c used tor the measurement of light eondnctor from a conduetor by light incident on
intensity ean be divided int;) two geheral cate- the interfacf". A eommon example of t.his type of
gories: (1) those which usc the heating effect of d('te('tor i~ the copper-cuprous oxide cell. All of
the radiation, :md (2} those which make llse of these deteetors-rhotoemissive, photoconductive, or
quantum pifeds of the radiation. photovoltaic-have a s':1leetive spectral response, as
In the first eategory, the radiation absorbed by do photochemical reactions, including photography.
th\' receiwr raises .its temperatur(1 which is sensed Thp spectral reSpOllf'P of photocnemical rea~~tions is
hy ;;omp appropriate means. The thermocouple selpetive because Clily the light which is absorbed
uses tIl(' tIIPJ';nJeleetric effect while the bolometer will produe(' a photochemical effect. Actiometers
lI;;es thp thange in resistance of a resistan(;c ele- 'lse photochemical reactions in which the quantum
ment, whicil may be a scnlieonductor, to sense this yield, whieh is equal to th.~ number of induced re-
temperature rise. Generally, both of these de- actions divided by che numbe,' of quanta absorbed,
teetors are speetraUy nDnselective in their response h'ls bpen accurately determincd.
to raJiation, i.e., tlu:,y absorb like gray bodies. In
another type of thermal detectur, which may he
sl'lediw in its response, tl \ radiation is absorbed 6-2.1,2 Measuremeht of the Light Output of Flarts
;)y .~ f~as. 'fhe tempet'ature change prounced in the Flare output measurementE' are usually mad~
gas, which is eOllfined to a very small volume, is in a photometric tunnel. This tunnel is a tight-
.~enspd as a prl:'ssllrp l'i<>e. tight structure with a fan to remove smoke and
Thl' secund eategory of (1eicctors are the ppoto- with instrliments to measure tte bright.neps, color,
(leteetol'H whieh, in prinl'ipk, count the number of and burning tim(1 of a flAre. The inside of the
quanta of radiCl.1;ion. A 11 example of a common tunnel is usuaily flat black a!ld hafDed to elimi(l.8.te
detector in tlIP se(~ond catc/~ol'y is the photocell reflections. The tunnel is usua.l1y built in three
whieh is II photopmil'si ve detector. 1t depends f(lr parts: a burning room, which contaim the lJurniiig
its opt'mtioll ell tile pjection of l'leeirons from a table, ignition apw.ratus, and exhaU''1t, fan: a long
specially pl'epared sur~a(~(' by the incident quanta tube section from 50 to 100 feet long which he.llses
of radiati;m. III a Vr:CUUIll photocell the rfsponse the photometric transdu('ers; and un instl'll.ment
tll in(jilent radiatiOll is a linear fmICtion or the room, which house& the recording iflstruL1ents and
light intensity. The dectrons PlIlitted I:lr(~ drawn provides a plaee for the persol'nel to work. More
to the anod., from dlP sensitized eaelOdp by a rela- ('(lIllplete lilcaS~lrement capabiliTY for a tUllllel
tiVt'ly slIlall \'olta~~(~ applipd to ti'e eledt·odes. Gas- WOUld ineluI)e the ability to c.eterwine t.be vi,iblc
filJ(~d j)hottw('Jls are nonlinl'ar in their resllOnsp spectral ontput of flares, ultraviOlet and infrared
to ineidelJt lig-ht intpllsity, but are mort' sensitivp outputs, and flam:' temperatures. 'rhe t'mnel must
than th yaClIl1m type beeause ionization of the gas have .~ulibratinh' lights and color filtc~ for caUbra-

6-15
tion of the :.nstrllnlCnts. Luminoas intensity mea· 'lteradians. A unit point source, emitting light uni-
surem~nts in tenus of eandlepower are often de- formly in all directions, radiates 471' lumens. The
termined by an ilJ~trument which consists vf '\ unit ot' luminous intensity--adopted by the Inter-
barrkr layer photocell, filt~rs, and a microammete::'. national Commission on IllUl.llination in 1948-is
This i.llmuinometer is placed at an accurately the eandda. It is of such a magnitude that a black-
kvown distaAlce from the point at which tile candle body rad,iatvr at the temperature at which pUl"e
or assembly is to h€' burned and is th~n calibrated platinum solidifieh has a luminance of 60 candela
by means of 1'. standa.rd illcandese.ent white light p~r square rentimeter.3o An earlier unit of lumi.
source. During the 'lUrning of the item, lllumi. ~lOUS i.:1tensity, the candlp, is equal tl) 1.02 candela.
rrometer readings ar'.l taken at p:redetennined time An·)ther unit, candle power, also has been widely
int<:rvaJs throl1.ghoat the btl.rning period and the used to expres~ the luminous inteIlsity 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 ti~splayed :;,n a discomaged, they have been widely used Ly many
graphic r~cor~er. Tn thi.s case, the OUt.Pllt of the pyrotechnic investigators. Therefore, the terms
photocell is feu into the recoreer which has been cannela (preferred), -.:andle, and candlepower will
ealibrat~d so tbat the anti':lipated libht output wiH be used inter'lhangeably iT> this handbook.
produce Ii nearly full scale reading. A graphic
r\;;cord is supL~:;"iJr to readings tal,en with an illumi- 6·2.4.4 Brightne.3S
nOP!0tH because all vari&ti(;ns during burnings are The concept of hrigbtness is required because
recorded and thus are available f01:" iutufP study. most sources are not points and the concept of in·
The area under the Cllrve thus obtained represents tensity is not readily applicable to extended
the candleeecond value of the t(Jst~d. item. An int('- sources. The brightness of an extended source ic
,~ra~o~, which gives the candlesecond value of t.h:l expressed in candela per squa..·e centi:;neter of
t'omposition cl.lrectly, is c!)upled with the photo- emitting surface.
cdI, thus avc,idillg the t.ime con~mmiLg and less
accu~ate method of estimating or planimeteriug 6-2.4.5 IllUMination
the graphic record. The illumination of a surbce is the limount of
-fhe stat:~ of the 8{lipncf: in photometry is not light flux (lumens) incident upon a unit area of
yet l1re~ise, and meast:Nment e"'rors within ± 10% sul"fa(·e. An illumination of a lumen per square
Oil flares :lre as good liS can now be attained. Speci-
fOOT is called a foot-candela. The illumination E
fication .MH~-C-J.8"162 covpr" general requirements of a spherical surface of radit:s r, enveloping a
altl.ough later refinement!'. have brei! made at each
po~nt source of intew.ity I, is given by:
milita7 im;t~llation. Refl"es~ntative facilities for
tbese meaSl;rements- are to be found at Pica tinny E --..!..... - _471'1 _...!..._ lum~~ (6.11)
A:'(l~!ir:d, Dover, Npw Jersey; Naval Ammunition - A - 41Cr'? - r2 una Ul"ea
1'e\.ot, Crane, h'f[hna; Nuv'Ll Ordnance 'l'est Sta-
for a plane surface at a distance x from a point
t;on, Chilla Lakt~, California; and NfI'm] Ord-
source of intensity I:
nante Lahor'lioI'Y, Wbitl~ Oak, SiI-:er Sprh1{~,
!.Idryland. I
E = -x2 cos () ( 6.12)

6-2.4.3 Inte:Uity whpre (J is the angle between the source vector EillU
TI:'e intensity of a point source, in any direc- th;> normal to the surface.
tion, is defilJl:!d af t.hf~ light fl~lX in lumer,s per unit
soiid angle (pel' sterarliall) in that direction, or
6-2.4.6 Ph9tometric Units
. ,11' The units employed ill photometry are a con-
1------ (6.10 )
- dw tinuing source of diffieulty, espec;aUy for the
when, I is 1.11(' inteDsity Hl ealldela and dP is the novice. A strong effort is being made to secure
IU'll,'IlS of flux within u s-nlall solid angle of dw greater ulliformity, rpduce U:e number, and pro-

6-16
AIICP 706-185

TABLE 6-1
CONVERSION FACTORS FOR PHOTOMETRIC UNITS

Physical Phycho Phys·ical


Radiator-source: of Radiant Energy Luminator-SOU1'CC of Lumvn01lS Energy

Radiometry Symbol mks units Photometry Symbol mks nnits


-:;:;.=.;=' ---- ..
Radiant Lumino1ls
energy joule energy Q talbot
density joule/rna 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-cm 2 radiance B lumen/sterad-m 2
irradiance H watt/m 2 illuminance E lumen/m 2
Spectral Luminous
reflectance reflectance r
Spectral Luminous
transmittance transmittance t

Inum,natioll
1 lumen/ft2 = J. foot-candle ,== 10.764 lumell/meter2 = 10.764 lux
1 lumen/meter2 = 1 meter-candle = 1 lux - 10-. phot
Brightne88
1 foot-lambert = 1 equivalent foot-candle
1 lambert = 3183 eandle meter- 2 = 296 candie ft- 2 = 2.054 candle inch- 2
Ezpo8'Ure
1 meter·candle-second = 1 lumen·second meter- 2

vide more logic m photometric units. 7 •s Some of tent of white light; only monochromatic color9 are
the more eommon photometric units are sum- completely satnrated. Brightness or lightness is a
marized in Table 6-1. The units of photometry are measure of the amount of light being ero~tted or
often I4pplied, incorrectly, to measu!'ements of in- reflected from the colored light sources OJ colored
frared or ultraviolet radiation, or to describe the object. Brightness applies to luminoru: 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 regiolls. color can be represented on a color solid (Figure
6-7) where hue changes around the circle, light-
6-2.5 COLOR81.82 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 heam. 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 retiml of the eye by these wavea-. Colors by a suitable combination of 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 el'd, blue-violet and red. As
sensation produced. Hue refers to the color, i.e., indicated by the additive color cirdes in Figure
red, g'reen, or blue. Not all hues are observed in (;.8, proper proportiGHs of red and green light will
the spedrum of sunlight. The purples are notably produce yellow. If the proper amount of blue-
absent. The sensation is a measure of the con- purple light is added, white light is produced.

6-17
AMCP 706-185

White

t -..-
I II

C
&.
.r:?
..J
Blue

Purple

....
Red

Block
figure 6-S. Additive Mtxture of Primary Colors
Figure 6-7. Dimensions of the Psychological Color Solid
type. It was found that only the mutual ratios
Colors such as yellow and blue-purple, that pro- of three primary colors are of importancc in de-
duce white light when added together, are caned 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- expressing each primary as a part of the total
purple (magenta), and for blue-purple is, as indi- impressio':l of the light type obtained by the eye.
cated earlier, yellow. 7 Thus, for red, green, and blue, respectively, the
ratios are:
6-2.5.2 Subtractive C610r ,. g b
The light incident on a nonluminous object may
be partly reflected, partly abl'K)rbed, and partly
which necessarily total one, and, as a result, only
transmitted. If the incident light is white, the
two need bp designated to determine the light
transmitted light will be the color which is com-
type. A particular color or .lor point, therefore,
plementat·y 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-degrce 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
~leetive absorption of light which pelll'trates a
determine the color points of the various light
short distance bene.ith the surfacp before it is re-
typrs. Each set produces a "color triangle" with
tleded.
its own shape.
In order to effect a standardization, the Inter-
6-2.5.3 Chromaticity Coordinates national Commission on Illumination (I.C.I.),· in
The tridimensional color stimulus required by 19:31, re('ommemled that all subsequent color data
the eye has been studied in detail and has led to a
• Now known as C.LE., Commission Internationale de
precise ml,thod for expressing a particular light 1 'Eclairllile.

6-18
AKCP 706·185

I.'
1.11
1.7
1.11
1.5
.?O(.
1.4
...en
::J
1.11 ,100
~60

..J 1.2 500

~ 1.1
.5",,0

Y
VJ
.~oo
::J 600
oJ
::J
:IE .:900-
640
t= 100
en

¢~./'
.200
II:
I-
J-
.100 1'o~\J. \..\
.~Il

380
.000
0,000 .200 ~~OO----'----;~f--660 -.- ~;60-'- .100
x
Figure 6-10. C.I.E. Chromaticity Diagram

WAVELENGTH, MILLIMICRONS Since, as indicated earlier, only two coordinates


are required to describe the light type, the values
Figure 6-9. TristimlJlus Values of the Spectrum Colors of X and Yare plotted on a chromaticity diagram
According to the 1931 I.C.I. Standard Observer
(:B-'igure 6-10) and form a loci of monochromatic
be expressed in terms of the same tristimulus sys- spectrum colors. The line drawn between 380
tem so that the results would be immediately com- millimicrons and 700 millimicrons fonning the
"base" of the triangle is called the" purple line"
parable. The Standard Colorimetric Coordinate
along which no perceptible colors exist. The
System (X, Y, Z color triangle) was introduced
cruter of the triangle (C) is th equal energy 01"
which is based on the color sensitivity curves shown
"white point" and haf been de8ignated by tile
in ,F'igure 6-9. These curves are the result of colot'
I.e.I. (or C.LE.; used interchangeably) as the
{'ompa"ison t('si's cOllducted on mallJ observers and
light produced by "Illuminant C" which corre-
compiled to produce those for the "standard ob-
sponds very closely to average daylight. COlllple-
server. " The primary colors were selected so as to
mentary colors will fall on a straight line PdSSing
produce no tristimulu:, value less than zero (avoid-
through Illumillsnt C. also, an)' color can be con-
ing tilt' use of negative values in computations).
sidered as a mixture of Illuminant C and spec-
F'urther, the eurve for the Y -factor is identified
trum light having a wavrlength given by the in-
with the eye-sensitivity curve for light, which forms
tersection Gf a straight line through Illuminant
the basis of photometry. 'fl:e values of X, ,1', Z are
C and thl' given color G, with the Chromaticity
the amounts of the three I.C. I. primaries required
eurvn D (Fig.ure 6-10). This wavelength D is
to color match a ullit arrllJunt of energy having
call1'ti the dominant waveleng'th In addition a
t.he indieated wavelength. The ehrol['.aticity co-
mixture of two ('olor oointl-i anywllP!"e on ~he
ordinates fur each wavelength are obtained from
dia~ram will produce a color whieh is located 01) a
til!' values of X, Y, and Z by means of the ratios:
line between the two initiJlI colorfo. Other usefnl
.r= as}1f'ets of the ChIomaticity Diagr.nn can be f(.u.nd
ill tht' refl'rences. 82
Till' assiglllnent of ehromatieity coordinates tJ

6-19
AMCP. 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 Y value A commonly used designation for describing the
by mt' ltiplying the ordinate of the Y curve in color of a pyrotechnic composition is the color
Figure 6·10 at each wavelength by the radi&nt value. This is defined as the ratio of the apparent
flux of the light source at the wavelr,ngth and sum- light intensity (through spccific filters) tv the tot.al
ming over the viRible spectrum. 1.'he X and Z (or unfiltered) intensity. This is usually accom-
vaines may be founu by a Eke 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 filtcr. '{'he ratio
culated. In practice, it is difficult to match ex- obtained is a measure of the visual depth of color
actly the I.e.I. trist.imulus curves; however, sev- of the flame.
eral methods have been sllggestt:d81 which give
fairly good result". The more widely used methods 6-2.6 ATMOSPHERIC EFFECTS
incorporate oar"ier layer photocells and correction Absorption and scattering can change the en-
filters. ergy distribution of light passing through the at-
mosphere. 'Nhile the absorption in parts of the
6-2.5.4 Munsell Cola! SystemS! ultraviolet and infrared regions may be very
The Munssll color system specifies a surface large, the more important effects in the viRible
color by giving, for usual viewing conditions, its region are due to scattering. A light beam passing
through a length x of the atmosphere is attenuat.ed
position or, a more or less arbitrary hue (Munsell
from the initial flux Fo, to a flnx F, by an amount
hue), lightness (MunS€ll value), and saturation
Wllich dept'nds mainly on the scattering coeftbient
(Munsell chroma) scales taving nearly percep-
a, ('ven t.hough individual layers ll~ay absorb light.
tually uniform steps. The Munsell value varies
from zero for an ideal black surface hMing a (0-13 )
luminous reflectance equal to zero, to ten for an 1'-'01' pal.'ticles whose radii are less than approxi-
ideal white diffusing surface having a luminous mately %0 the wavelength of the light )., the
reflect&nce equal to one. :Munsell ~hroma is ex- s(~attering coefficient a can be approximated by:
pressed in arbitrary units. intended to be percep-
tually of the same size regardlesG of value and hue. ( 6-14)
The strongest knuwll pigment colors have cllromas where A is effectively a constant. The theory for
of about 16 neutral grays; black and whitc have a spllPrical particles comparable in size to thc wave-
zero chroma value. Munsell lut\) is expr?,ssed on a lcngth of light results in extremely complicated ex-
seale intended to divide the hue circle (red, yellow, pressi01ls for the scatt(;ring coefficient.
green, blue, purple, and black to red) into 100 A8 discussed in greater detail in Paragraph
perc8ptuaUy equal steps. 7-2.1.1, smaller droplets preferentially scatter the
The pocket edition of the Munsell Book of Color shortpr wavelell~ths so t hat the color of the trans-
has been widely used at; a color standard. It con- mitted li~ht will shift toward the red. The pref-
sists of fort3 COllstant hue charts where all color l'rential scattering of the shoder wavelength~ de
Gamples n.aking up a ('hart ha'"e the same hue. The "reases with i:wreasing partiele size until the
coloI' samp!t·~ making up thl~ ehart arr arrangr,d in particle ra,!ii bpeornp sligHly gl'rater than that
ro\\:; and cclunms, the rt\WS being dlJ·oIll" a I con- ('orrcflpond.ing" tt) the maximum for red light. At
stant MUllseH valup and the C')lul!lns being value this timp tIl,' tra:mmitttd li/.;ht appears blue or
sl'ales at COllstallt Munsell ehroma, Comparisoll gTP!'I!. T "l~r<' is little prefl':·t·ntial scattering for
'If an unknowJI color \\itll these tWf families of paI'tidls WilO:.t' ra(lii arl' ~r"atl'r than one to two
sC'nleR I!ives, by illtC)·I~)latioll, the ',li,lIlsell value microns, Ijittl(· or 110 \'/lria:ioll ill transmbsion
awl l\1uns... ll chroma of the unknown (·olor. Inter- with wa,'ch'ng-th i~ obseI'\'l'(1 for fogs or thin douds
jlolatiOl! lwtw('cn tht· "ons~,ftllt hue charts gives the h('i',LU~l' th('il" drop sizl' di!>tributioll is hroad, If
,Munsdl h~l{" the scattering" pltrticl,:'s are polydispt!rsed, but
AMCP 706·185

smaller than I)ptlmum size, the transmitted light TABLE 6·2


will be more red than the ineident light, account- CANDLEPOWER REQUIREMENTS VERSUS
ing for the deep red of the transmitted light from HEIGHT OF ILLUMINATING SOURCE
the setting sun.
Ground Brightness,
6-3 CONSOLHlATED ILLUMINATING Height Above Gl'Ound 0.1 1.0
DEVICES
A eonsolidated;iluminating composition IS 100 ft 1,000· 10,000·
formed by mechanically pressing, eAtrud~ng, or 500 ft 25,000 250,000
casting finely di videa illuminating composition 1000 ft 100,000 1,000,000
into some solid shape which often has a candle-like
* Cantllf'power requirements neces&ary to providu speci-
form. When ~uch an item burns in a propagative fied illumination (0.1 and 1.0 f\) on the ground .f:rom given
fa;,hion, the fla~ne radiates energy in the uHraviolet, heightR above the ground.
visible, and iUlral'ed region of the spectrnm. In
most cases, less than 10 percent of the radiant above 1.0 foot-lambert will generally re4,uire au
energy is ill the visible ~egion. 'l'he distribution unreasonabll' amount of illuminant-.) Although it
,ma relative intensity ('haracteristies of the radia- is often difficult to produce, white light provide&
ticI~ produced, in any given region I)f thp- spe4'.l- thl' best illumination for the greatest range of pos-
tJ urn, are determined basically l'y t:l.e products of sible conditions in the field. Since illuminating
tilt; bllrnillg reaction which emit in that region and flares arl' used under field conditions where the
the temperature reached by the emitting species. lo~atioll and reeo~'niti(ln of unfamiliar objects are
Light-producing pyrotechnic devi'~es are char- important, suffici~nt duration and intensity are
acterized for military PIlL'poses by luminous in- required to r:omplet,~ the visua.! observation and to
tensity, ('0101' value (hue and saturation) of the rlistinguit;h objects III the field from their back-
flame, and bmniItg rate. Sensitivity of the com- ground. Canrllepower requit'ements neceSlSary for
position to impact, statie electricity, end friction adel{uat(' illumination, 0.1 to 1.0 fl)ot-Iambert, fl,
should be :J. minimum f0r safety. The ig!lition tem- when the flarl' is suspended above the ground, are
perature, ignitibility, stability, anri hygJ'oscopicity ~iv('n in 'l'able 6_2.33

are important in determ;uing- th~ certaint~r of A diagram of a parachute suspended flare is


functiolling. shown in F'igure 6.. 11 indicating the manner in
which grounJ lIlumination E Llay be approximated
6-3.1 ILY,UMINATTNG FLARES from values of II, the hei!{ht Jf the source; r, th':)
radius of the desiL'ed illumination; and I, the
An illuminating flare pruducl'S a f'lingle source
intl'Ilsity of til!' sourer. Intensity curves for
of illumination which is I~enerally of high candle
variou'3 lll'ights to prodilce a minimum value for
power and SIl bstalltial duration. l<"'lares may be
E of .02fi foot-eandle are shown in Figure 6-12.
pal"achutl'-"nl)rJOrU'~I, towed, or stationary. While
th!'ir primary fUlIction is illumination, they may be
Ilsed for j(lentificatioll, ignition, loeation of posi- 6-3.1.1 Aircraft Flares
tiol1, or warning. l<~larclS for aircrhft J. rovide illumination fo1'
III ~t'ill'ral, 11 PYI'(lteehnil' illmninating fllt'.'(· rpeonnaissClu('e, obsl'rvatioll, bombardment, land-
slJOllhl ::1:1 (1) prl)/lul'\' I'sspntially wIlite light, (2) ing. and. aJs(1 targets for practice firiag of anti-
h!l\'\' all intensity in f('Ot ('/llldIc" adelpmtp 1(\ pro- airl'raft gUllS. While detailS of flares vary with
dUl'l'lI bright/H'ss Il'wl from 0.1 to 1.0 foot-lambert their purpose, fiarrs for illumination have eer-
Ol\ at'eas or '!1rgl'ts \\itll miuimulIl refipctivity, and tll~n eharaeteristics in l'OllllllOIl in that they all
(:1) burn at peak int(,J1.~ajy for IlI~lilliIll'lJll of thirty product, high-intl'Ilsity whitt' or ('olored light for
~:\'('(Jl\(ls 1I1ll1, preferably. ill (,XC('SI> of onl' miuHt!'. an Ilpprl'l'iable h'llgth of tim{'. MO>lt air.~raft .!lares
(Tlvst' valups lirl' desirablt'; hO"'l'\'l'r, where neees- art' paral'hutt'-snpport('d to retard tl,eir speed of
sllry, 10wl'r ll'veilS may be adt'quatl'. Illumination fall Ilud thus pruvidt> illumination over a given

6-21
AMCP 706-185

TABLE 6-3
CHA~ACTERISTICS OF VARIOUS ILLUMINATING FLARES

Time
from
~Be I 1
I Max8peed
actuation
to full Burning Candle-
I Max
of airplane
at time of
jv.nction, time, POW1fT', FaU, MaxL, dia, Weight, release,
Item Method oj actuation .~e.c Bec 10' jps in. in. lb mph
-. ~

FLARE, AIRCRAFT.
guide, I min II
T6EI (white) 650
T7EI (red) Electricity 6to7 -15 to 60 700 ....... 5.4 5.46 ....... . . .. ' .....
'f8El (green) 90
:

FLARE, AIRCRAFT:
parachute
I
MBAI (w/o suspellSion
bands) (emergency night
landinFt)
Release from
airplane
3.0 to 5.0 r65 to 195 350 8.0
I 25.42 4.25 17.6 200
MBAI trailling) (w/o
suspension bands)
--- - - - -
M9Al Fired from PIS- 2.5 160 to 70 60 7.0 15.05 2.0 2.11 200
TOL, pyro-
technic, AN-M8
----_. - - - - - _.
M26Al (AN-M26) or 150
M26 (M26)
M26Al (AN-M26) or 5 to 92 195±15 800 11.6 50.0 8.0 52.5 350
M26 (wIblae band) 575 (fuzed) (M26Al)
---------- Released ----- ----
Ml38 (T10E4) from 360 1,500
MI39 (TIOE6) airplane 5 to 92 180 3,000 10 45.6 6.25 6')
., 440
---------- ----- ----- -.--- ---- ----
Mk 5 and Mods variable 180 600 . . . . . . . 27.0 4.75 IS.0 . ... . . . ..
------- ---- ----
Mk 6 Mod 5
. ........
Mk 6 Mod t)
AN-MkS Mlod 1
AN-Mk S Mod 2
variable
90
120
I 180
180
1,000
500
... ... .
S.O
35.75
25.12
5.37
4.75
30.0
18 250
. - - - . _ - - - - - - ------- - - - - ----
3 minute, electrically .. . . . . .. ... . . 1% 181) 200 9.1 28 4.5 22 .........
operated
3 minute, Wiley SA 8 ..... . . . .... ...... . . . . ... , .... . . . .....
... . ....... . ..... , .. . ....... . ........
-====-~-= =.-= =-.;
FLARlIJ, AIRCRAFT:
tow-target, M50 _._- 0 _.
360 65 .. . . .. . 22.S 2.62 7.13 120
=-==--~-.::::.:.:=----===---=== ===
FLARE, AIRCRAFT: towed Tow cable
Red, M77 (TiS) attached to air- 0 360±30 225 ... . . . . . 23.34 4.55 21 200
Amber, M78 (TI9) pbne 70
Green, M79 (T20) 90
=-====:; ~--=:=.--
- = . ::;::==

---------,----I
FLARE, SURFACE:
Airport, M76 Hand or 0 300 to 420 600 to 850 ... .... . 31.33 4.26 27.6
electric ~uib
Parachute, trip, MollS Pr~88urfl or trip .
3 20 110 3 9.75 5.5 5.0
wue
Trip, M4-..l Trip ~ire ---- 0 55 40 ', .. 6.75 3.0 1.5

area for a grellter time interval. Aircraft flares for bombing purposei;, are provided with shades
also haw some forlll (,f delayed ignitiull so that to shield air-erew In{'mlwrs from glart>. Data for
they will dear the aircraft and fuuetiuu at a de- S('\'eral aireraft flu res are prest'ntNI in 'fable 6-3.
sirt>d altitude below it. Certaiu flares designed A typi(~ul uireraft paradlUtt· flure for night bom-
for use below tht' air-emft, sueh as thoSt> intended burrim{'I1t is shnwll ill Figure 6-13, Imti its opera-

t-22
AKCP 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 coIQr.88
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 ~
brightness of the sky; the intensity of a signal
adequate for night use must be increased by a
factor of ten (twilight) to over 100,000 (bright
d
daylight). Relatively little is known concerning
h the effects of flame duration on the 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 W be
recognized in a relatively short period of ti.me.
----~-------.->. E
Since color differences are often the basis for
Figure 6-JJ. Illumination Diagram for Parachute communication by signal flares, the relative ef~
Suspended Flare fectiveness of the various color hues and their
saturation is Important. Since a signal URed
tion is shown diagrammatically ill Figure 6-14. A during daylight must often be observed against
typical tow-target flare is illustrated in Figurp- a sky (hlue) backgronnd, red signals, even though
fi-15. rrquiring slightly more intensity at night, are most
visible and most easily recognized in general
usagf'.33 Of the other methods, such as multiplicity,
6-3.1.2 Surface Flares
difi'pren t shapes, sizes. pattern!;;, or flashing of the
Flame-type surface flares are used for illUlni· sigllal-which eould be used for communications
nation during airplane landings in ease of p<>wer -only multiplieity appears to be ftelCible enough
failure at airports, or to outline boundaries of for lIormal ('ombRt use.
rmergency landing fields. Minl~- or grenade-type
surfal'!' flares /irc used to illuminate targets and
objectiVl's, to aid in deteetion of illhltration or 6-3,2.1 Aircraft Illumination Signals
surprise attacks by enemy troops, and for recog- Aireraft signals used dirt\ctly in connection
nition awl ~igJlalillg purpos!'s. nata OIl several of Willi combat operations were originally inteilded
tilest' Hart's are Prt'sl'uted in 'l'ablr 6·a. A surface ;'or signaling from air to air or air to surface.
fiarp whi(~h is primarily Ilsed to giv!' warning of Hint'(' the introduetion of the pyrotechnic pistol
infiltratioll by !'f1!'llly t.'·oops is shown in Figure and hand pyrotl'('hnie projel'tor. aircraft signals
(i·IS. huH' also bcen nsrd by gl'ouud troops for ground-
to.gnHllld and grollud-to.air sigualing. The sig.
lIab Ill'f' gPIlt'l"ally of Ollt' pie(·e, rllumed case con·
6-3.2 ILLUMINATION SIGNALS stl'ut'tiol1 with Ii st(,1'1 I.'!osillg ('ap. Aircraft sig-
Light-prodlH'illg signais art' Illueh smaller and lIals Ilrt firt'd fl"llm tlH' pyroteehuie pistol or hand
fast.,/" bUfllillg' thall !iart's and may l'OIlP.ist ot a p)' rutedllll(' projedor.
~CP 706-185

10
2oo2b34 4 5 . 1 •• ~

--12,000,000 C.P.
----·11,000,000 C.P.

C 500~O-=.OO=-.::.:c.:.:..;P.,---_ _ _ _ _ _~
1Hf-----IQ,OOO,ooo C.P

:
I H H - - - - 9,O<lO,oor.C.P.
- - - - B,ooo,OOOC.P.
1I+f/lf------ 7,OOO,OOOC.P.
3GG:.gg0C:: / + H / I f - - - - - B,ooo,oooC.P.

f ~
J.oHJ'I/H------ 5,OOO,OOOC.'\

81 ~oo~0 C.P.
.5
J.+HHI~----- 4,OOO,OOOC.P.
2. ._ _
lo. 2, J.+ffi/IHI-------- 3,ooo,OOOC.P.
H-H~iff------- 2,OOO,OOOC.P.
~I
.'---t--H-ffllllft-- - - - - - - I,OOO,OOOC.P.
I

~'1"
~I
~I
~
1

.
PARACHUTE ILLUMINATING FLARES
BOUNDARIES FOR
0.025 FOOTCANDLES,E

z~
" t"h"
E'~l'
-2.5

1 1.5

~~ !.:f ILLUMINATION.~,!.rJ ty!

Figure 6; : . Intllnsit/ ':urvvs for Variolls POtochute Flore Heights

':-inglr-star air('raft signals, It lULL··sta.' signals, iug fir!'. In som!' small arms tracers the gilding
cud traet'r double-star signals l"Hltain red, green, Ilwtal or steel build ja,·ket. has, as :.hm n in Figure
, . yellow light-producing ealldlP'l of pyrotechniC' {i-1R, a cavity into whieh tve tra! er,nd its 8890-
eompositioll. ~tars eall be disdnguished at dis- eiated ip-'lliter eompo);itiollS are I08it'd and com-
tam'es up to the mi\(,s at Ili"h and t.wo to three pressed at HO,OOO '0 125,000 psi ... "rroor-piercing
mill's ill daylight. tracpr ammunition eontaills a steel core which is
Data Oil airl'raft si~nals 1ft' prt'st'llted in Table inserted into the bullet jacket, as shown ill }l'igure
6-4(A) . 1i-19. The stpei eore has a cavity into which the
trUCt'r I'ompositions are loaded. Some artillery
6-3.2.2 Ground Illumination Signals proJt'l·tiit's have a cavity in the base into which
Tht'Is!' ,;ignais ('()JIsist of t1~'vices which product' the tracer ami igniter cOlUpot!itiolls are pressed,
a sign.:! I'.'ht'll tired wrti('" i~' into tilt' air. The liS show'l JJ: !<'igure 6-20, at a pressure of over
Iwight of projPl'tioll is f;"oll' {iOO to 700 fet·t. Data 100,000 Jlsi. Other urtilit'ry ..,tojeetiit·s USt' a sepa·
for SOliI!' groulld illlllllipati, II si~~J\als art' giVt'll ill I'att'ly-Ioaded tra('t'r assembly whieh is fitted into
Tabi!' li ..! (B). A typit'al h:.lld·h(·ld dl'vit,(, is shown tilt, bast· of tht· projt·etilt· as iliustrutt·tI in !<'igure
in "'il~Urt' (j·17, Ii-:n. III sOllie allIIn unit iOIl, t ht· t raeer eomposition
illitiult·s a dlarg!' whieh dest!'(lYs tbt, projeetile
6-3.3 TRACERS IIft,,(, a ,\t'iillitt, tilll!' illlt·r\'ui. III specifit~ ('uses,
Tral·t·r 1I111111Ullitioll fOl' both slIIuli l\~Il1S and this Ilia' ht, 1I1t' ollly fuudioll performed by the
artiJlt'ry is llsed for dl'tt'rlllilliHI! rllllK~' al.t! direct- "OlltPllSllioli loatll.·d ill the trltl't'r l'!lvity.

(;-24
AMCP 706·185

This page is reproduced .at the


b at:·k of the report by a dlffer~nt
reproduction me th0 d to proVlde
better detail.
SECTIONAL V'EW

E F
50'

,
ASSIM8Ult WITH FUZE AND
ARMING WlitE

A- Sl-.lp"ln" plug I Fla,e charg. Q Rel.g.lng cup dl.Ie


B Shod. r.toln., .uppa.t J Relay charg. R Cov., r.l.a.lng cup
K Cov.,
C
D
E
Rib retalne,
Stem
I.awe, lIPace,
L
M
D"lay element
Ba •• black .3 . . emt:.ly
Shack ahorber a .. embly
S
T
U Hangwlr.
v.
Stabilizing .. I ..

F Rib. H Sh,o"d. V Handl. a . . . mbly


G Shade o Thru.t .pac.r W Fin .tlffen.r
H Oulckm.ttch P Parachut.

Fig!)re 6-13. Typical Aircraft Parachute Flare

Hillel' tral'er ('ompositiolls arl' Tl'luti Vl'ly (lim· prot(·!·t Iht' trUN'I' ('olllpositioll froUl th:o t'ffects of
('llit to ig'nite. u more t·usilY-Ig'lIitiblt· ignition (,OIH- IHoist IJ.1·t'. If tht' hrilliunt light from tllt' igniter
pI'sitioll is loadt·d 011 tOI' of the t ra('l'!' (·ompoRitioll. ('0111 pw.. i t ion dault's tht' g'llllllt'l and bt·t rays the
(~()mpo~itioll, whil'}) llsuully l'ontaills
'1'11t' i!{nitioll h)(,l1< IOn of t 11t' Wt'IIPOII, It so-culled" dim igniter "10
a bindt·r, IIlol\~ with It t.hin Illt'tal s('al, Iwrves to l'owpositiOIl IIIIlY be uSI·d.

6·25
AMCP 706·185

_ _M

, I ... -.~.-"'-
........... -
:~

;Jr::::-Il
A-ARMING WIRE J--?uLL -OUT CORD
a-HmI';WIRE l:-RELEASING C.UP DISK
C-COVER L-THIWST SPACER
D-··fEAR WIRE M-SHADt: RET."'NER SUPPORT
I-SLEEVE N--!»\FETY DISK
F-DETACHABLE COVER LOCK '-SHOCK ABSORBER
G--COVER REL~C;ING CUP Q---FRICTION WIRES OF IGNITER
H-DET,II.CHABLE COVER .-LOWER SPACEK AND RIB RETAINER

Figur.6.J4. Operation of Typical Aircraft Paraclwte Flare

Tite pyrote(~hnic be"'ilvior of traeer composi. tior;;~should, iI. general: (1) produce maximum
Lions is sil'lilar to Lhat exhibited by other con- light output IInrl saturatf'd color for maximum
solidate!i eetllposition!< and the same charal.lteris- visibility, (2) burn long enough to permit the
tie,.. are illJportant. Tra(~er pyrotechnic composi. projectile to be followed to the target. and (3)

6-26
AMCP 706·185

T M L K A

~hr;,.1 ~
\
.-
d , -~
,W ::'(! !1----+'7"""'---+----:::Io...:::-l---+---\
/'
~
/
\:.r
/
J
, ~:.'::.J--+-+----+-I---+------++I \--+---+--4--+--+--\-

?-;: :t--\-+--+-~---I----+-H\
, t-i
f---
.:: ::.1---->.,.-+-- -+--->"..-f--+-Y
~·::.:f ---'*"r---..--+---''''=:+-- ~
_1!:.:'.
"'-
....,. F= ...... R
S
A- CA3LE RING G- RETAINER N- IGNITERS
8- PUL L COVE R H- BASE BLOCK p- FIRE CLAY TOP SEA L
C- SLEEVE J- QUICKMATCH Q- FLARE CASE
D- SAFETY DISK K- ILLUMINANT CHARGE R- CLOSING COVER (TOP)
E- SHOCK ABSORBERS L- FiRST-FIRE CH~RGE S- SEALING STRiP
F- FRICTION WIRE PULL WIRES M- PRIMING COHPOSITION T- CLOSING COVER (BOTTOM)

figure 6-15, Typical Aircraft Tow Target Flare

ignite easily frOl1l the igniter composition but re- (2) Binders which include resins, waxes, elas-
sist ignition by any propellant gas which may tomt'rs, plastics, and oils.
pf'lIetrail' to the tracer composition, Most tracers (;l) W tlterproofing agents whieh usually are
ar(' lIIade to pI'od,w(' n'd light lll'('allse red light n'sins, waxes, plasties, oils, and diehromating solu-
is the most visihh' color under daylight conditions; tiOllS, ('rht,y are llsed as proteetive coatings on
howl'''l'!', wid(, lIS(' of white tracers had also been lIH'tals such as magnesiulll to reducp the amount of
.r
madp by the (l1'l'lnanS and apalle:;c_ At times reaction with atm()sphe~i(' moisture,)
thert' llIay hI' l'pqllit'(,llIenti:; for Sl'veral different (4) Retardants which are usually inorganic
('olo!'s to illdi('ah' origin of thl' proj('('tiles, salts, plastics, resins, waxes, and oils, (They are
"'lIlok(' tra('I'I'S (Paraglllph 7-1.:3) have been uspd to dpcrpa:w til(' rate of the reaction between
PI'opos!'d alit! dt'\'eloped to previde a moI'l' visible thl' fill'! and tlw oxidant so as to obtain the desired
ll'1\et' ill (\:Jylight; howcVI'J', til(' advantllges do !H.t overall hUJ'ning rate,) Some retardants behave
justify pl'ovifiillg' two typl'S of allllllunition with merdy as inert diluents while others participate
difl't'I'Pllt 1ral't'l's. in thl' rpadion at mueh slower rates than the main
l'oJlstituents_
6-3.4 TYPICAL COMPOSiTIONS Typieal illuminating, signaling, and tracer
Pyrotedlilie i\lliminatj'lg compositions, like ('ompositiofls are given in Tables 6-5 (A) and
othcr PYI'ot('t'itni(' ('ompositioIls, are basicaay a (i-:> (B),
mixturl' of an o"idi~i!lg ag"('nt aad a mptal fuel.
Ot!H'" lIlillt·rials al'(' aeldl'd to this mixture to 6-3.5 FACTORS AFFECTING PERFORMANCE
Illodify t itl' bUl'lIing' mt(', l'olo!', alld radiant out- As illdieated in I"igurp (;-2~) threp ZOllPS ar'o
put, as \\'t'll as to inerl'(ls(' halldlillg' safety. Im- ('stablislwd whell 11 ('ollsolidated illuminating com-
portant mkiitiv/'s inl'iutle: po:dioll is ignited :!Ild burns propagativel;v. In
\ 1) ('0101' illH'nsifiers whieh art> llIainly highly ZOIlP A, pssential!y the burning surface both exo-
(,hlorillat!,d orgallic ('OIllPOllllds, e.g., hpxaehloro- t hrl'lIlal alld t'1Il1othel'lllal J'eactillns take place re-
I'thalH' (C~( ali), h('xaehlol'()ht'n~('IH' (C u( '16), Dt'- silltillg ill tIl!' formation of gaseous fuel and oxi-
('hlol'all,' ( ~IOCll~)' and pO!y\'ill,V !('hloridp (Crr~­ dizt'l' illterlllt'diatt's. TheSt' iutpl'IllPdiutl's react exo-
('II< 'I), thp.mally ill the flame zOlle. t'snaliy, the py-ro-

6-27
AMCP 706-185

TABLE 6.4(A)
CHARACTERIBT!CS OF V ARIOHS AIRCRAFT S!'\.';!'.·AL FJ.ARES
" TiIM !aPSe
from
aduation
I
tll/uU Burning
I~em Method of ,-ctuatton
funeiion,
aec
time,
sec
IMax·in. ", M in.dia,
Il.Z Weight,
Ib
----=--=-====-'== ==1'=-==-=-!=======~='I==='I=== ---
SIGNAL ILLUMDIATION,
A [,,"WRAFT: Fired I
Dot.ble star: from
Red-red, AN-M37 PIRTOL, 5 1.54
Red-red, AN-M37.\.1 pyrotechnir. ......... 10 ±3 25 (e~ 'lta.) Flee 3.85 1.57 0.35
Hed-reJ, AN-M:37 A2 AN-M8
or
5
-.. -.,-
.. -..-. - - - - - - - 12 (ea
I
8181°1------ 1.1':7
1. 54 - -0-.4-2-
Yellow-ye!loVf, AN-M38 PROJECTOR,
Yellow-yallow, AN-M3~Ai pyrotechnb, hand, ..... .... 1O±3 ZO (ea stl\r) Free 3.85 1.57 0.35
YeliGw-yellow, AN-M38A2 M9 5 ZO (ea star) 1 1.57 0.35
-------- - - -
Grf)vll-green, AN-M~: 1.54 0.35
Green-green, A~-r.1S9Al 10±3 20 (ea fit .. ) Free 3.85 1.57 0.39
Green-green, AN-M39A2 5 1.57 0.39
·1----
Red-yello"" AN-M40 25 (R star) t.54 0.39
12 (Y star)
Red-yel}ow, AN·M40Al Fired 10±~ 25 (:3. star) Flee 3.85 1.57 0.35
from 20 (Y star)
Red-yellow, AN-M4(1A2 PISTo.L, 5 25 (R star) 1.57 0.35
pyrotechnic, 20 (Y star)
AN-M8 - - - - - - - - - - - - --- - - - - - 1 - - · - - - - - . - - - - - - - -
Red-graen, AN-l'141 0r 25 (R star) 1.54 0.35
Red-green, AN-M41Al PROJECTOR, 1O±3 :lO (G star) Frep 3.85 1.57 0.39
Red-green. AN-M41A2 pyrotechnic, 5 1.57 0.39
hand, 1----- --------1--------- - - - - - - - . - - -
Single star: M9
Hed, AN-M43
Red, AN-M43Al
I· ........ 1O±3 25 Free 3.85
1.54
1.57 0.27
Rd, AN-M43A2 5 1.57
------ _._----- - - - - - - - - ---- ----
Yellow, AN··M44 o 15 1.54
Yellow, AN-M44Al 1O±3 25 Free 3.85 1.57 0.26
Yellow, AN-M44A2 5 25 1.57
- - - - --------- - - - - - - - - ----1----1 ----
Greeo, AN-M45
Grt:en, AN-M45Al
I: ...... lO±3
30
25 Free 3.i:S5
1.54
1.57 0.32
Green, AN-M45A2 5 25 1.57
- - - - - - - - - - - - - - - - - 1 - - - - - - ----- ----.
Tracer, double star:
Yellow tracer, \'ed-yellow star,
AN-M&3 . . . . . . .. . i .. ... . .....
Yellow tracer, red-yellow star, 0 T,2.5to4 T, 30 ·1
AN-M53Al Star, 3 to 4.5 R star,
Y fltar,
48
36
1 Free 3.85 I 1.57 0.40
y ~llow tracer, red-yellow star, 5 3t{)4.5 R atar, 48
AN-M53A2 Y star, 36
Green tracer, rcd-r~d star, I ..... . ...
T,2.5to4
. ... ....
T,
.. . . ...
25 I
AN-M5·!
Grecr. trucer, red-red star, 0 Star,3 to 4.5 Star, ea 48 Free 1.57 0.38
AN-l\l54Al
Green tracer, red-red sIal',
I 5
5
3 tv
3 tG 4.5
8t4r, ea 48

-Z2~~~:!r~-~;e-~rl~~d~~,----1 ----- ------1----·-



--- -. ---- ---.--- -----
AN-M55
(;reen tracer, green-red star.
AN-M55Al
1
.
" 0
...........
T, 2.5 to 4 T, 25
Star, 3 to 4.5 G star, 20 Free a.85 1.57 0.38
I
Green trf\cer, greIm-red star,
AN-M55A2 5 3to4 ..~
R star, 48
Gstar,W
.1

________~______________~______~________~I~R~s~ta=r~,~4~8~____~____~______~_____
I

ti-28
AUCP 706-185

--I' --'-I
TABL:i: 6-4(A) «(;out'd:'.

----~~'t-·me-laP-8-:'e- -
from
actuation

Item
to fuil
function,
Bee
Burmng
time, I' (;ancllepowe1',
'J _ _ _3_~_C_ _ _ _ ~_J_JP_t_
F.1Jl!, I
,
M ~ L, Ma1: dia, Wlli{lltt,
in. in. lb
Red tracer, green-green star,
AK-Mfi6
R6d tracer, green-gre-an star,
AN-M5nAl
Red tracer, gr<len-green star,
Fired
from
PISTOL,
"t'" ·t~~;i ~i{~'
3 to 4,5
t~r,'~~3~" ~n
Star, ea W
3.S5 l.Si I' 0.38

AN-M56A2 pyrotechnic,
AN-US --1----- - - - - - - --'- ---- ----
Red traeer, red-red star, or
AN-M57 PROmCTOR,
Red tracer, red..red Btar, pyroteclmie,
AN-M57J\.l hand, St.a::, 'U 48 Free 3.85 1.57 1./.39
Red tracer, red-red star, MI}
AN-MS'IA2
, - - - - - - - - - - - i - - - - - - - - - - - - ____1. ,__ _
Red tracer, green-red star, I
AN-M58

L
Red tra';llr, green-red swr,
.AN-M58Al 0 3.& 1.57 0.39
Red~~~~
AN-M58A2
'I, 3 to 4.:i I r:.G ;ita
star, 2S
. . , 48
5

--------------~-------~---.----~~--~--~-- ------
technic composition is fn"l rich hnd the ZXCfl'lS by .hese emitting species. The rate at whil~h a
fuel· reacts with vxyge'l fl"')m th\~ a~mosphe",e. pYl'otechnic mixture burns depends on t.1J,~ amount
30me of the energy requir~d to L'rn. tl',"se gaseous ,)lid r.'\te at which heat is 6yolved. Sufficient heat
intermediates results from the energy re] ~ased in mllst (,,> prrlduced to raise ihe temperature of the
exothermic r~actions on the turning surfact (Z"lie h\gred!ents to a point pt, whid', an eJ;.othermal
A) and some from the dame r.Qile. Energy fn,m reaction will be initiated, and the reaction rait:
Zone A is also transf,erred t,t) Zone B which may must ~e sufficient to more than comp;msate for heat
be eonsiderr(~ the prl'-igr, ition ZJne. D;rce~ly b~low losses in order for tVe comp'lsition to burn propa-
Zone f~ is thr remainder of the unrracted pyr0- gat.ivcly. As are comhlon t(l all comhustion pro-
te\,lmil~ cOll'}),)sition, or Zone ('
cesses, the rate of curning" the products l'ormed,
l"J/lul'e H-2a shows a typk:tl isothermal dja- and the flame temperature are affected markedly
~ram of the lewperaturr distribution of a pyro- by the composition of the mixture, as wen as by
technie flamp.~ The tcmpe.'atilre it'! not C(lnstant the t;hvsical condition of the materials and the
thro1lghoht the flam " , the hottest poction occurring aml:Jient c('nditions under whidl it is bmned. Some
approxiJ lately two il1(~h('s above ke hurning sur- of the more important fa~tors which affect the per-
facr in the middle of ~he ilame. formance pf light-producing pyroteehnie items
The flanlt' produced \J~' mO'3t pyrotechnic COIll .. ~1lI'lude: (]) heat of reaction, (2) composition,
positions is heterogeneous ;n nature, conta.:ning (:3) emitters, (4) color imensifiers, (5) binnel"l.J,
solid, liquid, and ga.<;eous product<\ of combustion. (f) particle size and distribution, (7) eon,':iOlida,·
As most of tIll' radiation produl'ed is of th8rm1:LI tiou, (8) flare dia:neter, (H) ca\ile materiall~ and
origin,S thl' dis~rihution of radiat.ion in any Si>ec- (oating, (10) temperature and pres~mre, (11) ro-
tral regioll is uetrrmjllt'J, baBil'l:Llly, oy the chemical tational spin, and (1~) moisture, In addition to
nature ~nd physical fltatt> of th? products which tht above factors, t:'w igniter 01' first ti~e used may
emit in that region and thr temlwrst,ure reached also iufhwT\l~p t~e output of a py,,;)t.e{~hn:(! de,ice.
• See ex'll'.ple J 'a.ragraph 3 ·:!.5, AllY ehanges in the pyroteehn;c composition, the

6-29
AMCP 706·185

TABLE 6.4(B)
CHARACTERIS~ICS OF VARIOUS GROTJND SIGNAL FLARES
--.-.- -
I Tifr..tlaPlIe/
from
actuation

Item
I
I .">1etlwd of actuatwn
to full
fU"I.cI:ion,
Bee
Burning
time,
Bee
Cllrnilepower,
loa
Fall,
Ip8
MaxL, Max dia, Weight,
in. lb in.
- .- -'- - - - - - -
SIGNAL, ILLUMINATION,
GROUND:
White IItar, c~uster, :"f!8'11 18 (lor ea
White etar, "luster, M18A2 5.5 4 t.,) Iv of 5 stars) }t'l'OO 10.14 I 1.88 1.09
---, -----
GreIS:! sta~, duster, M20Al Fired from
I 7 (for ea of
---
Green Ilt.ar, clwt.er, M20A2 LAUNCHER, 5.5 4 to 10 5 stars) Free 10.14 1.88 1.09
---- ------ grelUldt!, - - - ------
Amber star, ~luster, M22Al M7 series 2 (for ea of
Amber star, cluster, M22A2 5,L 4 to 10 5 stars) Free 10,1'1 1.88 1.06
- ___ 0_-. --
Red star, cluster, M52Al
5.1l 4 to 10 35 (for ea Free 10.14 1.88 1.09
Red star, cluster,M52A2 ......... of 5 stars)
------------ -.-~.

Green star, cluster, Ml25 (1'71)


----
Hand-held rocket- 5.0 4 t" 8 9 (for ea of 4.5
----
10.14
------
1.64 1.3
propelled launching 5 stars)
mechanism
--_._--_. ._------- - - - - - _ . ---- - - -
White star, parachute, M17Al mred from 5.5
LAUNCHER, 20 to 30 20 7 10040 1.88 1.04
White stA>, pamchlite. :M:17A2 grenarle, .. . . . . , ..
- Green star, pamchute, ..Mll}Al
-----
~ M7 series ---- ----- ---- --- - - - .
5.5
20 to 30 20 7 lO.4O 1.88 1.02
Green star, parachute, M19A2 .........
----_._------- ---- ----- -------
Ambtlr star, pallochute, M21Al 5,5
20 to 30 4 7 10.40 1.88 1.00
Amber star, parachute, M21A2 .........
-----------_._- -' - -_.
Red star., parachute, M51Al 5.5
2Oto3'l 20 7 10.40 !.83 1.02
Red 8tar, parl\chute, M51A2 . .. . . ...
-- --_._----- ----
,

-----_._. .- -----_._. ---


Red star, parachute, M126 (172) Hand-held rocket- 50 5 8 9.64 1.64 ........
White star, parachute, MI27 pmpelled type
(T73) launching 5.0 25 5:) 10-15 9.64 1.64 1.3
Red star, parachute, 1\1111 mechani'llll
(T66El) 30 10 .... , . lO.O i 1.21
I .. I
1.63

ignitCl', the I!ontainer, ete.-- -which might be caused (:ombustion should be high and products formed
by storltge conditions--may also markectly affect must be stable at the high temperatures necessary
the output of light-pl."Oducing pyroteebnics. to pr'Jduce the luminous intensity reqllired for il-
luminating aud signaling purp~·ses.
6-3.5.1 Heat of Reaetion The heats of reaction fl)r the stoichiometric
One of Ow imp()I'tant fuet.ors in. determining rNletion between several oxidizers, and aluminum
the luminous intensity of a. 1ight·produ~·ing pyro- or magllt~sium as the fu?l, are summarized in Tables
teehui(! de viet> is the ~.eIll'perature rea"hed by the (i-f; and (i·7. In generfLI, for both fuels, the per-
emit.ting sppl'ies ill the flame and produced by the ehlorate oxidizers are t.he best. solid energy pro-
bur'ling of t.he pYl'otedmic mi:tt.ure. 'fhe tempera· ducers on either a weight or volume basis; how-
ture reaehpd (iepe'uis, ill t.urn, on t.he amount and ever, SOUlI' of HII' nitrl.tes are almost 118 good.
rate at. w})ieh ener(.,"Y is released hy till' rea.ction. PhYl:'ieal data and burning' (·haracterist.ics of
In genrraJ, tJH'r(d'ore, the t!lJerr~y rdt'RSl'd during stoiehiometri~: mixtures or the alkali and alkaline-

(;·30
AMCP 706·185

PRESSURE CAP_

PARACHUTE

PULL RINC

SUSPENSION
CABl£

FElT PAD STRIKER

ILt UMINAI\fl
COMPOUI\fO
~ERCUSSION
CAP
lAMINATEO
PAPER CASE

'",-

,G"-UTIOIIj
(' H 1\ ~(.[
'" IGNITER

FE'T ....\f1

PROPlll'""C
(' ~I ,\ IH;l.

O£lA'Y , lJlf

. PROPHlING CHARG(

This page is reproduced at the


llack of tiw report hy a different
n·prodlldion method to provide
hetter detail.

Figure 6-16. Typical Surface Trip Flore

6-31
AMCP 706-185

OJ.

Figure 6-J7. Typical Hand-Held I/!uminating Signal

100 _ _ _ _ _ _ _ _ _ _ _ _ _
90
80
PERCENT ~
OF 50 _______ _

FUNCTIONING ~
20
I

WORLD WAR t WORLD WAR][ PRESENT OEV.


Figure 6-J8. Small Arms Tracer

('arth nitrates alld putassiulIl perchlorate are SUIll- IOWl'l' lIIolecular ',\'t~ight oxidant", ill each group
marized ill Tahlt' ti-M (A). 'rlH' Ilitmtl''i have been should be preferrt'd over t.hose of higlwr lllolecular
1l1'J'1I1l:,!('d ill at'('ol'dHlH't' wit h theil' molecular \I'pig'hL UllfortUl.ately, the 10\\'t'r wt'ight uxidants
\\'t'ighl. alld tilt' pt'l'iotii(' g'I'OIlJl of tht, llIdalli(' Il'wi to be extreult'ly h;'gros(~o]Ji(', whieh cOlllplicates
t'1('IIIt'1l1. Jt is {'vitiI'll! 1'1'0111 this arl'II11g'('lla'llt that, t1lf'il' liSt' ill pyrott'('llllil' l'OIll]HJsitiolls, and the
ill (',1('1t g'l'UllP, as tht' mult'('ulaI' \\'t'ig'ht of the oxi- slll'lf-lifl' or thl' stability of mixtul't,s t'ontaining
dallt illl'l't'aSl's, till' pl'oportiol1 of flll'l ill tIlt' l/ll'lll is lllarkt'(i1y l't·dlWl'U in the jll't'St'IIC(' of traces
st oidl iOllld I'i" mixt lIrt' !it'('rt'm;!'s, (;ollseljllt'ntly, of atlllOsphl'ri(' lIloisturt', (;l'ealt'r l'art' is tht'rd'ort~
tilt, twat of ('{'/tt'tioll det'I'('ll.'il'S, This is rt'fleett'd ill l'('qllirt',j ill sl'alillg' Iht' t'olltailll'!' alld it higher
it dpl'l'l'asillg' IUIllillOlIS illtcllsity, hUI'IlIl:,! I'atl', alld p!'obability t'xist,s for illad('qllatl' IH'rfol'ltllllll'e aftt'r
Pt1i('iPIH~,I', ()11 this basis. it \\'oltld appt'ar that tlll' j()ll~ storage.
AMCP 706-185

TRACER COMPOSITION
"----IGNITER COMPOSITION

HARDENED ALLOY STEEL CORE


INCENDIARY MIXTURE I M - I I - - - - - - -
GILDING METAL JACKET--------_J

Figure 6-J9, Armor-Piercing Tracer

6-3,5.2 Cumposition oxidizer used, ranging from about 10,000 candles


'l'}ll' luminous illtcnslties of flares eontaining per square inch for potassium nitrate to around
hinary mixtllrps of maguesiulll and the oxidizers 800,000 candles per square inch with sodium ni-
listed ill 'j'ablp G·H(B), t~hallge 'with incr"asing trate as the oxidizer, The difference is due to
mag'Il!'siulIl as shown ill f<'igurp 6-24. For a given several faetcH's, one of the mf're important of
oxidiz('r, thf' luminous intensity incrpases with the whieh is the metal ill the oxidan~, Sodium is a
amollllt of magllt'SiUIll until a maximum is reachEd strong emitter in the visible region while pot.as-
at. 70 ta HO pl'r(~ent magnesiuIll, A further increase sium is not,
in till' amount of magllPsium rpsults i!l a reduction Thf' plenlf'nts used to color l)yrotechnic flames
ill luminous illtpllsity, TIl(' burning rate also IS for military uses are strontium, producing red j
a lllaximulll at 70 to 80 pl're!'1Jt magnesiulll, as is barium, producing grcen; and sodium, producing
illllstratl'c1 in !"igul'p o-2i>. yellow, Copp('r (bluf' or green) has also been
As S(,(,II i" Exmnplp ii, l',ll':tg'raph :l-2.G, tlH' us('(1.~~ I.Jithium (rt'd) , boron (green), tnallium
amoullt nl' magllt'SillHI wltiI'h will TlJ'odncc' the maxi- (green), ruhidium (red), and eesium (blue). are
1ll1ll11 IUlIlillous illtt'nsit,\' ('all b" ('stilllated if it is also strong (~olor prodneer", but their usc is not
aSSUIllI',! that ollly that alllount of magllesimIl, in pral'tical tJe(~ausp of l~ost, toxicity, or nature of
t'X('pSS of j ht' stoil'iliollll'tl'it' alllllllnt, whi(,1t (~all lw their (~ompoUll(ls.36
\"apol'izt'd hy till' stoiehiolllPtr'ic' l'l'lleti"n will read '1'he ehromaticity eoordinates for a large Hum-
with thp OX,Yg'('1l ill tht> ail'. II I'('quin's about 1.i> bpI' ot' yt,llow (sodiulll ('ontaining), green (barium
kilo('aloril's to "apol'izt, Wit' g'I'alll of JIla~IH'sillm; ('ontaini.lg), allti red (strontium containing)
thl'['pfOf'\', til!' alllOlIllt of ('Ht'I'g'Y I'ell'a-';l'd by OIW flart's, wht'll plotted 011 a vhromatieity diagram,
g'I'lIlll of II stoi('liiollll'tl'i,' Illixt 11(,(' of [llag-IIt'sium fortll tl\l't,p stl'ai~ht lim's whieh ('Ollv('rge toward a
alld so<iilllll Ilitrat!' will vapol'izt' about 1.:l g'rctlllS ('0111 Ilion Jloi lit, as showlI ill l<'igul't, (i_26,:17
of 1l111~llt'silllll This ('(ll'l'l'Spontis to a III ixt 1I1't' eOIl- Th" llomillallt \\'aw1pllgth for the yellow flares
taillillg- aho1l1 7;' ppr~'Pllt lIlagllesiUlll, I. illdit'atc"\ hy tIl" intpl's('dioll c;t' the straight line
wilh 111,' pel'irn\'lc'!' Ill' tilt' l'hromatil'ity diagram)
6-3,5.3 Emitters is al',H\lld ;',!)() llIillilllil'l'ulls, HpslIIts uf some yel-
As showll ill I,'ig-ul't, (i-24, the light. intell3ity at low ilal'!'s did 110t, as illdieattd ill Fig'lre ti-26,
tIll' optilllUl1l llIagnesiulll eOl!tcllt varies Wilh the fall 011 tiI(, stl'aight liw', This is bplipVl'd \0 be due
AMCP 7oti·l~5

'<tI." PROJECTILE
.< " ,

~",'G DISC-----

This page is reproduced at the


back of the report hy a differenl:
r£prodlJ,~tion method to provid
better detail. e
.figure 6-20 Artillory ) (JC, flem6nt in Projf:C#ile

to mpasllrrm"Jlt ,'rr " as llltcl' mpaslll'('m,'nt:; of diat(,mie, awl p',ssihly triatOll1ic emitters whieh
flares witi) (,SSt'lltia: " th!' "IiJllP l'omposition fel ('an ('XiSl at tlH hig-h tpmperatures in It pyro-
dos!' to ':1" strati' line, Foil' tilt' ff>(; Illire IIn,i t.'chllit· tlaJlH',;l~ Net'IJIHlary t'mittt'rs, including
grr, II tian', hoC) I wh ieh "tllltaiu i1 SOUl'e,' (II jlurtiellllltt· matt!'l', will il1fiuen('t' the dominant
,·hll/,·in,·, tilt' dOli! 'tallt wav('lt'ngths are :lpproxi- 11'1l V('I"J1~~ '., Ill(> ('o)uriIll2trie purity, tht' saturation,
"a't'l .... (;·lO n,ill!: .iel'o);!, dnd ; 'proxim;,l;'iy 5~4 and tilt' (',[livp ilttl'lIKity of th(' light produced,
.ljl iUllt("l)lJS, }"I'.-'P l·tively. 'rypit'. 'fhlvtra .ailled 'l'hl'" -;pt·(" lUs('opil' Ktudies illdil'uted that the red
,'or It n~l, ,\it'll, 'II illil g-re!'11 ~igllaJ flart· are given lig-ht 1II'/IlIH'ell by flar!'s ('()lItaining strontium and
ill !<'il!,url' (i-~': Ii S(),If('1 /)1' ehlol'ille i,; du(' tu thp diatomic mole-

Sp(,('jrosl'oj>It' ,tuJi('1S ill(jil'ill'P~ tint mOISt of (·,i1i' 8r( 'I whil'h t'mits stt'(lIl!!ly Ilpar 640 milli-
til<' lig-ht I,ro, \lI,".! I Y illu'llillati(lll alJ(l sigud III "'I'OJJf'. }"or Hurt's wldeh did not l'onwin ehlorine,
tlart·,; is dilP 1 , " !ill!It.('d !lUlllber of 1lI 01: at: (I 1111 l', bl! t prod W'" It rN1 ligLt, i, \\ IS ('onduded that
AMCP 706-185

;
t:r
~". \,
it;ctOStNG"WASHER-

. , .. " '~',

" .,. .... "...

figure 6·20. Artil:ety Iwc",' flement in Pro;ediie

t.o measm'emellt error as later meallurem<"nts ,,1' 'liatnwic, alll1· p.'1'.... lh1)' triatowi,' "ulitters which
flares with esst>ntially' the same '. compositic.n leU' ';'!i, ,·xist Ht !II' hlgb ti'l\1pl>'l'atmes in 11 pyro-
close to tbe' straight line. For the red flare .:.nJ. ;:,'chnie fhuu~.;:> Secondal'.\· t·mittlr~. including
green flare, both of which ('ontain a sonrceof pa1'ticulat~ l!lntter. wHl illtluence thf' dominant
chlorine, the dominaut, wa"elE:ngt.hs are approxi- "a':"l;~llgth, the «oiorimf'tri(' plI!'ity, t hI' saturation,
Ilwt.ely 640 milllmicrons and approximately 524 a1Hl the 1'('!atiyf' illlf·nsih' of t]l!~ ji'!ht prouuced,
, millimicrons, respectively. 'l'ypicaillpe(lt.ra ohtainp.it Till's!' speetrnscopie studit:'~ illdicati:'1..l t.hat the red,
for a red, yenow. and greellsignal fl~rl?are give~ Jigllt' protlllce~l by lia1'Ni eontaining o;;r1'oHtmm and
in Figure 6-27. ' a S(lUl',~<,~ of ,i'hJ('l<jD~ i~ liu.? to the Jintmllie mllle-
Spectroscopic :o;tu·,\ies indicate that most of "1111' !-irClwhirh f'mits >:t!".!:):!"ly 11('1t1' 640 miIli.
the lightprod\]eed by' illumination and signal llllf'I,ons.For Ra1't->; which dit~ notcol1taul chlorine,
flares i!1l (illeto a limit.ed number of monatomic, hnt producf' a red light. it Wi\!! cOHcluded _,that
AMCP 706·185

TRACER

BAND

WINDSHIELD

CORE

Figure 6·2J. Artillery r.-acer

the red light was, most likely, due to strontium p-mission of cuprous chloride (Cur-I), 1'1U13h of
oxide (SrC). which is radi&ted in the 420· to 460·miUimicroD
Green flames are produced by the band system region of the E'rectfum. The blue-green (md green
of barium chloride (BaCI) in the 505- to 535- systems which afe also produced are usually much
millimicron region of the spectrum. Most green w~pJ:er.
flames show, in arld~tion to the hand emission h'om Y cHow light is priJ. ,arily du~ to the D lines of
bariulll ehloride, ('mission in th" orange and red sod:llm and aSbociaten. \~ontinuum. At high sodium
region, band emission fNm calcium ch1c,ride (CaCl) concentrations, there is strong continuous emission
and s~rontium chloride (SrOl) formed from stron· in II region whHl t'Xt"nds from 500 to 700 milli·
tium and calcium impul'itie"l in the bariulli, In mic!'Ons.
addition, there are contributions from an ".v:tenslve As shown in It'igur(' 6-28, which is tb~ !'pectral
barium oxidp (Rall) band system (400 to 800 (li~triblltioll of energy fron: 8 green fiare,811 the
millimicrons) . specifie emissiull. al~pr()ximately 52;j millimicrons,
OHI{'r stud it's iudil'lIt/' tllat the triatomie mole·· is sllJwrimposed 011 a coutinuolls haekground.· o
('ule ~r (011) (strong f'mi:lsion near ;140 milli- ThiH rt'snlts ill It IPHS saturated greel~. An increase
mil'Nlls) mur ('ontribnte to tllP pru<1netiol1 of red in llIa~llt't.imn ('f)ntenL as shown ia Fig-urt' 6 .. 29 for
light and that bariulI, hydroxidl' Ba(OlI) (strong H ypllo\l" til1rt',:17 !'1'SUitS ill n decreased saturation
emission frolll 4H7 10 527 millimicrons) way con- of thf ("oIOl"pd light p"odu(>ed. The continuous
tribulp t(, tht' pro<lw,tion of grt;'{'n h~ht. There is IHI(·!q.;roul1.1 1Ilily bt- dill', ;1\ part, to incandescent
SOIll(' ('"i<1t'I\('(' thnt part of the radiatioll from the ('arl'l)l\ (from hindpl') as a binary mixtUl'c d mag-
I'lIli11('!' Illay lit"' dill' 10 (,J,I"'lIlilllTllin('seence. 22 I!\',.\'lm al~ti an (lxi,lizl'j' show ~onH'what less ('on-
Blut' flllllH'>: are Il ')rn.ally P"('l;nt'Ni hy t.he tiliuol\s iJa('k:,:"ol.llHl. It is also (l11e, in part. in

6-35
AMCP 706-185

TABLE 6--5
TYPICAL ILLUMINATING, SIGNALING, AND TRACER COMPOSITIONS

SOURCE
- - - - - - - ---
COLOR
Mag-
ne&ium
FUEL

Alumi-
num
,--- :.fisc.
---'

Barium Sodium
Nitrate Oxalate
--- ---- ----
OXIDIZERS

Sndium
Nitrate
----
Stron-
tium
Nitrate Misc.
Oil
Linseed
Binder
,--- - -
Wax
leastor Paraffin Misc.
---- - - -
A White 26.9 38.3 25.2(d) 2.9 6.7
A White 28.5 6.5 57.0 8.0
A White 36 4 43 12.5 1 2.5
1
A White 48 21 5 21 1 3
1
(; YeUow 52 35 13~j)
C Yellow 58 37 5 k)
0.5(1)
C Green 23 53 2(m)
2O(n)
2}0)
C Red 40 18 22(e) 6t)
7o)
C 21 68 5 2 4~p)
D 58 .I> 37.5 /1.5 8)
(29)(k)

,
B Red 26.7 33.3 26.7(f) /6.7(Q)
5(g) 1.Il(Q)
B Red 28 55 17
B Red 26 52 1 16(r)
(')
D 90 (a)

D Dark
11)(a)
34(b) 28(h)
38 (i)
I
D Dark 2O(c) 50 15~t)
I) ul
I
.- I
A. Na','al Ammunition Depot, Crane, India~1I
B. Frankfu.d Arsenal
n. Pica tinny Arsr,m.i
D. NOL WhitH Oak, Marylana
u. Pyrotechnic compositions
~. Manganese
c. Silicon
d. Potassiun. Nitrate
e. Potassium Perchlorate
f. Strontium Peroxide
g. Strontium Cxalate
h. Bariulll Chromate
i. Lead Chromate
j. Thiokol
k. Laminae
l. Plul"Onic
m. Copper Powder
n. llexacblofoben~ene
o. Asphaltum
p. Sulphur
q. C'\\ciuDl Hesinaw
r. Polyvinyl Chloride
8. Binder COlllpogition
t. ZirccllilHlI Hydride
\J. Tetmnilrocal'bazole

N ott': De.tails of preparatioll and llla(.cri ..1 Hpecificatioll~ sboulrl be obtained from IfiOUrc6 illDtallatiOllll.
AMCP 706-185

TABLE 6-6
HEATS OF REACTION OF ALUMINUM WITH
STOICHIOMETRIC QUANTITIES OF VARIOUS OXIDANTS

Heat of Reaction
Composition Products
Oxidant Density, g / cc ll /(c(l.l, Total Callo Comp Cal/cc Comp· Assumed
---_.-
Al (C10 4 )a 2.70 est 1,603 est 2,96& est 7,990 est AbOa- A1C1 a
Mg(CI0 4 )!! 2.64 3,230 2,930 7,750 A120a-Mg C1 2
LiClO 4 2.53 1,590 2,97G 7,520 AbOa-LiCI
Be(C10 4 h 2.38 est 3,200 est :3,030 est 7,220 est A1 2O a·BeC12
KCI0 4 ~.[j8 1,598 2,530 6,540 A1 2 Oa-KC1
Be(NOah 2.51 est 1,880 est 2,810 est 7,070 est A1 2 Oa-BeO-N 2
Pb(NOah 3.90 691 1,585 6,190 A1 2 O a-Pb-N2
NaNO a 2.39 1,624 2,080 4,980 AbOa-Na 2 O-N2
}i'20 (liq) 1.95 1,038 3,850 7,510 A120s-AIFs
02(liq) 1.64 798 3,910 6,430 Al 20 s
F!!(liq) 1.37 622 3,700 5,070 AIFa
CuO 5.11 288 984 5,030 Al!!Oa- Cu
MeOa 3.81 219 1,105 4,210 A1 20 s Me
FczOa 4.18 203 948 3,960 AhOa-Fe
WO:1 5.46 198 6!):1 :3,780 Al:;;Os-W
V 2 Or. 3.19 876 1,075 3,340 Al!!Os-V
H 2 O(liq) 1.46 194 1,800 2,620 A1 2 Os·H 2

* BascJ on calculated trtll' density.

the visiblr, to thl' volume emission resulting from ('hloridt', 01' Dechlorane are generally uscd as color
seattpring by tht' solid partidt's of MgO whieh arc intellsifi('rs beeaust' thcy arc a ready source of
l'ssputially transpan'lIt ill that l'lIvironnlem. (·hlorilH'. As shown in Figure f).30, the addition
White Jig-ht eall be produced by: (1) devrloping of iUl'rt'lIsing am,)Ullts of polyvinylchloridc reduccs
all l'xtpllsivp ('ontillunm, (2) pX('itiJlg an cxtcnsive t ht' ('alldh'pow('r of a magllesium· strontiulll nit.rate
diserl'tt' balJ(1 systl'Ul, IUHI pn ('x(·itiIlK two nearly Hart' j how('\'('r, its ('olor value (see Paragraph
('omplt'llIpntary hand systt'Ill:'l. 'l'I1t' light produeed 1i-2.fi.5) 11:-> H r('d Hare increases as showH in Figur('
by ill(,lllldt'sc('lIt ('arbon pllrtid('s, (II' the ('xtl~nsive (j··;H. Re(} (Oolol' values of grt'llter than 0.40 are
sodiuJll ('ontinuuIII produ('''d by tlIP JIlllgnesium- impossihlt' to ob~ain llllll's~ th!' ('(liar illtt'llsifier or
su<1:UIIl lIitratl' illuminatillg' fill!'!', al'(' g'ood ex- bindp!, is a <'hlorine eoutaining eompOllild. As aI-
Illllpll's of IIIt,thud (1). 'l'IH' ('xtpnsive band system
rt'IHly illdieatt,d, ill the HbsPJH'(' of Ii ehlorine eOlll-
of hariulH oxi.!(' (RIl()) (400 til ROO III illilllil'l'ol1s )
;lOlIlld, tll!' rt·(1 ('(jIm lIlay bt' due to strontium oxide
is an ,'xlllllpl(' of Illt'th()(\ (~). Suitahll' hl('l1(iinK of
whil· I t.Ilf' prt'st'II('P of ehlorill(', strontium ehlo·
t hI' ('mission froll! st !'ont i II III d.lorid(' (81'( 'I) (r('(\) ,
rid .. ajl)lt'll.r~ to bt, tht' t·mittillg SI)('('i!'s.s~
,'ltI('illlll I'hlOl'itip ( 'IlCI~) (Yl'lIow), and bariuIlI
Tlip pro<illdioll of a saturated J,{r(,('11 light b)
(,hlol'idt' (Ha( 'I,,) (/!I't'('n) is 11I1 I'xauplt' of lUeth'.ld
( :l) . pyrott'l'illlil' 1IH'llllS is lIl()r(' d iffh'ult. than pro(Il1('-
lioll of II rt'ti lig-ht of rt'latiVl'iy hig'h ~lItuI'ati(ln.
6-3.5.4 Color Intensifiers III HlPst pyrot('('h)"i(' it-PillS, til!' protlu,'tioll of ~r'.'t'll
lIigldy t'lliorillat('d organi(' ('ompol!,,,ls slI('11 liS lil!ht apI't'IlI'S to dt'JlPlld Oil fhp gTt'f'll emittl'r,
hpxl\(,lllt II'opt 1IIIIlt', hi' XUI'll lu!'oht'IlZt' lit'. polyvillY I- 1,lll'illlll I'iliuridl', form('(l from tilt' dt·eolllpnsitioll

6-37
AMCP 706·185

TABLE 6·7
HEATS OF REACTION OF MAGNESIUM WITH
STOICHIOMETRIC QUANTITIES OF VARIOUS OXIDANTS

Heat of Reaction
C()mposition Products
Oxidant Density, gice'" L0al, Total Cally Comp Callc" Comp'" Assumed

Al(ClO,)s 2.14 est 1,732 est ~,810 est I ')10 est MgO·AlCls
Mg(CI0 4 h 2.11 1,163 2,785 5,380 MgO-MgC12
LiClO, 2.04 573 2,810 v 740 MgO-LiCI
NaClO, 2.10 est 581 2,650 5,560 est MgO-NaCl
I(C10 4 2.13 576 2,440 5,200 MgO-KCI
Be(NOsh 2.04 est 681 est 2,675 e8t 5,420 est MgO-BeO-N2
AgNO a 3.00 804 1,656 4,970 MgO-Ag-N2
14iNO a 2.03 631 2,430 4940 MgO-Li2O-N2
Pb(NOl.lh 3.03 '156 1,584 4,800 MgO-Pb-N2
Ca(N0 a)2 2.0!t 647 2,265 4,620 MgO-CaO-N2
Sr(NOah 2.38 627 1,880 4,480 MgO-SrO-N2
NaNOs 2.00 594 2,035 4,070 MgO-N~O-N2
Ba(NOah 2.54 616 1,610 4,080 MgO-BaO-N2
KNO a 1.95 570 1,760 3,430 MgO-K 2 O-N2
F2(liq) 1.29 264 4,230 5,460 MgF2
O;)(liq) 1.44 288 8,570 5,140 MgO
Pb0 2 5.37 222 770 4,140 ~gO-Pb
Ba02 3.53 137 680 2,220 MgO-Ba

* Based on calculated true density.

products of barium nitratel:nd IiU or/.;u,li,(, chlorine provpd the green color, but to a lesser degr€~,
eontaiuiug l"omponnd. Ethylcellulose, th!' oue nonehlorinated organic ad-
Maglll'siulll also eornbiues readily witt: chlorine ditiv!' trsted, irnprovPL the color of the flare slight-
dud, therf'fort" wilI cGmpete whh tilt' barium for ly liS a larger percentage of it was used. This
tht' aVl'ilable (·hlorillt'. There is also eompetition slight improVPIllPllt ill ('olor is believed to be due
h!'tw('Pu ('hloriup and oxy.gcn for tht' bariulll. To to tht' dpereast' in luminous intensity. The im-
sel('ct tht' bt'st ('hloriup litmor (( ~b is ideal but tDO prOYl'mPllt in ('oJor of the compositions containing
difficult to hand I!' ), fiPv('ruI ('umpo!;itiulls were l'hlorillated orgllnic additives resulted from an
tt'sted ,,,hidl ('ontaillrd org'llnie ('hlflridt's having illl'reas!' in th!' amount of barium chloride formed
di/fer('llt }H'ft·t'Uhlg't·:, ;li' ehlol'ine. 'I'}wse compounds liS Wl'1I as from dp('rrRSed lur!linous output.
Iowt'l'ptl tht' (·IlIH11epow.·r, with g'pnt'I'IlIly improved It has also b('l'n sllggrsted that the addition of
1'0\01', aud ill(·rtll~,!'d tht' IIlllollnt of barium ('hloride II ('hlorin{' ('ontaining compoUllll to a flare mix-

fornwd. Tht' tl!'st resuItH w('rt' ohtailwd with a tUrt· III liy , by shift of t'quilibriulIl, result in the
eOlu posi t ion ('OIl t II i IIi Ilg' ·to 1)('1'('(' It t IlHtl(lH'si nm, 4fi forllllltioll (If bariulll hydroxi.lto whieh ('mits strong-
llt'r('('llt bariu", ('hloratt', 10 Ill'rt,'nt polyvillyIidiJ}t'- ly ill tht' !!rt'en.1~
t'hloridt', alltl ;; {l('rI'I'1l1 LUlIlina\'. 'l'h(· diloriue·to-
iJariUIIl ratio was :IA~ to 1.0; th,· Ill/l;.!'/l{'fOi1l'n-to- 6·3.5.5 Binders
bariUIlI rill lfI wu., 11.~ If) 1.0, Hlld tilt' ddoriut,- Binding Ilgt'lIts-illl'lutiinK <,rrtain r"sins,
(!ivuiJabl.· ttl bariullI Ho-oariulll ratio was O.27~! to WlI XI'S,plast i(·Ii. /llld oils-,s('rn' Illultip I,' purposes
l.O. All otllt'r ('hlorillt, ('Ulltllilltllg' atlditiv('" illl- ill !'yrot,·l·hll;(· l'Olllpositiuns 'l'ht'Y an' added to

6·38
AMCP 706-185

catalyzed, they undergo a transition from liquid


gel tc solid as they cure, ~2
The results of a series of tests involving poly-
~ster resins, presentei in Table 6-9, led to thp
conclusion that the maj0rity of these resins would
_____ -pyrotechnic Flame
be satisfactory and that mixtures containing these
materials would be as stable and have the same
burning characteristics as mixtures containing
TJaminac as ~> binding agent,
Zone "A" The luminolls intensity fc·r all mixtures tested,
including J;\ binar), mixture not containing a binder
""""'"-----Zone "B ,. of any kina, varied greatly during the first month
Pre-IIIOItion Zone of storage. This strongly indicates that the binder
is not the caust' of this variation. Then> is, how-
ever, little, if any, cnallge in burning rate asso-
l'iated with this ~hallge ill luminous intensity,
--"-_---- Zone "c"
Unreacted Composition
6-3.5.6 Particle Size
The rate of reaetion of a pYI'otechnie composi.
tion is relatNI to the specific surface of the in·
gl'f'riiellts. Fadors such as size, shape, distribu-
tion, and surface of the particles aift'ct the proper-
ties of the particulate material and must be ac-
Figure 6·22. Zones iii Flame Propagafiun ('nratt'ly ('(lIItrol!efL Thl's£' faelors affect the pack·
ing prolwrtit's of tllt' ingrl'dients whieh, in turn,
prewllt :it'~rt'gatioll lind to obtain mon' U1liformly dfpet tilt' w('ig-lIt·\'olume rl'lationship of the pur-
blPmlc'd ('(Il11positions, In addition, they serve to tit'les,
mllk(' the lillely oIividt,(1 partieles of metal and ~\~ hl~s b(,PII illdil'uted ill the disellssioll of prop·
(lxidil'.t'r a<lllt'l'I' 10 e1H'h (Ithl'l' aud help to obtaill ag-at iw burlJillg (Pal'llgl'aph :!.a,6), the hurning
mllxilllllill dellsity and, t1:l'rt'fol'l" I'fticil,llt,y in ratt' alld l'alHllt'powt'I' of 11 pyrotl'chllie ('omposi·
hllrnill/!, Bind('l's also fl'e(plt'ntly dl'sl'nsitiz(' mh· liolJ tll'lH'lld Oil tht' partidt, sizt' of the Ilwtal pow·
tllrt'S whi('11 would ollwrwist, Ill' wry ~wnsitive to tit'!' fUt,!. 'I'his t'ff"d is shown in «'igurcs 6.32(A)
illlpal'l, fl'idioll, alld slati(' t'ledrieity Hnd, as awl ti·;t~ ( B ), IIlId 'rllblt, 6·10 for all illumillllllt
hilld('I' ('OlltPllt is ill('n'as('d, hurllill~ rat(' is dl'· llIixtlll'P t'olltailJillg' 1II1lg'IIt'siullI, sodiulIl nitrate,
,'I'('ast'd /lIlt! ,'ulltllt'powt'r )'('(lu(,t'd, poly\'illy/t'hlc"id(" Hlld [ . aminll(', A deerease in
~llIt('I'ials ;'lIl'h as lills('t'd oil, USt'd ('arlier in parti('lt' sizto fol' tilt' spill'ril'ul partidf's J'('sults in
Iitost sllllldul'd PYI'(Jtt','hlli,' ('oIllJlositiolls as binders, all illl'I't'IISt' ill tht' s}}('('ifie surfaee·--the surface area
ox idiz,·d 11 lid Ita I'd"llt'd oJ IIl'ill!!: stOI'Il!!!' ('Iluiiill~ a ilss(H'iatt'd with (lilt' ~l'ltlll (,f po\\,t!('r-·-an inert'llse
dtllll/!o' ill t h,· !IIII'll illg' l'hlll'lIderist i('s, Tho' I't'· III t IIr ;'III1l11t'pO\\'('r. IIlId lin illel'('ast' in thl' hurn··

pla""nlt'1I1 of ]illst','d oil by Lamilllll', Il polyt'stt'1' ill/-!' rnl(', ,(,hi" is ill lIg-rt"'IIH'lIt wilh tilt' tlipory pre·
l'psill: 1 g'rl'atl ... · l'l'o!lI,·,'d Ihis pruhlt'Ill," It was S,'lIt"" ill I'UI'IIg'I'<lph :1.:1.11.
I'olllld that s,·II'·hal'li.-lIillg' poIY"s!t'l' rt'sins tt'lItll'd '['h(, aho\',· I o'~lIlb W,'I'(' ohtained for ,'omposi·
to Illillil11iz,' !11t' 11\'0·d 1'01' hig-II "ulIsolitlatioll prt's, ()U!J.~ ill whi('1I t h., Illagllt'siulIl was "SSt'lltilllly 8
Stll"·S. ,\ltl~! "I' !h,· I'oly,'s!,'!' r('sins tlSt'" 111',' ('S' ~ph,·l"·. allY utll,')' 1'(1)'1 id,' ~IIHI'" will )"('sult ill II
"·lllialt.\" ,'S!"I's !l1l1lll1fadlll"'d frulII g-l)'('uls IIlld 1I11· larg't')' ~I",,'ili(' slIrfa(',· thllll that of II ('OIlIJlllI'able
~atllral,·d a"ids '11101 IlltlIlOllllt'ri,' '·I'uss.linkiIW adeli· "ph","'. I II 'I'ahl,' ,i· II. t hI' hlll'pillg- ,'ll1u'IIl'\('risti('s
Ii",·" ~Il,·h a~ "tYl't'II" alld diallyl phthllllllo' whii'li of "ilJJdlll' l'(olilp(lsiti,ql~; PJ"'}JI.l'l'd with I!l'oUlld and
II!'" IItiliz"d til "Ill'" th,' )',·~ilJ. \\·lit'll lh,' ro''iill~ an' witl; iltollliz(·d IlIag'IIt'silllll having' tht' salll!' Hieve
AMCP 706-185

21
11 1.

26 !

6 7 8 9 10 11 1~
I.S l'

Figure 6-23. temperature Distribution in a Pyrorechnic Flume

ti-40
AMCP 706-185

7~,000 1

%:
0
Z
700,000

650,000 .

600,000
Loading Pr...ure 10,000 Poun:b per Square Inch
\
\
350,000

'"D::
c(
500,000
;:)
450,000
a
U)
400,000
0::
l&J
Q. 350,000
f/)
300,000
'"
..J
0 250,COO
Z
c(
0 200,000

150,000 LITHIUM NITRATE

100,000

50,000

--,-~~~:==~~~J
eo
10 20 30 40 10 70 80 80
MAGNESIUM, PERCENT

Figure 6-24. Luminous Intensify as a Function of Magnesium Content of Binory Mixture. ContoininW Various Oxidizing
Agent.

sizl's arl' (·omparl'd. 4:1 Thl' j?ToUlld magnesiJlm 6-3.5.7 CODIOlidation4•


(which for SOIllI' sic\'" sizes will ha"l' tht' greater The dl'gree of consolidation (loading preaaure)
spe('ifie surfa('\,) gins a hight'r luminous intensity h~ s varying e/fect on the burning rate and lum-
and a faster burning ratl'. An ilH'rea~:t' in burning inoU!; intensity of 8 pyrotechnic mixture, depend-
rate and luminous intt'IJl>it.v generally follows the ing lJll the p!lysical eharacteristic8 of the COUl-
inert:a8t' of "pecifie surface of the ingredients. It ponents. InereIWt'd cOllsolidation pressurl' results
is to be lIot I'd , how('wr, t hat all i,wrl'as(' ill burning ill '1Il incrt'sscd pellt!t density which approaches a
ratt' and luminous intensity lllay :,(, lU't'ompanied maximum, whi,!h ill uHually five to U'll percent leas
by II rp(it,ct ion ill t ht' O\'l'rdlI effiei,"H'Y. thlill th,' thcoretiesl \·/llue. Til Figure 6-33 and
TIlt' hurning eharactf'risti(')' of pyntechnie Tabl!' 6-12 are shoWII tht' f'ft'ects of loading pres-
:';)fllpositions Itrt' al",o l'.1rectl'd by tht' spt'('ifi(' sur- sure Oil hurning ratl', iumillOll11 intellsity, and
f/l('I' of tilt' oxidizers liml other inln"'.'dit'llts. Whilt' other characteristic!;, lx>tWl'l'n 2000 psi and 25,000
rl'lativl'l.v littl!' data arl' lI\"ailab,t' on th" sppcifil' psi for ma~lIcsinm-sodium nitratt' flares. The lin-
t'/fpct produced. in a particular system, it is im- ear burning ratt' shows a slight decreGSt' with load-
portlillt thut th!'y hi> l'onsiul'red. ing pressm"1' whw' the mass burning rate and ium-

6-41
Allep 706-185

45

Loadi ng Pr... ur. 10,000 Pounds par Square Inch


40
l&J
....
~
Z 35
:E
a::
l&J
Il. 30
U)
I&J
:J:
0 25L
z
W
..
f-
e( 20
0::
c.?
Z
Z 15'-
a:
~
m
10

:L~_~_~I__20 30
L-_-4I_ _ ''--'-L_''--_.L.1
40 50 60
_-. L_~_- -'_-.JI,- - I. .- .J
70 80 90
MAGNESIUM, PERCENT

rigvre 6·25. Burning Ratll a. a Function of Mo~nesium Content of .8inary Mixture. Containing Variou. Oxidizing Agent.

ti·42
r----------------- --- ----

AMCP 706·185

TABLE 6·8(A)
PHYSICA.~ DATA AND BTJRNINU CHARACTERISTICS FOR STOICHIOMETRIC
MIXT'O'RE3 OF VARIOUS OXIDANTS WITH ATOMIZED MAGNESIUM

Stuic:~io- Calculated Luminous


metric h·eat of Reaction Intensity Burning Rate, Efficiency,
Ox,jdc".t Ratio Kcal Cal/y Ga'ndle/sq in. in./min candle-sec,l g
-.-- ----- ._,
LiNO a 53.2/46.8 631.0 2430 109,000 13.9 17,500
NaNO a 58.3/41.7 595.4 2060 102,000 13.1 15,500
KNJa 62.5/37.5 569.8 1760 27,.500 6.9 8,000
Ca(NOah 57.5/425 647.1 2260 64,000 6.8 18,000
2l'(NO g h 63.5/~~6.5 626.8 1881 50,51)0 7.7 12,500
Ba(NOsh 68.8/:J1.8 615.5 1606 45,000 5.1 14,000
KC10 4 58.8/41.2 515.8 2441 37,000 5.2 15,000

iI10US intensity show !til in':reasing trend. These other cases the resuits have varied considerably.
daLa huve been found consistent w~th the trends With certain compositions, investigators have ob·
observed in most pyrotechnic compositions con- served an apparent maximum in linear burning
taining magnesium althongh they are not as con- rate associated with a particular flare diameter.411
sisttmt '.'or eompositions containing aluminum. Investi 6ations of typical yello'v, green, and red
InsufficiPIlt consolidation of tracer composition flart' 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
fl111ction known as "blowout," whe::-e the pyro- intensity could be expressed mathematically by an
t.echnic compositioll is ejected frore its cavity. This t'quation of th(' form :46
mmally happens shortly after the ;>rojectile leaves =11 ax" (6-15)
~he gun. In &mmunition depending on tracer func-
(for diameters less than approximately 4 in.)
tiouing for self-destruction, this usualiy results where y is the luminous intensity (candela), a
in a prt'mature projectile functioning. is II constant, x is the flare diameter in inche&, and
The requirt'd loading pressure or extent of n is a ('011 stant. The value of n, which was ob-
cOllsolidation dept'llds Oil the st'tbllck forces and tained when the results were plotted on log· log
amount of rough handling to which th:, item i .. rapel', indieated that n is slightly greater than 2.0
to be subjected. Ot'IIt'rally, the greater the setback which may be due to some change in the flame
for('Pk, ~ll(> greah'r th,' required loading pressure. geomf'try, Ot· to an increase in the flame tempera.
ture The flame area tended to exhibit a direct
6·3.5.8 Flue Diameter proportionality with the square of the flare diam.
TIl(' illflUt'IIeI' of tlar(' t1iamt'ter on thl> linear t>tt'r. Yellow and green flares showed an ivcresse
and mass bU/'lIillg' ratt', luminous illtellsi~y, tem- in luminoUis effi~iency with increased luminous in-
peraturt' tlistr;butioll, ('010, va hit', luminous effi- tensity; however, (heir flames appeared to become
,.jAUt'Y, allll flllmp g'1'O II ll't I')' 1II11~' vary ('OlHyid!'rably Ipss "atllratpd with increa8ing flare diameter. Red
dppt'lldillg' ou gt'lIprlll ('OIlfi~llratioll of tilt' systt'm fillrt's l'xhibitl'd maximum luminous efficiencies for
ii/hI t h(, pyro!<'('hll il' ('omposit iOIl. A bllsi(~ end, illlt'rlllt'<iiate \'81tH'S of luminous intensity and the
hl"lIillg' flllrl'. fr('p frOll1 th!' illfllH'IJ.·('s of CIlS(, ('olo/' l'illlra(·tpristies did lIot appear to change with
g'('ollwtry Ilud ('olllpositioll lIud 'lsslwiutl'd mate- all jllt'I'past' ill flart' diameter.
rials, should l'OSSf'SS a lillPar burlliug' i'att' I'SS(,Il·
tally illl\I'Pl'!Idt'llt of tht' flllrl' dinlllt'tpl'. This lIas 6-3.5.9 Cas.: Materials and Coating
h '('11 th(, ('IISt' ill 1Illlily iJl\'t'stig'atioIIS ('olltlu('tt,d Both tlw physie8l and chelllied eharacteri"tics
m'('r rathi'r Iilllit,'d diamt'tl'r rallgt's; howl'ver, ill of pyrote('hllil' ('ase matl'rial lind associated coat-

6-43
AMCP 706·185

IT
O.eoo ~-
I
-- -- ~+-------+------_1-~---l
---~-~
-------- -----+----+--t-----

. '00' -1--;'--4-
I
-+---
i
.100 -~ -_..
o
-
.• ?O
X

.400

500

.too
( ---

100 J
j I
000 ..;-.--------+---+-........
0.000 •~
I I
!fIII'f--..--.-.--r+---~-----+~---f--.~~r~
400
I • I ... Ioo.!.ao
.SOO .
\'
x
Figure 6.26. ChrOnKf;city Data for Ilt>d, Yellow, and Green Flare.
1)-4.4

- ---- -- --- - - --------------- ------------------~


----- -- -- -- - - -------
dCP 706-185

45001
J
5000
, a5CO
.I
lOOQi
I
Il00'''
. " I .
"
;
"


\ "

1$:;4""
,>,

BaNO, EMISSION (GREEN .. LAM)

"


.
• •

.
• • • •
'

-
',' , ~ --
..


.

' , ,'"

"
"

,
",':
~

'
~
'"
..
• >

'7
'.
i,'
"

'-". . " ..' , "


. . , , ": ,".
SrCI Z EMISSION (IN CARlON ARC)

Figure 6·2i' Typif.;.:.I'Spectra of Signal Flar••

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 those con- positions. 8<>me compositions also have been ob-
structed of paper or other materials, may preheat served to burn more rapidly and produce a greater
the com1Josition and thus tend to decrease the time luminous intpnsity in laminated plastic C8ses than
to ignition and increase the burning rate. In addi- when loaded into paver eases. In this casu, the
tion, thl! increased wall temperature may aifeet character of the adherence of the eompooition to
the ('oatng material and promote side burning. the waH may be important; however, a completely
Both of these eonditions tend to increase the lumi- satisfactory explanation is difficult.
nous intensity; however, they ean 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 eharacteristics of illuminating flares, depending
when using steel cases as opposed to paper cases. on the composition. In a studr8 made on yellow,
Wben paper-lined steel cases w('re used, lun.inous red, and green compositions it wars found that at
intem.ity val ups were mIdway between those for a reduced temperature, - 65°F, the candlepower
steel and thosp for paper, although burning rates and burninr, time of the flares, except. for gl"el~n,
wl're comparable to thosp obtained for paper cases. deereased. The color value was found to he affected
I II l'onti'llst, HI(' rt'\atively eooler-burning green differently, depending on the eomposit'o;1 at this
composition gave lower luminous intensity values tempt l'ature. (See Tables 6-13, 6-14, and 6-15.)
in the steel ease than in the paper case (for which At high simulated altitudes, the burning time in-
intfMlwdiatl' values wert' obtained) even though l'reasell I"hilt' the calldlepowcr deereased for most
the bumin;.\' rates rellUl:ned essentially the same. Hares test!'d ill this study_ Color values were in-
In this casp, the heat lobS tt, the surroundillgs from ereast'd at tll!' higher simulated altitudes with the

6-45
AMCP 706-185

TABLE 6·8(lt)
CHARA.CTER.ISTICS O.F BINARY MIXTURES CONTAINING OXIDIZING AGENTS
AND ATOMIZED M.AGnESIUM, GRADE A
---_..__._-_._.,---_.
p~:~~~
_ _ "_ _ _ _
HoritJ>ntal
LumiMU' 1.''{1(Id
p.ndulum Frirtio"
Ted Rtaclwn .lIiIh II IBO'C
V_um El!idC1lCII,

I__~~~__'_~__::~~~::!__ ._. ._. .~_.__. _1_,:,1.":......I~~:.. .~~'.!~O lar~:...\ ____~/.,,~ _.2:':~_


AJoo..Gr.A Itll.wv. Burni"" Y",llow Ian. ilion StolYJilv Candle-
I
1""ilWiliiy 1'''' - _ ..... _ ... - .. _..
Sodium (1'6Ji/.) CantUa)'er Rat" Cc.lor 7'eml'erature A. Bl.ck R.I!". App"t SIt',1 Fib-ir Tell, ce, lJentilv s,.'J)M,
....!!..itrat, I~aium Squo. .. ,1ldI ._i'~~'__
n ~ 3~:~ U = ~ ~~ ~ ~~~~.. g:~ U~ ~:~
68
54
50
40
42
46
50
00
102,C)o
!M,OOO
180,oeO
386,000
13.1
15.6
16.0
26.1
II 0.025
0.024
0.026
0.029
tl30
63~
6a~
UW
0.5
Q.~
l.:lIi
1.1b
100+
100+
100
IOU
Non,.
Non.
NOlle
Now'
I 0.32
1I.3t
0.36
(l,',I'J
1.02
1. 7g
1.74
1.71
l!i,1IOO
20,(100
20,000
31,000
30 70 686,000 39 0.036 620 1.1'5 100 None 0.32 1.65 36,000
26 15 '185.000 43 o.caa >5 100+ None I 0.33
..- I
1 B2 41 000
20
16
Barium
80
85
Akm.Gr.A
670,000
445,000
43
3~
0.038
1),041
670
~'10
2.75
>5
100+
100+
NOlle
Noo. _. II C.2:> I 1.<19
1.1>1
30;000
~3,QOIJ
NitroU Maan,';um I
80 20 6,500 2.9 pcle green 680 ;>5 lOOt ,",ou. o.~~ ! '2.48 3,300
68 32 46.000 5.1 pal~ gl'OOD ~70 :--5 100+ N<lIlo r..25 2.24 14,000
64 36 63.000 6.7 pal. green 640 :>t 100+ Nooe ._., r..IS 2.21 13,000
~
""
~
""
n,1\OO
186,000
IQ.7
16.8
pal. kloon
pale gre....
630
615
>6
1.26
100+
)(10+
Non.
No<>.
I 0.1.8
0.2i 1.9\1
2.0~ 9,800
13.11(1()
40 60 348000 38.1 palell1oo/l 625 1.25 )(1(1-\" NOll. il.lS 1.tl6 17,600
30 70 360 000 40.3 pale green 6~5 >~ H)(I.j- N<o<le O.:W:\.84 17,Il00
20 80 r.rratic Burning 62~;>5 HIO+ NOlie 0 22 1.83
Slrontium A1.?m.Gr.A Rid Clilm
NUrat, Maamaium Yol~c 0.1,1 :1 :!2 6,Il00
80 20 10,IlOO 2 " 0.20 61~ Nl.>n·
600 None 0.16 2.:15 10,000
70 30 34,000 6:0 0.19 l. d6 12,600
63.6
60
60
36.6
40
50
60,1\00
68.500
162,000
7.7
8.9
21.1
0.18
O.I~
0.22
80.1
600
6\0
None
Nc".
Hone
.- I I 0.15
0.14
0.14
1.112
1.7\1
12,000
14,500
6!0 Nl)IlC 0.19 !.7~ 22,000
40 60 200,500 24.8 0.24 0.27 1.6a 24,000
30 70 307,000 28.0 0.:!6 615 None
620 Nc)oe 0.18 1.57 27,600
26 75 286,000 24.0 0 ..31 1.52 33,000
20 80 260,000 20.4 0.27 610 Nooo
LilIIi"m Atom.Gr.A Rid Cole,
NUrat, Mogneaium Val". L08
80 20 Erratic Burning 1.71 7,200
70 30 21,000 Q.01 0.17
60 40 18.Il00 13.3 0.16 1.68 12,600
0.18 1.62 17,500
63 47 109,000 13.9 1.54 20,000
40 60 236,000 27.9 0.20 20,000
30 70 350,000 41.6 0.21 1.49
0.2(J 1.43 22,000
20 80 310,000 45.1
CaIci".. Almn.Gr.A Rid ('.010,
NUro/. Magnuium Val,_,
1.8 0.2), 1.9Q 3 500
80 20 3,500 I.g6 11)00
70 30 26,000 4.0 O.lb
0.111 1.86 18,500
67 43 64.000 6.8 1.81 :W,OOO
~2 46 86,000 8.4 O.IB 1.73 32,000
40 50 188,000 12.6 0.2[,
22.0 0.2~
1.68 40,000
30 70 382.000 1.01 41,000
26 76 400,000 23.3 O.2~
0.30 1.60 41,000
20 80 362,000 21.6
Polauiu.. A/Qw\.Gr.A
NUrat, MOl/fl4leium O.ltl 1.81 tlOC
80 20 000 2.3 White >h 80
3.15 &Xl
1,100 4.1 White 2.'15 HO 0.13
70
62
68
30
38
42
27,500
36,000
M,OOO
6.9
8.6
13.3
Wbite
White
Wbit..
1.6
2
1. 76
00
76
00
I (1.l6
(L11
0.16
1.7:l
l. 72
1.68
S,1()O
9,()(lI)
9,()(\()
60 IiO I. 76 O. ~ 1 1.62 9 .000
II
21.8 Whiw \14)
40 00 86,000 0.1:\ 1.61\ Q~I
29.3 Whit<· J.5 100
30
26
20
70
76
80
119.000
11&,000
70.000
31.1
26.4
Wbite
Wbit<, 0:10 >5• lOO-i
.00-+.
, I
O.l~
O,U
1.6:1
1.63
Y:lJOO
6 ••100
PoIouiUII A/Qw\ .• Ir.A
PorcA/mat. MDqIUIium
80
70
20
30
2.500
17,500
Z..
:1.8
WWhibi·~.
~
100
710
I >5
>6 I I()')+
lOOt
No".
NIl\,.
0 :10
1l.~4
I.g1
1.78
2.100
~.5OIl
().Z~ \~',OOll
69
60
40
41
50
60
37,000
46,000
M,OOO
I 6.2
7.0
10.;1
Whil<-
Whit.o
Wbije
706
71&
700 I
>6
>5
>6
IllH
100+
00+
Nu,.
NOM
Nooe I 0.:(5
(l.\ll
I.n
I.M
1.1>0
I It.OOO
1'1,0.'10

~ ....;.._,__
,__ ~ ..\...~~:5J
___ .1..1.._-47:~.~ ~~E
_ _..:...._-
____ 7_00 _1_...__I. _._.!·,:.t .._~~J'_
___. .~_ _8·~aJ
._.z
,_'__,_U.~
.....~~_~~.:.~.,,_
1.64

0Loldiac ~wre 10.000 pair ill I." SqIlAlll Inch C.~dIo COOl.
t Bureau ill MiD. ApparatUL

6·46
,----- - ---- - - - - ------ -- - - - - - - ------------ ------ - - - - - - - - - - - - - - - - - - - - - - -

AMCP 706-185

TABLE 6-9
CHARACTERISTICS OF PYROTECHNIC COMPOSITIONS
CONTAINING VARIOUS POLYESTER RESIN BINDERS

I-B~'- -.. """.


Total Integral CIE Coordinata
Candlepow"., Light, 10·
Polyuler ReMns 1000 Candles inch/ minute C(l1Idle-&fCOOl8 z II
-- --.
Hetron-92 84.0 4.4 3.7 .>.52 0.&5
Paraplex-43 70.3 3.5 4.0 0.54 0.30
Paraplex-444 65.0 4.2 3.2 0.50 0.35
Lamh'lac 4116 64.5 3.8 is.3 0.5:, 0.36
Paraplex-13 62.5 3.3 3.7 o.5:'~ 0.35
Faraplex-47 ~2.0 3.4 3.5 0.52 0.36
Glidpol-lOO1-A ·J1.2 3.5 3.4 0.52 O.M
Interchemical-401 60.5 3.9 3.5 0.57 0.32
Pleogen-ll50 60.3 4.0 3.2 0.54 0.34
Aropol-7120 60.0 3.8 3.u 0.56 0.33
Polylite-8001 59.3 4.1 3.3 0.5(; 0.a3
Interchemical-937 5&.0 4.0 3.3 0.57 0.35
Polylite-SOO7 56.8 3.8 3.2 0.55 0.34
4116-85%:4134-15% w.6 4.1 3.2 0.55 0.33
Aropol-7300 06..1 4.3 3.0 O.b\. 0.33
Pleogen-lOO6 56.4 4.1 3.0 0.00 0.34
ED-l99 56.2 4.1 3.2 0.57 0.32
PLL~j262 56.0 4.1 3.1 0.58 0.32
Vibrin-l088-B 54.5 3.4 3.4 0.56 0.3:S
Paraplex-49 54.4 3.4 3.1 0.52 0.30
LamiMc-413·1 53.7 3.9 3.0 O.t",f. 0.34
Vibrin-1l7 52.9 3.9 3.0 0.55 0.00
Interchemical,,312 51.7 4.1 2.9 0.56 0.32
Celanese-MX-314 51.4 4.0 2.8 0.00 0.34
In terchemicul· !J 91 51.4 4.0 2.9 O.~j 0.33
In terchemice.l-'/30 51.4 3.'7 3.1 0.5j' 0.32
In terchemical-ll54 50.2 4.0 2.9 0.56 0.33
Stypol-4051 49.5 3.8 2.8 0.55 0.33
Stypol-405 49.1 4.0 2.7 0.55 C.M
4.2 2.7 0.56
Aropol-7110
Sclcctl'On-5027
Cdsilese MR zs..c
43.0
48.4
46.0
I 3.1
4.0
2.1l
2.6
0.55
0.55
0.33
~.34
0.34
EpOZIIIlu-i-/
Bakelite EHL-2795 81.2 5. 1 3.8 O.'ill O.:'t)
.--

t'XCI'ptiOIl of gn't'11 which relllairwd essent:.aUy con- resistanre off~rt'd by die air molecules. lliter-
:-;taltt. mediate reaetiPJls oceur further away froIn the
Thl' rangl' of Hliitudt's at whieh flyroteehnie fiart· surflll'l' alld. in many cases, a. "dark ~~lmlO"
it,·tlU; may Iw used is frOlll UfO to approximately t:HlI be obi·wryer! just Ilbovt> the flare surfacb ".lId
:~;)()_Oll() fp"t. Thc dl't'ds prod IH'I~d \lndt~r reduced initl il reaction zones. If the presI>ure lJecomes low
!,l'('N,.;lirt':, ",tll Ill-' attributl,d to both thl' reduction ('!lough. a poillt will be reached wht're tll!' read.ion
ill OX.r!,(t'!i and H!llbil,,·t pressUl·p. Tltl' effects of will Hut be sf>lf-sustaining.
tlxygr'Jl rpducti,)11 lIlay IH' grl'atl>r whl'll fW'l-rieh The inversl' rt>l!\tionship lwtwc-en candlepower
mixt.III·('S 111'(' burrlt"!. ["or stoil'ilifJlIlt'trie )r nell.r- /Iud 1'0101' vutUI' is attribut!,d to the inl~re!j&ing im ..
-,tuil'hioll\t'tr',· ('(lmpositioIlS, tlH' piT(",t is main,y portullcl' of tlt(, ('0101' litl(' and hand emissi,H.\ from
Ihal of Pl'l'SSIl rt'. It has lW'.'1\ sllOwn t !>at by main- c)('itl'd atoms and molt'cules at the hig'her uHitudes
Li( inillg' H prt''>snrt' ow'r th,> tlul'P imr'fl\('{' througb
Jlar: iii! (·O/dlnt'mPllt by lise ,If' Ii Ilozzlt" till' burning
"1.' I,' at high simH!."-': alt.itlld •. · (,('\tld br rllis('d tu ( 3.5.11 Rotational Spin
tli.· sam(' It'vd a, dlht at sea 1.-\e .. 411 'rhl' efft'l't uf rotational :;pln 011 the bllnlill(~'
Lar,"!'i' nalll,·· phllll'" lirt- Pl'oJw.'I'd as thr am- (,ltaral'tl'risti(':' of ('ompo"itiollS has bi-.en invNlt!-
bit'lIt l'n'.~S\lrt' i)l rt'dlll':·d ,~\lI' to tht' dperpR.'w ill g-ated. It has been found that th(" rotil.tionaJ "ipin

6-47
AIrICP 7()6.185

110

gO

ACTUAL. EMISSION-,

70

(f)
~
z 50
::::>

)-
cr.
«
D::
.... 30 _.
co
D::
«
SELECTIVE EMISSION
10 -

I
450 500 550 600 6~0 700
WAVFLENG ..... H. MILLIMICRONS
Figure 6-2B. SP«fral Energy D;atribution of G,..,.., Flar~

of a 105 lI11n illumiuatinJ.{ projectile canister con- sted by the fact that flares which are rotated at
siderably silOrtellt'd th~' bl:rning tiLle of the il- the slow('st speeds (which have the longest burning
lllmi.nant. 'l'h!' e/fp\'t \,f rotational Kl,m on flar(>JI times) show much less slag residue than thuse ro-
/uad.,d in I.;'-llwh O. D.. steel flare ':!lI>CS was also tated at higher speeds. }<'lares tested at speeds
stud i(·d. EX8milillt iGll "f burllt'd out flare cases of a,ooo to 5,000 rpm, however, all contain ap-
indielited that dll' f"l·niltHlg et'lltrifugal forces pre- proximately the same amount of slag.
Yellts tll(, ,'xpulsioll ot Hllt';\ of the slag. The slag [n anotht'r study, tht' trace duration of a tracer
huills Ill' and \·/fcl'tl·dy deereases UP internal WI1S found to br shortened, as shown in Figure
di';lltldt't of th,· 1~1USt'. This deCrt'IUli.' in int 'rnal \!,\&t' ti.:14,~o by rotational spin. Burr.iug rates fo!' tracer
<li'li'ilet!'\" pr(".'t·nts thl' t'ffi,~ient ...xPIIIsion of gages \ ompositiolls increastd with an inereast' in diam·
for'lIf'd and thus (,Hllses an incre"sf' in the internal der. or lellgth of tracer column and this increase
pri'!,SUrf' As II rNllilt of the prl'SSllrt> increase, the was more pronounced as angular speed was in-
illllmillulits hurn mor,' ral··ldly. This is substanti- \·rea.'il'd. In geiH'ral, for Clwh eompositioll the per-
,-------------------------------------- ----------------

AMCP 706-185

TABLE 6-10
EFFECT OF PARTICLE SIZE ON BURNING RATE
AND CANDLE POWER FOR MAGNE3IUM-SODIUM NITRATE-
por.. YVINYLCn~ORIDE-LAMIN AC MIXTURE

A'I.'erage ParUcle
Ingredients Size, microns Percentages

Magnesiu:m, At., 20/50 437 48


Magnesium, At., 30/50 322 18
Magnesium, At., 50/100 168 48
Magnesium, Av-", 100/200 110 48
Sodium Nitrate, DR, UljP 34 42 42 42 42
Polyvi llylchloride 27 2 2 2 2
Lmminac &sin 4116 8 8 8 8

Time-Intensity Data
Candlepower, 103 candles 130 154 293 285
Burning Rate, in./min 2.62 3.v1 5.66 5.84

~ 40
:J
in
....
Z
, 315 400,000

C)

"'
~
30

.... 2iS
Z
IU :i 10'),000
U
0
•o
~:r
IX
w IL
0.. 101
I I I I I I I I I ..J
Q
66 68 70 72 74 76 18 eo 82 84 Z
PERCENT PURITY ~ 200,000

Figure 6-29. Magne;~um Content Verw. Excitation Purify


for a Y.llow Flare

eentagt' loss of slag decreased for {,Reh diameter 100,000


with an inereas(' in rotational speed. Total light
'. j
~~~~~~~-=1
llutput rxprrssed in eandlerower seconds decreased
with all illerpas{' in rot.a.tiollal spped. ftO

10 20 30 40 0.0 10 '10 10 10
6-3.5.12 Moisture and Stability
MAGN£SIUM. PARTS
\ hlP t)f tilt' illlPortant factorfl in detprmining Figure 6-30. Effect of Polyvinylchlorid. on the Candle-
tllp stability and shelf life of a pyrou>chl'ie item power of Mixtur•• Contai,,;ng Stron;ium Nitrat. and
is th{' s{,ll"itivity of' the pyrott'ehnie eomposlf,on Ground Magnesium, Grado A
to lltU\o~phi'Tie moisturl'. III the presenee of
mwsturt', tht' oxidallt will react with t.ht' metal ltydl'Oxid£', or both. This lIonreactiw layer (~hanges
particles to form a lay"r of metal oxide, metal tilt, ilo{uitioll Ilud propag-atiV(' charae!eristics of the

6-49
AMCP 706·185

TABLE 6·U
EFE'ECTS OF CHANGE IN SPECIFIC
SURFACE OF MAGNESIUM PARTICLES
0.110
Ground Atomized
Magnesium Magnesium
--------------_.. _--._----
COMPOSITION, %
0.40
Ground magnesium 66.6 a.J
:)
Atomized magnesium 66.6 ...l

Sl)dium nitrate 28.6 28 . 6


4.8
'"
>
cr
Resin 4.8 0
..J
(100.0) (100.0) 0
(.)
OliO

CHARACTERISTICS

~
Candlefl per sq in. 200,000 178,000
Burning rate, in./roin 9.4 .57 I
Density 1.56 1.65 0.20
Candle-seconds/ gram 50,000 69,200

I
pyrotechnic mixture so that reduced luminous
intensity or nonigni tion may result. 0.1 0 '-----;I~O--;;20~--;:lI:;.0--:40~-!.1I0=--~IO=--~10=--~.0=--~1O
The critical relatiw> humidity is a measure of MAGNESIUM, PARTS
the sensitivity of .xidanb; to moisture. It is deter-
Figure 6-3J. Effect of Polyvinylchloride on the Color Value
mined by t'xposing samples of the oxidizcr~ to at~ of Mi:ftures Containing Strontium Nitrate and Ground
mospheres of knowll relative humidities and deter- Magnesium, Grade A
mining the change in weight of the oxidizer. The
l'ritieal relative humidity is that at which, with re- In ~me eases, it has been found f'xpeditmt to
spect to JIloiflture (~ontent, the oxidizer is in equi- ''''mpromi!>e 'hH' to an oxidizer's excellent oxidizing
librium with its surroundings. Roughly, t!le ltigutlI' ability. Thif; has hren thf' case with sodium nitrate
the ('riti('lIl relatiw humidity, tht' lesfl soluble tht~ t hat formerly had a critical humidity of 50 percent
oxidant. Small t rlll'ps of impuritit>!,; may lowel the for the specifieatioll gradf'. 'rhe use of U.S.P.
I'riti(':.1 r(>lativl' humidity of a ('()mpoulld. tloubll'-refilled sodium nitrate with a critical
TABLE 6-12
EFFECTS OF LOADING PRESSURE ON BURNING CHAR.ACTERISTICS
OF MAGNESIUM·SODIUM NITRATE FLARES

Luminous h"n~'"ow C/)<mpo,UwlI


l,oading Intensity. Total Light. Burning Burmng Chromatirity F /fIciltf&C1l. Dmnty,
Pre ..ure, 100u I X J(J!I Cantlle- R/ltf, IIlchl'll Rate, G Color Cordlnatel, 1,)(0 C-S~o Or""
Pri Candle ... Seconds Per .\lin ute Per Sec01\tl Ratio PM' Gra~h P~r
CG
.'
II)
.-~- - -.. - - " -----------
2,000 27H 7.2 (j.:.w 6.54 (J.036 0.48 0.46 42.6 ).54
~,OOO 292 7.0 Ii. :1:1 7.20 0.036 O.4H 0.46 40.7 1.64
7,000 262 7.1 ;).62 6.75 0.037 OAH OAti as.7 1.74
lU,Ol)O 270 7.:1 Ii.n 7.12 o.oat) 0.48 0.+6 :37.9 1.90
15,000 286 7.4 ii.6:! 7.69 0.035 1l.4H 0.45 :17.2 2.03
20,000 29] 7.6 ii.li7 7.55 0.035 O.·Hi 0.46 as.G 1.95
25,000 290 75 /i.92 7.69 0.037 OAt-! 0.45 37.8 1.88

6-50
,--------- ------ - - - - ----- ---------------- ---- ----------- --------------------~

AMCP 706·185

TABLE «:·13
EFFECT OF SIMULATED ALT.l:Tl.)DE AND TEMPERATURE
ON ILLUMINATION CHARACTERISTICS OF YELLOW SIGNALS

LOT Y-1 LOT Y-2


----
Average Average
Simulated Luminous Burning Yellow" Luminous Burning Yellow"
Altitude,· Temperature, Intensity" Ti'me, Color Intensity, 1'ime, Color
Feet OF Candles Second.~ Value Candles Seconds Value

70 53,300 19 .038 ]24,000 9.3


°
10,000
20,000
70
70
39,200
19,200
21
24
.047
.058
113,000
91,000
11
9.5
.052
.062
.062
40,O(}O 70 6,650 49 .064 55,000 12 .072
0 -65 44,500 15.5 .055 78,000 9.5 .074

• Pressure reduced to simulatc condition at altitudes shown.


** The color value was determined using the procedure given in P A Tech Heport No. 1385.

TABLE 6·14
EFFECT OF SIMULATED ALTITUDE AND TEMPERATURE
ON ILLUMINATION CHARACTERISTICS OF RED SIGNALS

LOT R-1 LOT R-2

Average Average
Simulated i,uminolts Bunting Red" Luminolls Burning Red"
Altitude,· l' empcrat II rc, Iniemity, TinH', Color Intensity, Time, Color
.Peet OF C(tndles 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 .4(1 :18,000 14.5 .60
• Pressure reduet'd 10 simulate ('OIl(litiOIl at Itltilurles sho\\lI .
•• The color valllt' WIlS dl" ,'rlJlilll,t! using tht' procedurc given ill PA Tech Heport No. 1385.

humidity of 7fi IlPn'l'lI! partly alleviated this mosplwres of nitrogen and oxygen exerted only a
problell1. 43 slight influem'{' on the corrosion rat~ whereas hy-
Thl' t'ift,,,t of lIl11isturt, 011 /I filll'ly powdere(l drogen al\fl ('arbon diOXide were observed to have
lIlt'tal ('all hI' dptprlllillt'd by ph!t'illg a sltn.plp ill rt·tur!llllg and accelerating ('tfeets, respectively.
distill!'cl watl'r Hlld mailltaillil,g till' system at a }<'urtl\t'r, thl' ralt· of (·orrosion increa&ed with an
Sllt'('ifit'd ('ollsIHllt tl'llIlH'raturt·, By (·ollecting thp iUert'ast' ia sp('{~ifi(' surface.
gu:o. ('v(Jlvt'd III ('Ollstallt prt'ssurp, tht' ratt, of cor- Om' way that the deleterious t·{fect of moisture
r,)sioll of tht' IIlt'!!ll c'all bt, t'stahlished. For Oil maglH'siullI or other mf'tal ('an bf' avoided is
atOllliz('d lJIagl\,'siulII,~) it was. found that thp ratt' to ('oat tilt' metal with a thin l'hromate film. Pro-
of t'orrosioll inrrl'ased with time hut only slightly It,!'tioll of tht' atomized magll('sium i:1 consolidated
bl'tWt't'll th,' tt'ml'l'ratures of :Wo(' and 65°(" At- illuJllillatillg Hlld signal (·ompositions 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 Luminous Burning Green·· Luminous Burning Green"
AlNtude,· Tempera,ture, Intensity, Time, Color Intensity, Time, Color
}I'tlet oF' Candles Seconds Value Onndles Sec01l,ds Value

70 14,300 16,5 ,36 :18,700 16 ,35


°
10,000
20,000
70
70
14,300
11,500
21.5
26.5
.39
.37
20,500
20,50tl
15
17
.36
.36
40,000 70 11,000 30 .41 1!l,500 26 ,35
0 -(j5 27,800 20 ,36 :15,700 15 .25

* Prel!8urc rcduccu to 8imuJa t t' condition at :tltituocs showll .


.. The color value wos dctcrlllillL',\ using 'the procedure gin'll ill PA Tech Heport No. 1385,

400

.
t'
~4

~
! ------
r I.

o
'AI/leu SIU (MIClONsl
Figure 6-32.1. Bur~i"g Rate vs Particle Size of Mag".';um Figure 6-32.2. Ccmd/epowe, va Particle Size of Magnesium

ll!'eolllplisill'd Ity tilt' IISI' of bill(lt'I'S Illld water- luill/nlts bPI'HIIM' tlw,\' do 1I0t (·ontain billders and
pr()otill~ a g-I' II ts, IIslIltlly all oil. wax. or plastic ill'l' loosl'-loutl!'d whil'lI t'hllllW'S till' IIlHl1ner in
I','sill. ('ontaill('I'S /lilt I lIoll;lYg'rOS('opi(' first-fire \l'hi,'" thl',\' rl'al'! to Pl'otlll('!' lig-ht. COllsolidated
,'olllposit iOlls 111'(' 1l~.',1 to k('PJl moistllrl' from th,' ('(llIll'osir ions "lIrll ('mnpllntti\,ply slowly while m.ll-
maill illlllllill/lt in:.! '·()lIIpositioll". "ollslliitiat!'tl III i" til n's, 1II111!'r ('olriiu!'lIlent, reset
rupitlly prod\ll'ill~ a hright ib~h of light.
6-4 NONCONSOLIDATED ILLUMINANT Th .. Illajol' 11 .... ·' for lIolleollsoii<illtl'd illuminant
CHARGES dlll!':.!'·s III''' ill I'''ototlll~h hombs Hud "artrid!!!'!; for
As P,\'l'ot",'hlli,' rl'll('tioIlS, ill :.!('lIernl, It 1'(' baspd lIight Il'Tilll pliotU/!l'1li,hy, IIlld ill spottillg eharges
011 tht' ..!It'llli,'ni r('lletioll of a flH'1 with 1111 oxillizer. 1'01' tru,·kill:.! alld 1I('qllisitioll plirpoSl,'s. NOfll'onsoli-

tl ... 1II1111111'!' ill whi,·h th,'s,' two basil' illJ,{!'('dif'llts dut,·" till .. rs I II'" l/IlI' : l I \ intllllllt(' mixturl' of a
:tl'l' IIl!'orp"l'at('d illto 11 flY rott't'hlli" dp\'i('" will pOII'fi('r!'d 1II(·tal Itlld po\\'d,'!' oXirlllllt, (21 II pow-
~r('lItl,\' illtlll('III'" its 1If,d'O!'IIl1l1l'·'·. \'(>lII·tilt ...ul;· .I,!',d IIld.d, ~lIdl 01)0, II IiIl{l lI'si 11111, or
,dIUl.illlllll,

<latrd illlll!.illllllts difT('!' frulII ('Ollsl,litillt,'(1 ilh~ t IH·ir alloy.;, /llld (:1) II pow(krl'l\ lIletal IUld II

ti-fi:!
AXCP 706-185

~
::>
z
... 14

...
i 4.7

.,.. 4.6 12

~
...J:
u 4.5
~
~

~~
~
10
~ 8""6"-
'. Pit
..; 4.4
~ "i"3.?~~
.. ~~~ t--
I-

.,z'"
4.3
:g
li'r'i" . . r--..~ __ R-284
8
r----:.;
....
Z
::>
4.'! -
0
Z

4.1 iJ36 r---


1.11 I
-..;;...~--~

4.0
0 5,000
I
10,000
I
15,000 20,000 25,000
R-~ r-- I---
4
LOADING PRESSURE, PSI

Figure 6-33. Effect of Loading Pressure on Burning RClIe of 2 --


Pyrotechnic Compositions
o
powdered oxidant segregated from each other 2 3 4 !i G 7 8 9 Ie
in eoncentrie cylinders. 10,000 RPM

Figure 6-3 .... Effect of Spin Upon Tr'lce Duration 0 1 Various


Standard Tracer Compositions When Loaded loto Caliber
6-4.1 AERIAL PHOTOGRAPHIC .50 MJ Jaclcet
ILLUMINANTS
The mission of aerial photography is to obtain tion of tlIP light reflected from the area to be
information rf:'garding the static content of an Ilrea photogrllphed which rl'achcs the photographic film,
(buildingH, roads, etc.), and the movement of per- and
sonnrl ancl I'quipment. At night, this requires a I'. EXpmHlr(' timt' which, for night aerial pho-
light sour('r that will pl'Odlll'e suffi(~it'nt illumina- tography, IIIlly bt' thl' duration of illumination and
tion to obtain usablt, negatives. High intensity hot the shuttt'r speed.
light sou reI's for night arrisl photography may Th" intensity of tilt' light source and ib. rela-
be brollllly !li\'iliell into two dasst's, pyrotechnie ti\',' jOt'lltion dl·trrmine thl' illumination received
ligH SOU;!,!,!!, and tlir ('lectrollil' flash tube. 1I2 As by t h" ur('a to be photographed us well as tae uni-
flash TIlbes 111'1' unllblt, to produce liS much lijrht as formity of till' illumination produced. As shown
pyrotl'/'hnil' light sour/'t'S, theil' use is limited to in l<'igurt' ti-:lii, tilt' I,wation of a pyrote(,hnic light
low Illtitudt's. At higher Illtitudt's, photoflash I'ar- sourt',' ('IlII b(' sl)('l~ltit'tl by "riving tht' trail angle
triligl's lind photollash bomhs Ilr" the only practit~al anll tht' hurst Illtitu£i,'. 'I'h,' trllil angll' must. be
SQur(,I's (If illt"IISt' illumillation for night aerial sufiieit'lltly ~J'l'utt'l' thun tl1l' I'umpra half-uilgle w
photography using ('oll\'('I:tiolllll Ill'rial canwras IISSllft' t hilt ollly tlit' rt'ftt'l'tt'tl lil{ht fl'om the area
lIud pilotogrllphil' film. Ilt'iu~ pitotoj;trllphNl will rt'lleh th" l'Umt'rll leml.
'I'h" him spI'l'd, basi('ully, Jetl'rllliut·s tllt' IllJlount "'or Il Borllllll trail Illlgh- valu(', th,' optimum
of IiI{i1t wltieh IIlUst full 011 t ht' film in or<il'r ttl burst llltitllllt' I:as ht·t'll dt'tt'miille() to be about 0.6
tlbtaill It :,111 isfl:dory III'gatin'. 'I'1.t~ amount of light of tht, tlij;tht Illtitutll', wht'lI tht' rt·(luil'l·tl iuti'nRity
wilH'1! 1"'Il"h,'s thl' photogrltpili,' film dl'pl'll()s Oll: of th,' Iigltt sour('t' is a minimulll,lI3 At the opti-
II. AlIlllullt of li~ltt r"tl"l,t,·.! 1'1'0111 till' 111"'11 to be IIII1I1l burst IH'i~ht tilt· Illllollnt of light r'!4uir"d for
phoio~raph"d, whil·h tlt'pl'lIds 011 the' illuminatioll II slitisr~II't(Jry llt'~lIti\'t' is Ilpproximattly :5~
':nd tht' t,'rrllill ,'('tlt'd/IlIt'" llf !hl' un'u,
.- 1\"
t ' '(''j\),
b. H!'lllt iVI' illwrtu:-t' of til!' ('umt'ra h'lls which i!l 1= .--"" }.
(6-16)
llu.-mully t'xpn'SSt'tl hy I \'!llut'!! 011 u Il'lls barrI'l art' l'
th,' tlialllt't"r of till' )I'LS Illwrtu:-t' di\'id.'d b:! thl' wlll'rt· J iN till' ('untll,'pow"r of till' light source,T
f')('1l1 1t'Il~th of tltt' It'IISt'S. Ti,t' trHllsllliSHitl1l l'har· is tilt' expOSllrt' tilllt', I is tilt' t,tft,eti\'t' f value for
/It'tt'rist i.,s of t ht' II tlllusph!'rt' dt'It'rmi lit' tht' POl'· I ht, It'IlS, A is tbt, slant distant't' from tht, camera

6-53
AKCP 706-185

-.,.... ----------- _... -


pelting charge whi('h ejects the inner charge. At
the same time, the. delay fuze is initiated and, at
the end of the delay time, It relay explosive charge
is initiated and, ill turn. initiates the ph0totlash
mixture. As the delay time determines the location
of the burst behind (and below) the aircraft, the
proper delay time will depend on the 8peed 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 ill Table 6-:1.7.

tJ .. TRAIL ANGLE H .. FLIGHT ALTITUDf. 6-4.1.2 Photoflash Bcmbs


d .. CAMERA HALF-ANGLE h .. 80MB BURST ALTITUDE Illumination for high altitude night photog-
raphy is provided by photoflash bombs which are
Figure 6-35. Diagram of 80mb Surd and Trail Angle
released from the aircraft during the photographic
run. A typical pho~oflash bomb is shown in Figure
lens to 'irea being photographed, and U, is a fac- 6-38. Descriptive data and characteristics of photo-
tor best determined experimentally. However, as flash bombs containing photoflash powder are sum-
showf. in .F'igure 6-36 (which is a typical charac- mari.zed in Table 6-18.
teristic curve for black aDd white negative ma- Photoflash bombs containing a relatively large
terial), it is impossible to estimate the exposure U, amount of flash powder can be very dangerous
required to produce a negative of satisfactory since they can be exploded by impact. Because of
ohotographic density. Miritary specification for this danger, dust-type photoflash bombs were de-
film is based on the reeiprocal of twice the ex- veloped. The characteristics of dust-type photo-
posure of a point on the curve at which the slop,} 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 aoo 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 charaeteristic curve, i.e., was started. Such a configuration appearec tc
for this material an exposure of approximately offer the possibility of safety frorn impact initia-
0.05 log E units. tion, and also of producing the high peak 'candle-
power of the flash powder bomb, along wi h the
broad peak associated with the metal dUB ·type
6-4.1.1 Photoflash Cartridges photoflash bomb. No photoflash bombs of this
Illumination for relatively low altitude night were standardized. Results obtained with s me
aerial photography is furnished by photoflash car- experimental segregated oxids'lt bombs are s
tridges. As shewn in Figure 6-37, these cartridges mari~ed in Table 6-20.
contain a photoflash charge and a delay fuze assem-
bled into a c!large case. This subassembly is put
into an electrically primed outer cartridge case 6-4.1.3 Other Photographic Illuminant Systems
along with a small expelling charge. The cartridges Attempts have been made to u:'crease 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 af) a night aerial photographic il-
by an electric pulse which Muses the electric luminant. Unfortunately, it was found that this
primer to function which, ill tUI'Il, ignites the ex- increase could not be obtained without incurring

6-54
AM.'CP 706-185

TARLE 6-16
DESIGNATION AND DESCRIPTION OF PHOTOFLASH CATRIDGES
- ,-
Powd"
-------- I '0
T,m.
I nJoqraJ Uglol,
10" c•• &utu,

TlO
Carjridg. D.,ignation
Silt, in.
Lx Dia
7.7IXl.56
Tolal
Woi~lol,
Ib
-----" - - -
- 5.25
0'
-_.---
Typ<
--~-
/<ormuf,a

l)
(Ion
-B-
P""k
'""""~t!
10 6 Can
2(
IPm",u_
••,
5
----- 0'Duration
CPS
-0.77
a""
Telal CPS ••
- -- -
FIIl,A,
mile C""pU FlU.
flt.ad ..d M11 Time delay
Signal cue 1 to hec
1'12
-0.72- -5.75
- - _.- . - - - 5 0 - - 1-,-5- - -- -- - - - ---
7.73X1.57 II D I 30 Modified Mil Tim. deb.y ,2. or 4 j

--_._-- ----- ---_. - - - - - lOe


~1112
---.--.---------- - - - -
MI23 (T89)
1.73X1.57 )

8.37;~2.9
:-1,:):;~I:--------1---
: : ,. :- 1.(

-.-----
5
-.

4.8
30

40
Modified MI;

Al
Tiru. delay
1.2. oc 4 sec
Obtun.tod delay hllle.
2.~. or 6 sec
1'90 About same - About - -..-- - ' Eac~
as MI12 same as
I:-r
- - 'stat:
_ -(b)-
1
aNO .• /atom·
X.6
---~.---
2 b '.,' 600 Outer .....
.imilar to
Obturated delay rUle.
10r2_
-

MI12 iJed Mg bind· M112; COil'


er. 30/70/2 wos 5111...
- - - ' - ----,_. ------ --. -'--- ---~-
------ - - - - - - --,-,----
Tt02 ~X1.75 1.25 12 fll A 16:) 4 2.4 -- 31(0) AI. 0051 in.
~~~L::':~I~1 rUle
wall
Tl03 llX 2 .375! 5.5 27.2 III ~ 325 4 7.2 H.6 mal AI, 0.051 in. Similar to M123
...a11
, I I
I
(0) to 0.1 max.
(b) Conlain8 a high intensity illuminating COlD;HlOition, liOt phototlaah flO..-der.

(li'iadvullt.agt's whil'h essentially nullified any gain as well as thl' u:,:e of small arn projectiles as- spot-
ill output. ting' rounds for majOl' ('aliber weapOIlS, Jed to Ii
Otht>I' PYl'otp('/lllic li~ht sourl'(,S have been tried rt>q lIiremPllt for mort> efi'cctivr spotting charges.
which "'1'1'(' design(,<1 to produce illumination on a
eontillllons hasis rath('l' than ill short bursts fl)r 6·4.2.1 Small Arm Spotting Rounds
IISP with strip-typ(' ('ampras which do not contain Small l'illilwr spotting rounds ('an be used to
a shutter. Tht' film is moved contillUOll.<;ly I'eross a aim It m;.jor ('aJibei' weapoll. III operation, the
slit at a speed whi('h matches that ot the image smail ealihf'r spotting' rifle, which is rigidly at·
motioll. 011(' of thp early at:('mpts was the use of tal'lled to thl' mail! weapon, is fixed and the point
the T90 photoHarl' ('artridf{e. This eOllsisted of the of impact is indieated by a flash of lir,ht ana a puff
sam I' ('a<;ing a.~ thp ~\I11~ with a (hargp of fivn stars of !oiJlIOkl' fOl'lned by the fun(ltioning of the small
whi(·h wer(' wadt' of 1l. high i!ltensity consolidated (·;tlilwr sppttillg' pro,j(·dill'. As thl' trajectory of
illuminating (·onlposition. The light output was the small arm spotting' projectile :mo that of the
not. t;deqlIate as 110 yisihlc imagp wa~ obtained on maiu round ar!' Iwar:y identical at the critical
th(' lIPgati\'('s ('xpost'd ill flight test. at 1000 fe~t..M range', tit(' burst provides information for 'tdjl'st-
Another aHem;)t \\'as a blll'lwr fOI' ma;,\"nesium el l .1st IIlt'lit of ainl. A hit with the spotting' round rr,eans
which was <1c\'('lopprl fot· use on a.ircraft. 55.00 that Ul(' main projedil!' will a1/l0 strike dose to the
t arget. 5•1.:iS
6-4.2 SPOTTING CHARGES A typi(;&i 20 mm spotting round is shown in
~potti!lg' (·hargops ai'e used for locating point of Figure 6-~H!. This round contains about 6.5 cubie
impad, for targ'f't acquisitioll, for tra.cking, and fOl' ('(,lltiUJ('ters of a fla,,}) mixture and ('an produce a
illdi('utioll of item or ('ompollent functioning. For flash of 1.5 millioll ('andl!'powoer with a Iluration of
maJlY ypars, spottiug' chargf's of bla('k powder wert' 700 III illis(,(·onds.
used ill pra<~ti(·t' bombs· and projectiles to locate
poiJlt of illlpad. Bl'eause the observation distances 6-4.2.2 Tracking
\1'('1'(' rplatiwly short alui becaw;p a rl~latively 11 ig/!ly .wI'urate trajectory information is re-
largp \,Ollllllt· was l!\'uilabl<' for the spotting' charge, (jllJr!'d ill till' dpwlopment of a missilt' system.
all adl'(juat.> flash (·ould be prod\1('('d with bla('k ()I!(' method of obtaining' this information for a

[lowder. TIlt' d('vplopllH'nt of long rangp missii')s, missill' at high altitude·s is to photog'raph the tiash

6-5fl
A)lCP 706·t85

------T- T-'- /
/
./

~LSHOlJLDER
,,.-

2 ----+-_._--+----_.- // l
I--::;".c.j
I /1
/~~--L--_+--__:I'~....:e. I.~- ____ •

O.b3

1--- -------------~~~----~~--_r---

£2 ;; 0.002
S2 = 500
1
ASA EXPOSURE INDEX = 125

LOG EXPOSURE METER CANDLE - SECONDS

Figure 6·36. Typical Characteristics of Block and White Negative Material

produ('t'(l by it photoflash cartridge ejected a dis .. ean be accurately determined. 66 •8 ! A typical flash
tall('(' sufficiput to prtven~ (lalliage to the missile ('har,!?e for this purpose is shown in l<'igure ().41.
in flight. }<'lash ('artririg!'s of the type silOwn in
F'igllrp fl··iO (whi,'h are of the same general type 6-4.3 TYPICAL COMPOSITIONS
discnsspd ill Paragraph 6·4.1.1) were dpveloped Typical nonconsolidated illuminating composi.
for thi~ purpose. Modifi('ations to reduce weight tions USI'<l as photoflash and spotting charges are
and simplify nh>unting problems resulted in a flash ~umma I d in Table 6-21.
dl'vicp whi'~h produces a series of fla"qhes with a
known timt· ilJtt'rvfll bptw('en th!'m.IIO 5·4.4 Light Production
As has been indicated, nonconsolidated illu.
6·4.2.3 Indication of Functioning rninants differ from consolidated illuminants in
F'lash ('hargf'... art' llS£·t! also to provide !l. visiNe the manner in whieh lhcy rElict to }.iforluce light.
indi(,dtioll of tllP functioning of lin item or com. Com;olidated compositions propagatively hl~rn in
pOIlPnt such as a warhead fuze. The fll'sh signal II rrlativply slow manner while noneonsolidated
provid!'s II brilliant light !lash and can b(> photo. ('om positions react rapidly produeing a bright
graphil'alIy re('ord!'d I,y r!'IIlotl' camprHS, providing' fla:lh of light. B!'ellusP of the rapidity (If the reac.
oata so that til(' tilllP and locatioll of fUllctioning tion, functioning of d!'vices containing noncon.

6-56
-------

Alt'CP 706-185

TABLE ti~17
CHARACTERISTIC':; OF TYPE HI PHOTOFLASH C'OMPOSITIOII

hlt)"cdicnts: Specification Mi.;ron.~ Pe~'(len~


------
Aluminum, atvmized .JAN-A·2~9 15 40
Potassium Perchlorate ~ A-PD·2J<J. 24 30
Barium Nitra.te PA-PD·253 147 30
Physico-Ohemical Data:
Heat of Re"lctiQD, caljg-2774 (calc)
Reaction Temperature, C 0-approx. 3500
Gas Volume, cc/g-24 (c,llc)
Tapved-l.67
Vac. Stab, 120°C, ce gas/40 hrll-{},H;
Sensitivity Datil:
Impact: P A, incCes·-4(}+
Friction Pend: St~el-Crs.cklf's;
Fibt)r-No Action
Ignition Temp, °0: 5 see value-oIG: D'J'A--No Ignition
Hygroscopicity: ;)7% HU, room temp; lirs 24; % Wt Gain < 0.:
Electrostatic
Sensitivity: .Tonl!', M:ro 2.14: 50% ?t-3.5; 100% h-4}i
'l'emp-65"F: o/(l R.H~O; Unconfined-Yes

soiidatcd illuminants can caust> disruptive effects ration of the !lash (milliseconds). The total amount
in their surrolmdin~ similar to thl' I'tti'cts pro- or light p!'oduced lletermines th,~ maximum ex-
dnl'ttl by high \'xplosiYt'~. posur~ which (an be obtained at any a.ltitude,
using open shutter techni<:ues whl')fp the duration
6-4.4.1 Light Output Charactf..-istics of the flash determines the exposure t.ime. Unless
The light produced hy the functioning of & image movement compenAAtion techniques are used,
devic,) containing 3. non~onrolidated illuminant i~ the speed of the aircraft must be low enough that
characterized by its relative high peak intensity imagr relative movement win not result in uoac-
anil the relatively short flash duration. eeptablr photographic definition. DnW the devekp-
ment of image motion compensation techniques,
6-4.4.1.1 Time Intensity62·83 many night aerial photographs Were made with
A typiC'll time-intensity curve for the Hght an exposure time of %~ second (40 milliseconds).
p:,oduced by the ft.J;ctioning of 11 photoflash device In this lase, the exposure obtained depended on the
containing- 1\ fillsh jJowder (intimate mixture of amount of light produced in 40 milliseconds, and
powdered metal and oxidant) ~!Jarge is shown the maximum photographic exposure was obtained
in I<'igure 6-12. The curve for most spott:ng with the shutter open for the best 40 milliseconds.
charf!'es wouid be similar. As indicated in this (See Fig-ure 6-43.) Peak candlepower is important
figurp, the important (:haructeristics of the light as it greatiy influences thp amount of light pro-
output of a photoflash device are: (1) t(ltl1l amount duced in the be>1t 40 milliseconds. The time-to-peak,
of light produced (candlespconds), (2) amount of llnd the variation in the time-to-pt>ak are important
light prod'ed in t.he be"t 40 milliseconds, CPS 40 for sYlleip'oniz8tioll of the shutter oven time and
(cand1eseconds\ (3) peak intensi'.:' (candles), (4) the bt'st 40 miJIic;ctonds of the light flilsh.
time to peP.l{ m tensi ty (Jr.illisecoll ds), and (5) du- Dust-type rlwtoflash devices produce flashes

3-57
I..MCP 10(;..185

M59 PRIMER
8.41 MAX

Figure 6·37. Typical Photoflash Cartridge

whieh have lower peak intensities and longer dura- 6-4.4.2 Nature of the Photoflash Burst61 ,68
tions than those produced by devices containing 'rhe light-prodUl:ing characteri(Jtics of a flash
flash powders, as shown in Figure 6-44. Image itf'1ll depend pril1l'ipally (as discussed in greater
(·ompensat.ion tl'rhniques are normally required delail in Para!!raph (j-4.5) on thf' composition, the
when (lust-type photoflash bombs. are used in order amouut and shape of the explosive which is used
to efficientlY utilize the light produced. to initiate the eomposition, and the case. Flash
radiographie studics show that when a relatively
6-4.4.1.2 Spectral Distribution small amount of high explosive-crntrally located
As shown in Figure 6-45, the spectral distri- ill Ii (~ase containing photoflash powder or metal
bution eurve of tltl' light produced by a photoflash dust--fUlwtions, a bubblr of explosion products
de vier (~()nsists of all intense continuous back- is formed in the fir!>t few microseconds of the
ground 011 which a discretf' spectra is superim- initiation of tht' explosiv('. Thf' shape of this
posed. IH The speetral di&tribution of the radiation bubble and the rat!' at which it expands are de-
produ('ed by a (!lIst-type photoflash bomb is similar. pendf'nt on the properties of t.he material sur-
While the mort' l·ffi(·ient photoflash t'ompositlOnf> rounding it, as well as that of the explosive initio
at low altitudes produce light whi('h is mainly ator. I<-'or t'xamplt', the shape of the bubble pro-
(,(JIItiIlUOUS, the more /·fficient {'om positions at high <111('('<1 by a small quantit.y of explosive in flake
altitudps (100,000 feet) Ilre thosc whieh produe(' aluminum which has a low density tends to be in-
an t'xtewm'e diserete &peetra in the visihle.65.6~ (Ree fhlt'lll'ed mort' by the nature of tht' (>xplosive and
also Paragraph 6-4.5.) its eonfinemf'llt than the bubble produced in an-

6-58
AilCP 706·185

TABLE 6·18
DESIGNATIONS AND DESCRIPTIONS OF FLASH POWDER PHOTOFLASH BOMBS

Pow.,. lnJ,,,,al Liolll


Bumb To/al
---- Formula Ptak Tim,to
loe Candl,'«OM. Dundio"
o! y;,ull.
Dt'41Q- Size, in, In. WI. - - ' - - Int' ..u~. f'tok. CPS B,n """(0
nati('n L X Via. Ib Ib 1'~p< Cia" JO' Candia mItt ToCal CPS.o 0.1 mar. CIUiAq
----
MI2 (Tl)
- - - - - --- - - -
32X7.25 32 25
--~~

1 .- 326
------
10
----
-
---- ----
- 250(0) PaPf!r tube divided inlo 2 comr.!Im",,"';
pGwder filled 4/6 of Yo/UIM; ywcod S
~itiOll; 2 gronade lUi ... &II parachute
In 1/5
----- 25X4.25 -- -10- ----- -- --- ---- ---
M23 (T2) 7 [ 100 10 300 - 13.5 - I - Fiber cylinder; Iat..,r filted "ilh aleel ou"'r
_ r~ improved baI1ialics
---- - - - - - - - . - - - - - - - - - - - _._-- ----- - - - - - - - -
M46 (Ta) 48X8 50 25 11 A.ll 7;0 18 50 26 140 :ero~~:~Ji container; aula o\eol
' -_.- - - - - - - - - ---- - - - ----- ------
n Enlarged 1>146 50 II Il 970 20 65 36.4(0) - Light wei«hl aheet meW ..... po"der in
fiber cootainer
T5 Enlo.rged M46 --
- -
100
- -- -- ---- -'--
1670 20 132
----
71.5(c)
----
--
~-.--

Light "ei&:>t ah..t meW ..... po.d.. in


----_.
T6 (MOO)
- - - - -----
_I_'I_A_
-----300
---- - - - -
fiber cootaincr
-

_I_II~_
31.72X4.92 25 10 1I 15.4 8«) O.023l1-in. wall. Thin met.al CallI'
T6El - - - - -- O.026-in. "all
~- 500 - - - .- O.04S-in. "all
---- -----.- ------
~DRC
Tyl*'8
80
58Xl0.75 200 to Varioua
\leat
17oo lb ) 15 1b ) 118(b)
Ileat
6O.5Ib .• ) - 250-lb TI cuing
141
T9
TO!>I 36X8
-- ----
U5
115
88
70
35
-nTs-
II B
----
8&J
- '-
2 99
-
30
--
-----
270
- :2f>-lb demol.itioo bomb. <:Me, O,I~ in.
--
-163-- -
TY!>4-6
_._--- - VarioWl - - - wall
T9ES 35X8 70
-!II- -A - -----
-~---

2100
- - - - ----
5 140 65 163 M70; 0.19·in. ,,&II
---- ---
----~-~-
-III- -A - - -3490- - - -6 - - - - . ---_.
-~-- , .--
M120 52.25><.8 150 70 75.6 1631~5 Modified M70 chemical bomb body. bol
tyPf! 60. 0 .1SS-in. wall
----- ~--~-.~
- - - - - . - - --- - - - - ----- - - - - ----- ---
MI20 IH B 52.25X8 165 85 III A 6 4~90
223 96.9 188 Same ... M120
------ -- --_.---.-- - - ._-- - - .- . - . - - ----- ----
T92 39Xll 280 138 III B 5840 6 290 140.5 226 Optimum design to fit in RB-4 aireralt:
sballow. "ide fin
----- -----
T93
---
S9.16X!4.18 496 224
- - - - - - - - - ----- ----- - - - _ .
-~--~

III A 4000 5 373 108 2M 1IOO-Ib G.P. bomb c:asing. AN-M46;


MI09 6n _mbly
69.5)<18.8 926 450
- -
--~-

III A
- - 5600 M
--'--
66e
- -
163
- - ----
I()()()"lb G.P. bomb r.aaing AN·M65
T94 29\l
----.- - - - - - - ' - - - ---
---~
'---' - - - - - -
Tyg 4.250r 13 95 70 -- - - - . - 42. - Tbin eoPPf!f caein&. at ~ 0.0626 to
to 160 O.II-in. "all
---- ---"-- - - - - 64
- ---
III B (Eod 00)
- - -
Tl04
or 104 2900 4 IS\) 82 163 Modified M30A1 1000Ib G.P. bomb body;
(thin 3570 ~ thin ..... model. modified M47A3
cue) (thin oaae) 6 284 88 228(.) oh.mical bomb body

(a) Total duration (b) Witb Type II. Cluo B powder

odized alumi!lulll. The subsequPllt sha.pe of the indel' of metal dust. In all cases initiation and
uubblp in tbl' metal dust depends 011 th!' resistance burnnng of the dust takes place in the air after case
PJIl'ountprrd in ditl'prent directiollS>. If the con- breakup.
fining' ('as\' ,l\,fol'1lls ... lowly without nlptlJre, the If the surrounding material can react rapidly,
shapl' of t lH' pxp!OSiuil produets will tend toward gases resulting from the vaporization of the reac-
tIl(' shap" of til\' ddoI'lllt'd easr. If the ('ase rup- tive material at the outer surface of the expanding
tUft'S quiC'kly at OIl(' point, th,' (lust may be forced bubble of explosive products will increase the
t hJ'OIl~h this oppning whil{' HOIllP of th!' dust will rate at which the bubble expands. The amount of
J'('maill in tIl(> (·ase. 1-'01' small quantities of ex- this contribution depends on the reactivity of the
plosi ve, tIl\' ,:,hap{' of tllt' explosive is of little im- mixture. The piston action of the expanding bub-
portallce. For larg!'r quantities of {·xplosive, the ble forms a spherical shell of compressed flash
shap,> alld Its Illethod of iuitiation must be con- composition, Rapid chemical reaction starts at
sidered. Au extreme \'xamplp is an end·illitiah,d the shock front when it reaches the case and the
lillt' eharg!' axially loeatcd in a surroulldiPls cy1- increase in pressure results in case rupture, After

6-59
C'>
en
o
>
fiC
TABLE 6·19
o
~
CHARACTERISTICS OF DUST PHOTOFLASH BOMBS .....

Bomb
I
I Su<o In.
To/ai
Wt. In. I
I

I Peak
i'a","cr
r---- ----- --- ---I
I lnt".iJv.
T,me (0
P<lJk.
I Inl<tJ1aJ

CPS B,,(
L,~hJ
L_I_06_C_andl_u_fC_'-
I
.4!tltud.
II t~~~e II~Fa;;~h.
and m..c to
-
~
00
(Jt

DuigTllJlion LXlJul - ~-- __lb_-,-_~mUla____ llO. Flou:•. ~JPo"hon, It ~_ _ _ _ C~s\"o Bunler

__
Candlu __rn." _ To/aJ CPS," .
T,
_ _ _ _ _ _ , 46. 72X8
I __
65_(r_) I_~ M_g_._u_,a_de _1_1_ _ _ _ _ _-_-_ _ _ _- _ _ _ _-_ _ _ _-_ _ _ _ _ _ _ 1\ _ _ _ _ _ 1 - ~~,~h!~46 caae WIth

T8 I 1200 I ,0 Flake ~!g, Grade B 41 44 ~ I l.v(a) ,Modlfied


I-G. ?50-I" A~-Mfi7 Tetryl; conical;
T8Et 140XIQ.7~ ------- -------,---
I I P.Bon.bcaae,O.3-in. tinplate conf;&iot=l

T9E2 - - - - I36XS.--103
150 1 35
-1--,-
Flake AI. G ....de...
Flake Al
1100
42
10 49A I 35.1
- -:;;;--I-=----- -I----I--.=--
I
",aU
125-lh demohtion bomb
case. 0 .19·m. wall
!TritonaI5Ib---

~:: I:::~-- ~II---~--- ~;;;ent AliS, 75/25 38 __ -_J4-fi-_-II=---_I_--~~=_-_I=-----r----== s:ru-e-""-T-9-E-2---II~n. diameter each:

Type 1 I . 52 Atomized Mg 650 14 21l - I i - S h e e t steel. 0_06 in. Trit<nal. 6.S-lb


I
I II
==
2 1 52 Ato!Uued Mg 600 13 2U ' u U ; casing/burster Sodatol e_l-Ib
3 00
2fi
Atomized Mg-M alloy 1300
non
13 30 1
' .I diam. ratio: 4:1 'fritonal5.S-lb
4

, =55. - ------=-------------
.-- 60
21
21
I ... . =I=--=
..,
Atomized Mg-AI alloy
Flake A!
=I
I.12\-,. AI
750
~r;,!lO
15
13
14
23
2(\
I
~ I
SodatoIS.J-Ib
Tritonal 5. 8-lb
Soda!.ol 6. \-Ib

D:~~lliati~_
T O. 2-m case thickness
MX8 -/IOO(!)

T S6EI-4 35x8
3~XIO
I ~5
Vamus metal dust. ',&noo: Varied:
:l~-
Vatie<!: I Varied' 25,000- 5,000- 11\1--
~12
M 47 chemical bomb
---------
Vatious
70 UOO-- 164.a- 50-94. 35,000 15,000 case; 0.()6 in. wall
I
N1122 (TB6G,
2~Xll
i 24XI2
5-IX8 11Q -15"- Atomued fi
U5'l

(15/35 ;g-AI -- ---g;;-- - i i -


alloy (20o!: microna)
121 600

-CC·-I'"
I

1_ - ·'.""'1....'· --=-1-
20,000 30· trall
1-----
M2~, I-in. diam.
cylin<lrical; 2-lh caot
70/30 triton&l;
Ml47El fuze

--·--1---- - II
1_ _ angle best
T B6E5 13 diam. - - I Atomued Al - - Thin AI or steel TST and booster
~9
()..6' 27 .aX. ~ ~I AJ dust and KC\Q, 672 --Z-S--I-·---'lo.2 B2 , Coneentric burster. QU- Hand packed TNT;
otgreg..ted I I dant, meW dust tube! Tetryl booster; Mli6
fuze
------ 4"8-:6X8 96 ~ S';:-mt as 0-6Y- - - - ~ - '42- - - Best, I-T-Q--(A~ - - - I Mi6 caae adJ,pt<.! to
0-
3490 I I 130 30,000 13.000; ! coneentrlc loadmg
Il"ud packed TNT;
Tetryl booIter;

T ------I5-IXB ilO -M--I "•.• "'" 1-';;;;:-1--2-~--1---


U70
iTo--' ::° -----iI Best.
4B,9 30,000
1: :
13,000
1
Modified M47A3
chem. bomb case
M146 fuze

Larger than 0-70


bunt.<r

I---=--- ----I~I---- ---- --I--


30' trail

x - - - - 39-.;00---
I J7:; 114.2 ~me as ()..69
I Best, - !
angle best
Concentric casing~ I
I 4890: ,
y
_ _ _ _ !B!"'ciall designed
Hand tamped err.-
I tallill. 2-in. TN .
!
\227g--\-----SO- '34.:l\ ~--'I----I--~=-I--'---
t-Ib; Tail fuse
I ..
XS3 AI ..ith 3':< SiO. gel.
, KCIO.
- -----
I '
--
I
I Con~enUlc cas~.
"peciaUy design
1.7-lb hand tamped
TNT. Tellyl
.: I I 1 I . l>oosW; Tail fuo.
I
lolDuriDl 0--60 mote
AKCP 706-185

TABLE 6-20
SEGREGATED OXIDANT PHOTOFLASH BOMBS
- Integral Ligh8
Total Powder Peale 1O'Candte3ecl!,
Bomb Size in. Weight, - - - - - -- Cenb'al I nUmity, Best 4Oms.
De.ffignation LxDia. lb Outer Shell 1 T<11eT Shell Hw'stm- JOI Candles Period
--- - - ------- ----- -----~~--
-----
(k)() 4x27.5 18 8Alb a.IIb TNT burswr 672 20.2
Al dust RClO.
------ - - - - - - - - - - - - - -------- -------
()'70 M46 casing 95 Al dust 70 It> KCIO. TNT 3490 130
total chg.
.
--------~~ ---' -------- -----
1'115 M47A3 110 Al dust KCIO, TNT 1470 48.9
Chemical 84lb
bomb case total chg.
------~---- - - - - -- ----~ ------ -.
X52 10 x 3(i 175 Atomized 361b TNT 4890 130
A1781b KCIO,
-~--~ -- - - - - - -
X53 8x22 50 Atomized 121b TNT 2200 74
AI251b-3% KClO, (expected) (expeoted)
silica gel

ARMING
WI

~------------------~-----------4lm .A.----~--~~~------,-------------~

.,I

80MO PHOTOFlASH M 120


WITH 11125 FI N WEIGHT I60LB APPROX

Figure 6-38. Typical PhotoRast. 80mb

I~ase rupture thr cloud t'xpHnds against the at- Soml' of the more important of these facwrs are:
lIlospherie pressun" resultill~ in tooling of the (1) charge weight, (2) l'()mpositioll, (3) particle
cloud. Thl' doud Illus-t eontain fairly large sized size, (4) hurst diameter and shapC', (5) igniters
partic'Ie aggrrgates (approximately 2[>0 mierons)18 aIHI hursters, (6) confhwment, and (7) ambient
so as to reach the size ohs,-rved experimentaliy. pressure.
Thl' light output rl~aches a peak value and then
~owly decreases, 6-4.5.1 Charge Weight
Generally, flash powder in itC'ms which produce
6-4.5 FACTORS AFFECTING PERFORMANCE a burst approaching a spherieal shape (see also
Thl' light outpnt of bright flash-producing de- Paragraph 6-4.fi.4) develop a total light output
viees is dep.>nticnt upon many interrelated factors. which is proportional to the eharge weight (as is

6-61
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ------ --- ------
I---~--

I
AMCP 706-185

TABLE 6·21
TYPICAL COMPOSITIONS FOR PHOTOFLASH AND SPOTTING CHARGES

Type Class Nominal Composition Remarks

PHOTOJ;'EA.SIl POWDERS
I :14% Magnesium Used at start of World War II
26% Aluminum in 1\146 Photoflash Bomb
-!O% Potassium Perchlorate
II A 60% 50/50 Magnesium- Dev~loped bt'cause of shortages
Aluminum Alloy at start of W orld War II of
·10% Potassium Perchlorate Aluminum and Magnesium Powder
B 4fi.fj% !i0/50 Magnesium- Later devt'lopmcnt It'd to
Aluminum Alloy substitution of Barium Nitrate
54.5% Barium Nitrate for Potassium Perchlorate
III A 40% Aluminum, Class C
:10% Potassium Perchloratt.
:~O% Barium Nitrate

B Same as III-A except that the


Potassium Perchlorate is eoarser
IV HW,Yc, Calcium Experimt-'ntal Efficit'ney at
~ZW;" Sodium Perchlorate 100,000 feet is 45.7 X loa
(~andlesec / g

SPOTTING CHARGES
:W% Atomized Aluminum Dt'veloped to givt' short time to
J 0% Flake Aluminum peak but wit.h less brisancr than
60% Barium Nitrate photoflash powderR

the light product'd ill the best 40 milliseconds, gives bettel results in noneonsolidated illuminat-
CPS. o). The duration of the flash increlJ.S('s as the ing compositions.
eube root of th" {'hargt' wt'ight, while the peak in- Thermodynamic data for stoichiometric mix-
tensity inercases as the two-thirds power of the tures of aluminum and various oxidizing agents
(~hatge wcight. 6P •7 ().ll The efficiency and light out- Ilr~ giv('1l in Table 6_23. 73 The trend is similar to
put for a ~vf'n wright of charge, thcrefot'"e, 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 CompoEiti()ll mrtri(~ mix turf deerrasrs so that the heat of reac-

As indieated in Table 6_22,66 aluminum and tion also decreast's. Of the oxidizers listed in this
magnesium are th£' best fuels for use in photoflash tahl(', potassium p('rchlorate produees the highes;t
mixtures at low altitudes. 18 •72 \Vhile atomized mag- hefit of reaction with atomizt'!l Illuminum. Lumi-
nesium gives higher luminuus iutenSoities than Ilosity vahws for varions lIitrates with atomized
other fuels in consolidated illuminating composi- aluminum and atomized magnpsium art' given in
tions, it has been founel that atomized aluminum Table 6-24. As indicated hy th~s table, which is

6-62
AJfCP 7(l6...185

XMIOl Spotting projeotile


Figure 6-39. Typical 20 mm SpoHing Round

---

Figure 6-40. Photoflash "Daisy" Cartridge

)'PS;UllI. alld atomiz!'d rnaKlIl'sium-alumillum al-


for flld-I'i('h (·OIJ1positiollS. th!' light olltput of
loys. Atnrni1.PlI alumillum is difficult 1.) i~mite and
~toi("hiolll!'tl'i(' lIIixtllrt'!o\ are relativrly low; and
ha~ not hpl'll Ilst'cl dfh·it·JltIy ill metal dust photo-
alkaJiJl(' earth IIlptal lIitratrs al'l' mllt"h mot!' satis-
tlllsh bomb". l<'lakP allllllinu:n, whi('h r'~quircs a
ru(.tory than alkali IlH'tal nitrlltt'>! ill T101H'OJlsoli-
wpight d hllr'stl'l' IlPPl'ox i ;natl'Iy p(pIal to that (If
datt,(l illtllllillatillg ('()Illpositiow~.
(1](' (I liSt, pl'Odll(,('s a flash of relativpiy short dura·
For dust-typP hombs, j her!' ar!' marked II iff!'r-
tioll alld II rapid timp to peak. Atomized rna.g-
(')\('('S ill llPhuvio)' of flak!' alullIillum. almniz('d mag'-

6-63
AMCP 706-185

TABLE 6·22
LUMINOSITY CHARACTERISTICS AT SEA LEVEL OF PHOTOFI.ASH COMPOSITiONS
CONSISTING OF HIGH-ENERGY FUELS IN STOICHIuMETRIC AND FUEL·RICH
COMBINATIONS WITH POTASSIUM PERCHLORATE

Time to Integral Light, Duration, Efficiency, Increase


Type of Peak, Peak, 1()3 candlesec, maec 10 3 eandlesee/g in
Fuel Composition(a) 106 candles lIlBec (1A.o mu) 1,10 max Total Fuel Effieiency. 0/0

Aluminum
s 41 1.2 147 9 14 10.3
35
x 41 1.7 226 11 16 13.8

i\:Iagnl'sium
s 18 1.2 142 16 24 10.0
X 20 2.3 um 17 25
15
11.5

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

'l'itanium
s 18 0.4 65 9 15 4.9
4
x 16 1.3 80 12 21 5.1

( 'alcinrn
s 12 1.2 75 16 5.7
30
X 13 1.7 115 15 19 7.4

Bor01l
s 0.5 23.0 IH GH 89 a.5
85
x 2 14.3 51 ;'5 92 8.5

l::;ilicon
s Did not ignite
X Did no t ignite

(a) S = Stoichiometric. X = }4lii "XCt'SS fuel.

Iltsil\ll\, whie'h rt·quirrs a mIlch smallrr burster, 1'1"111,in<ii('atl' that these additi"l's do !lot increllse
g-iVl's 11 Hash of much longer duration and has a ttl(' out put of thost' photoHll.qh itpms which arc near
longf'r tiUH' to p,·ak. Tht' magnt'Siulll alloys are optimum. ('()utlirtillg rpslllts hn\'!' bePll obtained.
intrrlJlrdiat,· ill tll{'ir hrhavior. The ilifi'erencr in Some purlier illvl'stigators obt.aint'(l results which
tht' mt'tlll dust.tn-burstrr ratio may iw du(' to the i IIdielttf'd improvement with somt' additives. 18
rplatiVl' ignitibility of th(' metal fuels. Powdered
Illugnrsium is ('asipr to ig-nitr than powderpd alu- 6-4.5.3 Particle Size
minullI; as II ('OIlSNIW'IH't', atollliz('d aluminum hllH ~f ueh of thl' rpsearch und development (·OIH'ern·
not llt'PH Ilsrd rffi('i('utly in It II It·ta 1 dust bomb. in/! photoflash !'ompositions has ('('nh'retl arOlmd
Tilt' longer tinl!' to ppuk anti flash duration of til,· d<'tt'rlllinatioll of tht· opt imum partirll' sizp
maglH'sinlJl ('1111 Ill' t'xplained by thp rradion bl" Hlld shupt'. Whilt· it has IflnlX bt'plI known that
t Wt't'll magnrsiutll and nitrogen whit'h prt,(,pdrs thp t ht' a vt'ragt' partil'lt, sizto !lnt! parti('le sizp rangp
r'('artion with oxygpn. art' important IlIll'IIII1l'It'rs ill d(·tt'rmining thp lumi.
Small amounts of additiVl's, prill('ipally m!'tals nosity ('hanwt/'risti('~ of Jlyrote('hnit' Hash mix-
alld silic'a /!rls. hav!' het'll tried to int·rpas,· thl' light t\lrt'~, 1M d!'tllil(·t\ r!'lationships W('rl' (lifficult to es-
output fr'oll1 photoHash d,'vil·'·S. IV'sults, in gpn- tahlish llntil l1wthoos ht'('aml' availahle to riaSllify

ti-64
AMCP 706·185

systems in which the aluminum was in the 22 ± 8


micron partieie size range would produce enough
light for pyrotf~chnic applications. H Regardless
of th(- 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 sizl:' wa..<; held constant, de·
ereasing the oxidant particle size resulted in an
inereased l'ffif'iency (candle seconds per gram)
at both spa 1~"pI and at 80,000 feet simulated alti-
tude. (See I<'igure 6-46.) At high altitude, the
}wak and integral lip-ht intensity vary similarly.
At sea I('vel, however, the composition \\ith the
(·oarse oxidizer produced the highest peak and in-
tpg'ral light illtensity, due to the greater tapped
(1Pllsity with thp ('oarsp oxidizer fraction, s(\ that a
)!reater samp\(' w!'ight ('ould be loaded into the
tl'8t (·artridge.
Thp markPd differences in the behavior of the
dusts uSt'd in dust·type photoflash bombs (Para·
graph 6-4.5.2) result in the existenc(' of an opti-
Illum partielt· size for each meta} or aHoy and each
IllPthod of dispers~oll.73 Excessi.vely large particles
will lIot ignitr after dispersal. Efficiency tends
to det'Tl'asp, in the eaS(> of magnesium Ilnd mag-
lI!'sium-aluminum alloys, if there is too large a
Iwn'elltage of fines in tIlt' dust. A" a consequence,
Figure 6·41. Typical Plash Chcrge for "Indication of tht' llSI' of "run of the mill," less than 100 mesh,
Functioning"
atomizpd maglll'slum is preferable to the use of.
lJIixturp8 ('ontainillg a largp amount of 325 mesh
TABLE 6·23
filii' partides.l~
THERMODYN AMIC DATA FOR STOICHIO·
III ordt'r for t hI' diamett·r of tht' burst produced
METRIC MIXTURES OF OXIDIZING AGENTS
hy !lust-t,vpt' photoflash hombs to bp as large Sf'l
AND ATOMIZED ALUMINUM
ObSt'fVt'd experiuH'ntally, calculations indicate that

{'alculatetl !lH' IIlt'tal (lUst pllrtil'lf's must "clump" together


StO'ich i(mtdri4.~ Heat of (possibly dut' to thl' prt'ssurf> produced by the ex·
Rfaction, Cd/u plusi"I' bUl'stt'r) in fairly large particles, at least
Ratio
:![)O lIlil'rolls ill diallwlt'r. Tht'se" dumps," due to
Sodiulll Ilitrat!' fi5.4/M.6 1955 ail·-tlr!\~ brl'tlkuli as thpy mow through the air,

PotasHiulIl Ilitralt' 1i!!.:U:1O .H 1766 !t'II\'t' smllH pllrtit'lt's (psrtie\ps having tht' initial
Strolltium lIitl'ldt' iO.::!/:!9.H 1899 sizt' distributioll of tlk llH'tlll dust) which burn in
BariulIl Ilitratt· 74.4/25.11 1598 tht' air.n
Potassilllll pl'n·hloratt' 65.Hj:i4.~ 2529
6-4.5.4 Cloud SlIl; 1le
thl' fllt·l IIlld oxidallt Jll)wdpn; illto narrow pnrti('l" Sillt't' II 1lI!'I I Jlh(ltotla~h bllrst:; ar.. I'sstmtially
SIZt' rllllgl's. sJlht'rit'al ill shapt· alld t'sselltially 0PIlIjUt' to visibl,'
}<'or potassiuIII pt'rehlorntl'-alumilllllll ( 60/40 by rlld luI ion. I ht' Illllount of 1il"'ht mllia!!'(} i~ propol'·
wI·jght) tlash t"omp"silit>lls. it was fO\llld thut ollly t iOllul t() th .. sqlwr .. of thl' burst rlidius, provided,

6-65
AJlCP 706-185

TABLE 6·24
!UMINOSITY VALUES OF VARIOUS OXIDANTS WITH ATOMIZED
ALUMINUM AND ATOMIZED MAGNESIUM TESTED
IN 11.112 PHOTOFLASH CARTRIDGE

Time Total
.Peak to Integral
Intensity, Peak, Light,
Oxidant 106 Oandles msej 1(jl O(1lndle-Seconds

Aluminum Composititms
Sodium nitrate
-----------------
Burned without detonation
Potassium nitrate Burned without detonation
Strontium nitrate 124 3 1.61
Barium nitrate 139 3 1.64
Magnesium Oompositiom
Sodium nitrate 4
Potassium nitrate F"iled to ignite
Strontium nitrate 21 5 0.33
Barium nitrate 42 5 0.65

sidf'rably by enlarging the effective surface area of


the burst. Theoretically, I].n optimum system, as
long as the temperature remains high, cODsis~ of
an infinite number of infinitesimally small point
sonrces. 711
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
CPS
practically. IS As a result of recent improvements
I
I in aerial photographic techniques and equipment,
I which permit the utilization of light over longer
:- lEST _~!~

L------- __ TOTAL ~lASH ~URATIOL_ _ _ _ __


periods of time (up to 250 milliseconds), pellets of
presspd illuminating composition have been used in
figure, 6·42. Typical Time-/ntenlity Curve place of short duration photoflash chargf's. Results
indicat.e that efficiencies are much greater than
the tcmp(~rature of the surface of the burst re- those obtained with photoflash compositioDS. 711
mains constdnt. Sinc(' the volume of the sphere is
proportional to tht' charge weight, and the maxi- 6-4.5.5 Bursters and Ignite:rs
mum temperature is limited to about ~~OOO°C, the A great many ('xplosives have been tried (Table
peak intensity should, as has been verified experi- 6-25) as bursten; in dust.type photoflash bombs.
"H'ntally (Paragraph 6-4.5.1), v r ry as the charg? In g'pneral, thp most. powerful or brisance buster
weight to the two·thirds POW( r. 'PJlre efficiency of se('IllS to perform best. RDX is bettpr than tetryl
the larger charges is, therefore, less than that of which, in tUrII, is better than TNT, oth('r conditions
thl' smallpr eharges but could be increased con- being equal. Aluminizpd explosives at optimum

6-G6
;------1
I I
I I
r- --- SHuTTCn OP"RATIO~
.. <
I
~
.
I
\
5
I
\
I
..
~

I TIIolE INTENSITY Ii
'- -- --'-CHA~ACTrRISTIC 3 2~
MI20 PHOTOFLASH 801018 i

~-- -
zo
TIME. MilLISECONDS

- TIME
Figure 6-44. Time-Intensity Curves for MJ20Al Flash
Figure 6-43. Syrn.hronizafion of ShuHer Powder and MJ22 Dust PhotoRash 80mbs

eoneentrations have greater power than the pure appreciably influence the output of the dust bomb.
explosive and, therefore, perform better as Centrally located bursters, all Eactors considered,
bursters. l8 gave results comparable to those for any other 10-
As has been indicated, there are marked dif- ration. 'I'he 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 magnesium .. should have little influence except to change the
aluminum alloys when dispersed and i~nited as a Cf'nter of tht' gas bubble formed. (See Paragraph
dust cloud. Flake aluminum requires a weight of 6-4.4.2. ) 88
burster approximately equal to the weight of 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 of the weight of ble, the effect of location, shape, and amount of
the metal dust.n The maximum radius of a ruag- initiator are important. The use of an initiator
nesium dust flash depends, approximately, on the too powerful for a particular case and composition
cube root of the dust-to-burster ratio for the lower might cause too rapid expansion of the gas bubble,
ratios and on a somewhat lower power at the higher resulting in casp rupture before a desirable initia-
dust-to-burstf'r ratios. At a constant dust-to-burster tion of the photoflash mixture. For a long column
ratio, the radii of magnesium dust flashes increase, of flash composition with an initiator in one end,
roughly, as the cubp root of the quantity of dust. a stage can be reaehed where reaction in the
In general, for magnesium and magnesium-alc.- photoflash mix will propagate through the mixture
minum alloys, an inereasp in the dust-to-burster resulting in some measure of independence from the
ratio results in an inereast' in time to peak, an in- mode of 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
integratNl light values, and, to e lesser extent, an have adequate ignition of the balance of the photo-
inerpase in light intt'nsity. B?cause of the large flash mixture.
dmoulltH of bllrf:tt'r required for flake aluminum,
variations in the dust-to-burster ratio within the 6-4.5.6 Confinement
llst'ful rangl's Sf'pm to hevt' liUII' effect. The characteristics of the case surrounding a
Other fadors-including shape of the burster, rt'active photoflash mixture affect the amount of
loading tt·ehniqucs, and confinement-have been time available for ignition of the mixture as well as
studird. Most dust-typt' bombs that have been the way the mixture is released and. disseminated.
studird Ilse a cylindrical burster Or a trlmcated A caGe of excesshre strength, requiring an ap-
l~Olle. ,{,lw ml'thod usrd to load a burster did not preciable amount of enerfn' to rupture, may divert

6-67
AMCP 706-185

" 140 -
-iT 10

[N[RG'J I~T£G""TEO T~AOUGHOUT ENTIRE


\-~- "LAS", BY ElECTRONIC SIIECUOM£ T[A 100
.
u
!IO

ftc ~;
0

3
a 110
"~
~I 10
"'
i
~:!;
.
10
103
w
> " ..
;;
i
g i 40 - 00
'0
~
o L-->- --L.~ _~_~ --'-_-'---_-L_~...1--~
'It' 5.0 0600 140 fI(I 71:0 1.., 100 • .0 "0 ~lO MO 1000
0
.." 1.0
TIM(I:, MILLISECOND.
WAIIELENG"It, t.lILLIMICRONS

Figure 6-47. Size and light Output Qf Flash Cloud VI Time


Figure 6-45. Spectral Energy Distribution Curve of M120
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 of the flash. This effect,
which would be emphasized at low ambient pres· N o1&metallized MetalUzed
sUres, was illustrated in tests conducted with metal Compo A-3 AI/KClO./cellulose nitT'it~,
and plastic cases. With tbe metal case, the ex· Compo C 49/49/2
pected light output was obtained at ambient con· Gunpowder Compo A-J/AI,BO/20
ditions and 80,000 feet and with the plastic case Photoflash Powder ('(lml'. B/AI,80/20
at ambient conditions; :lOwever, a sharp drop oc· 1'ype III, Class- C HBX-3
curred for plastic cases at 80,000 feet. Variations Primacord HBX-6
in thickness within narrow limits f(lr metal oases Pyrotrchnie Compn. Minol 2
were found to cause negligible changes in light RDX RDX/AI/wax
output. 68 RDX/TNT RD:'~ 'rNTIAI,
RDX/TNT, 60/40 42,') 'lS (Torpex 2)
Sodatol 20 I ~ ~ (L
".."" e 'retryl RDX/TI, //AI/Cnroon,
% 0"

-......,.~
Tetry!/TNT, 30/70 20/55/25/2.5
:g 6 -0--.-----.- TNT RDX/ AI/PIB,
z
o 78.5/20/1.5
~ !>
...-' Tetryl/AI
o
~
u .-----------. TNT/AI
Tritonal: TNT/AI

80,000 FEET

AvERAGE ALU~INUM
-----------------
PARTIt:LE SIZE' 50 MICAOHS
70/30
75/25
80/20

L - . _ l . - !_ _ L_
8 12 16 20 24
1 I
28 For dust.type photoflll8h bombs, Ule casing ma·
AVERAGE PARTICLE SIZE POTASSIUM PERCHLORATE. U'CRON$
terial has a relatively unimportant influence on
the light OUtput. The thickness of the case has a
Figure 6·46. EHed of Particle Size of Potassium Perchlo· limited but not critical effect on tht' output, espe·
rate on luminous Efficiency of 60/40 Potassium Perchlo·
rate·Aluminum Compositions cially with large bursters. 78.77

6-68
AIltCP 7()6.185

TABLE 6·26
LUMINOSITY CHARACTERI; "~C~ OF PHOTO FLASH COMPOSITIONS CONSISTING OF
HIGH·ENERGY FU~~l.S IN STOICHIOMETRIC COMBINATION WITH
POTASSIUM PERCHLORATE'"

Composition Time to Integral Light, Duration, Effieieney,


Weight, Peak, Peak, 103 eandlesec, msoo lo-~
candlescc/ g
l!'uel g 10 6 candles msec (homax) %~malC Total Composition Fuel

Sea Level
34% AluruinllDl 42 41 1.2 147 9 14 3.5 10.3
41 % Magnesium 35 18 1.2 142 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 4!J 1.3 103 7 14 2.5 7.3
41 % Magnesium 3n 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 % Titanjum 33 29 O.n 49 4 13 1.5 3.7
58% Calcium 23 26 0.5 176 2] 29 7:l 13.3
17% Boron 31 No deflection
29 % Silicon 35 Did not ignite

• Test vehicl"" MUZ charge case reduc&d to 1.72·inch length.

6-4.5.7 Ambient Pressure of light results because the flash diameter at alti-
As indicated by the data in Table 0-26 the tude (l<'igure 6-47) is greater than at sea leve1. 68
light output of most possible photoflash mixtures The effectiveness of photoflash mixtures con-
is less at an altitude of 80,000 feet than at sea taining calcium depends on thp. formation and
level. Of th'~ high energy fuels evaluated, alu- energy content of discrete bands. 78 The phenome-
minum and magnesi. ,n were most efficient at sea non of increasing light output observed with com-
level and raleillm was most efficient up to 100,000 positions containing calcium metal, calcium aHoys,
feet. 66 As the bciling point and extent of diss(lcia- calcium perchlorate, and calcium nitrate also re-
tion of the rea<'ti.oll products dcpend on the am.· sults when adding an inert calcium salt such as
Lif'nt pressure, the final flash temperature will ('alcium oxi,ie ::lr calcium fluoride to a composition
dect'pase with increasing altitude. The radiation producing a high temperature such as aluminum-
prop.ue(>d by most photofia~h items is continuous pota..<;sium IH'rchlerate. The magnitude of the in-
(see Paragraph 6-4.4.1.2) approaching thet of !I. aease in light output, however, is considerably
graybody with a high emissivity and lower light less thlill for otht'f ealcium-cont&ining composi-
values obtail1{'d. Some compensation for this loss tions. H6

6-69
AMCP 7()6.185

REFERENCES
1. Alan St. H. Brock, A History of PtrewOf'ks, port 1758, Picatinny Arse~al, Dover, N. J'.,
George G. Harrap and Co., Ltd., London. .January 1950.
~. Jean Appier (alias Hanzelet), La pyrotechnie, U. S. A. Richer, The Photoflash Bomb, Picatinny
Pont a Mnusson, 1630 (quoted in Brock, A Arsenal, DOVfJr, N. J., April 1935.
History of Fireworks). 15. H. J. Eppig, D. liart, flom"'J, Photoflash, T9
3. Claude Ruggieri, "Elemens de Pyrotechnie," Series: A Study of Light Emission Oharacter-
Fortune, Paris, 1801 and 1821 (quoted in istics of Safe, Dust Type Photoflash Bombs,
BrG~k, A History of Fireworks). Picatiilny A.rsenal Techuical Report, 1757,
4. Claude RuggiE'ri and Thomas Morel, "Die Picatinny Arsenal, ThJver, N. J., "B'p.bruary
Pyrotechnie," N ach der Vorschriften, Leipzig, 1950.
16. S. A. Rieh~r, The Photoflash Cwrtridge, Pic&-
1807 (quoted in Brock, A History of Fire-
tinny Arsenal, D<>ver, N. J., April 1955.
works).
17. M. G. M. Clarkf\ Developmer.t 0/ the Photo··
5. Claude Ruggieri, "Pyrotechnie Militaire,"
flash Bomb, ORDWES Repol·t 1949-5, Wes-
Fortune, Paris, 1812 (quoted in Brock, A
leyan University, ~'diddlet()wn, COrlllccticut,
History of Fireworks).
April 1949.
6. James Cutbush, "Chinese Fire," American
18. The CO'mpilati,')n of Flame and Shockwave In-
Journal of Science, VII, 1823 (quoted in
formation Applicable to Photoflashes, Final
Brock, A History of F'ireworks).
Summary Report, Contract DAI-28-0l7-501-
7. Summary Technical Report, Vol. 2, Chapter
ORD(P)-1096, Arthur D. \Ji.ttle, Inc., Ce.m-
4, NDRC Division 11, National Defense Re- bridge, Mass., September] 955.
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 Dct'elopment Progress sance Photr;graphy, Contract DA-36-039-SC·
in Military Pyrotechnics, Research and De- 7833Z, Denver Research Institute, Denver,
lelopment IJecture No. 24, Picatinny Arsenal, Colorado, August 1960.
Dover, N. J., 1955 (DDC-AD 82 6'78). 20. George Shortley llnd Dudley Williams, Ele-
9. T. Stevenson, E. R. Reche!, Delay Actwn ments of Physics, 3rd Ed., Prentice-Hall, Inc.,
T racer Ammunition, Frankford Arsenal Bu- Englewootl Cliffs, N. J., 1961.
port R-44, Frankford Arsenal, Philadelphia, 2]. S. Gladstone and B. Lewis, Elements of Phys-
Pa., 1940. ical Chemistry, Va~ Nostrand Co., Inc., Prince-
10. T. Stevenson, Delay Action and Dim Igniters tou, N. tT., April 1960.
for Small Arms Trucer Bullets, Frankfortl. 22. B. Donda, The Theory of Colored Flame Pro-
Arsenal Report 708, ~-'rankford Arsenal, Phila- duction, RDTN-71, Naval Ammunition Depot,
delphia, Pa., 1946. Crane, Indit/.lla; Bureau of Naval Weapons,
11. Develop, Manufacture and Test F;asklig}:,t Wa:;hington, D. C,
Bombs, Picatinny Arsenal Technical Report 23. E. J. Bowen, The Chemical Aspects of Light,
80a, Picatinny Arsenal, Dover, N. J., Mru:ch 2nd Ed., Clarendo~ Press, 0xford, 1946.
1937. 24. Intet'national Encydopedia of Ohemical Sci-
12. J. H. Robinson, Investigation of }i1 ailures of eMf. Van Nostrand Co., :nc., Princetou, N. J.
M23 Photclfl:z,sh Bombs, Picatillny Arsenal 25. A. C. Gaydon, The Spectroscopy of Flame,
Technical Report 1068, Picatinny .Arsenal, Chapman ann Hall, Ltd., I;ondon, 1957.
Dover, N. J., January 1941. ~{i, A. (t. Gaydon and H. C. Wolfhard, Flames,
13. H. J, Eppig, D. Hart, Bomb, Photoflash, T9 Their St ..1tcture, Radiation an{i Temperature,
Serifs: Development of Improved Photoftash 2nd Ed., Ohapman and Hall, Ltd., London,
Composition, Pica tinny Arsenal Technical Re- 1960.

6-70
AMCP 706·185

REFERENCES (cont'd)
27. Wal\acp R. Brode, Clwmi,cal Spcctroscopy, tion Chm'ltctet'istics oj Transparent and Trml-S-
John Wilf'Y & Suns, N. Y., 1943. lucl'nt Material Under Nonisothert'ltal Co'ndi-
~H. A. Fran14on, S. K\tz, lWeI E. Rais{~n, "Radia- tions. ASDTDR 62-719, Air Force Systems
tior.. Charadf'ristics of Black Body Sources," Command, Wrigl;t-PnttersOll Air Force Base,
SymposiulH uri Temperature,.lt~ Jlf cawuren,ent Ohio, .T \lIle 1964.
:znd Control, Reinhold Pnb1ishin~ Co., N. Y., 41. B. Jackson, S. M. Kaye, G. Weingarten, Resins
1962. Other Tha.n Laminae 1116' as Binde.rs in Pyro-
~!l. fi. Kinglake. Ed., Applied Opt~'.cs twd Optical
technic Cmt'pos'it'w7ls, Picatinny .Arsenal Tech-
En.oinee r'i '!(j , Vol. I, Academic Press, 1965, nical Note 40, PicatinllY Arsenal, Dover, N, J.,
p. 8.
,January 1960.
:n .f. 'i'hcwl;s, ltJd., Encyc/,opcc/;i{l Dictionary 42. 11. ,J. Eppig. ,J. D. Stracham, Self-Hardening
Physics. Pel'gamon Press, IJtd., London, 1961.
Pyr'otccitnie e'mtpositions, Picatinny Arsenal
:11, 1\I. G. l\1pllon, Ed., Anclytieal A bsorption Spec-
Te'~llllical Heport 1801, Picatinny Arsenal,
troscopy, .John Wacy & Sons, Inc., N. y"
Dovel', N. •T., December 1950.
195J.
43. D. Hart, Rcsrarch and Devclopment in Mili-
:32. R. h Weber, lVi. 1.V. ,;Thite, K. V. Manning,
tary Pyrotcchnics, Picatinny Arsenal, Dover,
Pily~'ics f01' !.h:ic)1cC and Engineenn)7, McGraw-
N. J., February 1955 (DDC-'fIP U10769).
Hill Book Co., Inc., N. Y., 1957.
H. B. ,Tackson, An Investigation of the. Effects
:]3. R. C. ('aSpp.rsoll, H. P. Lenzyck, R. C. Chau-
of Loading Pressure, Flare Case Coating, and
nel, Visibil~ty Data as It Lippl'ies to Pyrotech-
:lIagrtcsinll! Particle Size on the Burning Time,
nics, Contraet DAI-2H-017-501-0RD(P)-1294,
Luminous Intensity, and Color Characteris-
Dunla 1) awJ Associates, Stamford, Connectl-
tics of PY"otechm'c Flarl? Compositions, Pica-
ent, April 25, 1955.
t illllY Arsenal Technical Note 14, Picatinny
:l4. E. Frl'emun, G. Weingarten. A Thermal
Arsenal, Dover, N. J.
Theory for Hates of Propagative Bu'rning.
.til. R. M. Blount, R W. Evans, Exycrimental In-
Pieatinny Arsenal Technical Report 2596,
vestiaation of Infrared Radiating Sources,
Pi(~atillny Arsenal, Dover, N. fL, June 1959.
Denver Resl}arch Institute, Denver, Colol'ado,
:{5. D. Hart, H .•J. Eppig, Long Range Research
,July 1!J61 (DDC-AD 324 807), March 1962
011 Pyrot('chmcs,' Burning Characterist·ics cf
(DDC-AD 328 6aO), November 1962 DDC-
Biliary Mixtures, Picatinny Arsenal 'rechnical
AD 332 848),
Report 1669, Picatinny Arsenal, Dover, N. J.,
46. B. ,Jackson, The Effect of Cross-Sectiona,lArea
Octubu' 1941 (DDe-ATI 6G 289).
and Case Material on Burning Characteristics
:36. Herbert Ellprll, Modern Pyrotechnics, Chem-
ical Publishiilg' Co., N. Y.! i96I. of Pyrotechnic Compositions, Picatinny Ar-
:n. B. E. Donda, Rclat'wnships Obserued in Col- s(,Ilal ':.'echnical Note 7, Picatinny Arsenal,
ored Flare.~, ItDTR--15, ~aval AmlPllllition Dover, ~ .•J., September 1957.
Depot. Cralle. Indiana.; Bureau of Naval 47. A. 1<'. Taschl('r, S. M. Kaye, Effects of Mag-
'Veapolls, WashingtolJ, D. ('., Scptembl>r 1964. I!('"iunt Content C(U!e Material and Case Coat-
:{R. R. Ii'. Barrow and E. E. (,aldin, "Some Spec- ino 011 Burnina Characteristics of a, Flare
troscupi(~ ObservstiollS of Pyrotcch!lic l<'lames," SYldem, Pir'atinllY Arsenal Techilical Note 42,
['roen:din(/s uf Physical Socidy of Londmi, PicatillI!Y Arsenal, Dover, ~. J., April 196C.
62 (194!)) -ttl. S. Rrsniek, Simulated lliah Altitude Tests of
:{9. B. E. Donda, Emissioil Studies of Sr/ected Py- Illumination Compositions, Picatinny Arsenal
l'ottc/'llic Planlls, RDTN-77, Naval ·\mmuni- Hrport ~161i, Pieatinny Arsenal, Dover, N. J'.,
tion Dppot, Crane, flldiana: Bureau of Naval April ]955.
WI'apolls, WashilH.~tO!l, n. C., Aug-llst 1964. ·W. W. A. :-;l'hJllt'lill~, Applird Rlsea.rell for Threat
-to. R. C, f<'olv,'pil('r, W .•.1. Mallin, 'l'hamal Radiu- Si(Jlwtuff (hnl'ratioll Tahniqll()S, Final Re-

6-71
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 :140411). Flash, Guided M'issile MK 37 Mod 0 for the
50. R. Shulman, Effects of Variation of Cavity Spar?"ow III Missile, NA VORD 5860, Bureau
Geometry Upon Small Arms Tracer Burn- of Naval Wf'apons, Washington, D. C., May
ing, !<'rankf"rd Arsenal Report 1421, Frank- 1958.
ford Ars')nal, Philadelphia, Pa. 61. ,J. W. Haldeman, Development of the Signal,
51. E. S. Freeman, "The Kinetics of the Under- J<'lash, MK 19 Mod 0 for the Terrier BT-3 Mis-
water ('orrosion of Powdered Magnesium," sile and the S£gnal, Flash, MK 56 Mod 0 for
Journal of Physical Chemistry 59, 1009 the Corvus Missile, NA VORD 7055, Bureau
(1955 ). of Naval -Weapons, Washington, D. C., Sep-
;)2. R. ~1. Blount, G. Francis, Study of Light tember 1960.
SOlt;'crs for Niaht A_erial 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.
~~orce, Washington, D. C.
53. ,J. R. Quick, R. T .•Johnson, Simplified Method
64. S. Haffner, A Survey of Available Literature
of Determim:ng Optimum Burst Altitudes for
on the Rapid Combustion of Metals in Air,
Aerial Photoflash Bombs Under Various Con-
Picatinny Report 2061, Pica tinny Arsenal,
ditions of Light Output and Flight Altitude
Dover, N. J., September 1954 (DDC-AD 44
for Fixed Camera Trail-Angle Combination,
543).
WCIIR-55-5, Wright Air Development Center,
65. A. A. Shidlovsky, }I'1tndamentals of Pyrotech-
Air 'l'echnical Service Command, Wright-Pat-
me, Government Publication of the Defense
terson Air Forct' Ease, Ohio, November 1956
Industry, 1st Ed., Moscow, 1943 (Library of
(DDC-AD 110 518).
Congress Call No. UF 860.85), 2nd Ed., Mos-
;j4. Night Aerial Photography, A Technical His-
cow, 1954 (Library of the University of Cali-
tory, Wesleyan University, Middletown, Con-
fornia, Berkeley, Calit).
necticut, July 1954 (DDG-AD 46 595).
55. The Magnesium Burner: Uses Other Than 66. S. Lopatin, Sea Level and High Altitude Per-
Photographic, Wesleyan University, Middle- formance of Experimental Photoflash Composi-
town, Connecticut, May 1951 (DDC-ATI 168 tions, Picatinny Arsenal Technical Report 29,
202). Picatinny Arsenal, Dover, N. J., October 1961.
56. The Magnesium Burner, II. Fll~ls, Wesleyan 67. J. Hershkowitz, The Action of an Explosive
University, Middletown, Connecticut, October on Surrounding Nonreacting Metal Dust, Pica-
1952 (DDC-A'l'i 171 350). tinny Arsenal, Dover, N. J., December 1957
;)7. R 'r. Eckenrode and F. L. Marian, The Spot- (DDC-AD-150 486).
ting Technique: The Question of Spot vs 68. .J. Hershkowitz, The Mechanism vf Ignition and
Smokr ami Spot Duration, Memo for Hccord, Propagation of Oxidant-Metal Flashes, Pica-
Project TS 4-4020, Frankford Ar.,enal, Phila- tinny Arsenal, Dover, N. J., April 1958 (DDC.
delphia, Pa., November 1964. AD 156424).
5~. R. 'r. Eckenrode, ThlJ Spottiny Tr.~hni(i1te: Ef- 69. R. M. Badger, A. L. Wahrhaftig, F1trther
fect of Ambient Illumination, Spot Intensity Stlldi(;s of the Effect of Co'mposition on the
and Color, Memory Screen Information, Memo Properties of Flash Powders, Contract W-535-
for Rt'eord, Project 754, :F'rankford Arsenlll, AC-24521, California Institute of Technology,
Philadelphia, Pa., October 1955. Pasadpna, California, .July 1942.
59. D. D. Collins, Pyrofuhnic ll'lashes and Flares 70. R. G. (~lark(', W. C. Nelson, R. W. Stallbaum,
in (hn"ded Missilr Trackiny, RedslOne Arsenal, Photoflash Boml). IV. The Effects of Cast and
Huntsville, Alabama, December 1959. /land Packui Bursters, ORD 1951-2, Wea-

6-72
REFERENCES (cont'd)
leyan University, Middletown, Connecticut, search 118boratory Technical Report 44, Pica-
June 1951 (DDe·AD 51 317). tinny Arsenal, Dover, N. J., November 1961
71. Further Investigation of Photoflash Powders, (DDC-AD 266 486).
Memo Report ENG-M-59-676-15-26, AAF Ma- 75. S. Lopatin, C. A Knapp, Pelletization of n-
teriel Center, Photographic La.boratory Sec· luminants to Improve Photoflash Efficiency,
tion, Air 'l.'echnical Service Command, Wright- Picatinny Arsenal Technical Note 24, Pica-
Patterson Air Force Base, Ohio, February tinny Arsenal, Dover, N. J., August 1959
1943. (DDC-AD 207 077).
72. P. Tavernier, Contribution to the Study of 76. R. G. Clarke, The Photoflash Bomb. Ill. The
Plash Powders, Translation by U. S. Joint rasing and the Dust Oharge, ORDWES Re-
Publication Resf'srch Service of report from port ORD 1950-4, Wesleyan University, Mid-
Liberateire de la Commission des Substances dleto\'1n, Connecticut, June 1950.
Explosive, 17 May 1944, Picatinny Arsenal 77. H. G. Clar!:e, C. B. Ford, The Photoflash
Technical Memorandum 1072, Picatinny Ar- Bomb. II. Technical Developments in 1947-9,
senal, Dover, N . •T., October 1963. ORDWES Report 1949-11, Wesleyan Univer-
73. G. Weingarten, Ohemistry of Pyrotechnics, sity, Middletown, Connecticut, May 1949.
Presentation at Picatinny Arsenal, Dover, 78. S. Lopatin, High Altitude Flash Oharacteris-
N. J. tics of Oalcium! Potassium Perchlorate and
74. S. M. Kaye, J. Harris, Effect of Fuel and Oxi- Standard Photoflash Compositions, Picatinny
dant Particle Size on the Performance Ohar- Arsenal Technical Rf'pnrt 2646, Picatinny Ar-
acteristics of 60/04 Potassium Perchlorate! senal, Dover, N. J., October 1959 (DDe-AD
Aluminum Flash Composition, Feltman Re- 313 204).

6-73
AIfCP 706-185

CHAPTER 7

PRODUCTION OF SMOKE

7-1 HISTORICAL SUMMARY, GENERAL filters for industrial purposes, dispersion methods
The military use of smoke for screening and/or for chemicals used in the control of insects,S and
signaling is probably as old as warfare itself.1.2 cloud travel and contamination behavior for use
Before gllnpowder and other pyrotechnic mixtures in the solution of industrial pollution problems.
were available, smoke was made by the burning
of natural materials such as grass. The wide- 7-1.1 SCREENING SMOKES
spread, planned use of smoke in military opera.- The tactical pOMibilities of using smoke to
tions may, however, be considered to be a develop- screen friendly troops and terrain from enemy
ment of World War I. During this period, smoke observation, were comparatively late in being ap-
was used extensivdy for signaling, screening troop preciated. Isolated tactical uses are recorded, such
movements, and as a fear mechanism due to the as the screening of a river crossing with the smoke
rrsrmblance of screening smokes to certain toxic produced by the burning of damp straw by Charles
chemical agents. l •a XII of Sweden in 1700.1 However, for the century
The reseal'eh and development concerned with prior to World War I, the dense clouds of smoke
tht> military uSe of particulate clouds started o'.ur- incidental to the use of black powder had been a
ing W o~ld War I and was continued at a limited growing nuisance; and methods for the artificial
rate in the period between the two World Wnrs. gel1t'!'ation of umoke for military purposes were
Thc tactical significance of the planned nse of neglected until just before World War I when the
smoke, which was not fully realized until the close first experiments of this type were made in con-
of World War I, was strongly considered early in nection with naval operations.
World War II where the requirements for smohe- The German Navy performed with ship-borne
projucing devices were much grea.ter. Consequent- generators using sulfur trioxide and ~hlorosulfonic
ly, e~tensive research and development programs acid from 1906 to 1909 and used these methods for
were established early during World War II to producing sllioke in exercises carried out in 1914.
obtain the information necessary to develop thf' At about the same time, the British and American
tactically required smoke-producing items. Navies inve'ltigated the use of "funnel smoke"
After W orld War II, research and development produ'~erl by restricting the air supply to the fur-
programs on particulate clouds of military interest naces. The navll.I use of screening smoke developed
were continued again at a reduced rate. In spite rapidly enough so that the German Navy employed
of this lin,ited effort, information obtained from it with great success in the Battle of Jutland.
these programs proved valuable during the Korean Scre<'ning smokes played an increasingly impor-
Conflict. Since that time, work has progressed tant !'ole in later naval engagements.
in the development of improved smokes and in During World War I, the dense clouds pro-
fulfilling new requirements for ahlR in the tracking duced in damp weather from chlorine gas alBo
and 8 !quisition of missiles and aircraft.
1 llerved to musk other activities and clearly demon-
The research and development in exploiting the strated the tactical value of smoke in land war·
ul'lefulness of particulate douds for military pur- fare. The British, in 19]5, were the first to make
poses have also proved to be of great value for use of smoke 0/1 land to simulate gas attacks and
civilian applications. These include the physics to scret'n advane;ng troops. The material used to
of atomization, tIle production of high.efficiency grlWl'ate this smoke was the British type.S smoke

7-1
AJlCP 7Q6.185

mixt 1'1' of pitch, tallow, black powder, and salt- rial or a sllitablr method for producin~ large-area
peter. Thl' obscuring pom'r of the smokfo Wa.<J due s('rprns,
to inrompl~tp combustion of the solid particles in The smoke munitions available in 1940 included
the pitch. Rrreening smoke WIiS used on a large proj(,(,tiles, bombs, smoke pots, grenades, and air-
seal(' by th", Canadians in their attack on Messines planp spray tanks, whirh were sufficient to enable
Ridge in Septembpt 1915. During the following ground taciical 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 tal·tical employment of small, smoke-produc-
f'rents.l ing munitions was established as a result of actual
Both rrd and white phosphorus were soon intro- experience in field rnaneuvers and demonstrations.
duced as smokp-producing materIals. White phos- Th(' principal screening materials available in-
phorus prov('d to be the more efficient of the two and (~lllded sulfur trioxide-chlorosulfonic acid (FS),
was by far thi' most effi('ient smoke-producing ma- a liquid solution for USf' in projectiles and airplane
terial introduced during World War I. Sulfur spray tanks; hexachloroethane-metallic zinc mix-
trioxide was the next most efficient smoke-produc- ture (He), a solid mixt.ure used in burnine--type
ing material used, in spite of t.he fact that humid munitions such as grenadefoi and smoke pvts; and
air was required to fonn the sulfuric acid fumes. white phosphorus (WP), used in grenades, pro-
Other materials whirh produce sulfuric acid fumes jeetiles and bombs. These materials were superior
on eon tart with humid air, such a.<J oleum, chloro- to similar materials d~veloPed and used during
~ulfonir acid, and sulfuryl chloride, were also World War I.
widely used. The two latter materials also pro- Thf effectiven('ss of German air operations
duced hydrochloric Ilr:d fumes. Metallic chlorides, against British cities during 1940-41 was consider-
including till tl'trachloride (British K..r., French ably reduerd through the use of large-area smoke
Opacite), titanium tetrachloride (Germall F-Stoff; scrpens whieh prevented accu:rate aiming. The
British protected important industrial eenters with
United States PM), and silicon tetrachloride, were
smoke pots of an oil-burning type similar to the
also used.
smudge pots uSl'd in United States orange groves.
Another group of materials, producing the so-
Unes of smoke pots were laid out in such a manner
('aIled zin(' smokps. wrre basically mixtures of rinc
that the vital area was s~reened under any wind
dust and an organi(' ehlorine-eontaining' compound.
dirpetioll. The operation of this type of stationary
Tht' Berger mixtur(', used by the French (!uring
:o;mokp pot line required an extensive supply system
World 'Val' T. was composNI of zinc dust, carbon
since all important areas needed protection. As a
tetraehloridp, ziu(' oxidp. a!1(l kipst'lguhr. An im-
result. the British developl'd truck-mounted mo-
prov('d mixture wa" dr-veloJl('d in 1917 hy the U. S.
bil" gt·lIPrators. the most suitable of which was
Bureau of Mines alld was known as the BM Mix-
known as the "Haslal''' whieh produced a gray-
ture. This mixtur(' ("ollsistN} of zilJl' dust, carbon
brown smoke by burning and vaporizing crude
tetrarhlori<ie, t:odiulIl chlol'idp, ammoIliulIl ehloridc, oiI.··~
and mSj:..'1\,'siutn l'arilonate.
In the tTnitl'd States, the Defense Department
TIl(> intl'oJuM.ion of militn.ry aireraft. especially and the National Defpnsl' Resesl('h Committee,
bombt'rs whi('h ('ould attat'k important r('ar·are& alollg with several universitips and industrial con··
targl'ts, en'at('d a definite lH't'd for large-area ('('rIlS, eooperatiwly pm barked on a research pro-
smok(' Sl'ret'lls for prot,(·('fion. ('oIlse<jllt'ntly, much ~ralll to produee lurgp-area smoke sereens, 'F,l\r~y
of tht' effort bt'twe!'11 tlw two World Wars was di- ill 1(14:!, the optimulIl particle size for a hydro-
1"I,(,tt"d tow8rtt developing tt'ehniquI''i for produeing ,'arholl slllokt' was detprmilled and meehanical
fht'S<' largt'-art'a SDlOke s('reens. iTlL'ludillk tht· use smoke ~'\'nerat{lrs wert' devt·lopl'd to produce this
of airera!"t for this pllrpost'4.~ At the begiilning tyP(' ,If scrt'I'n,6 Work on smoke pots based on the
of World War II. howt'wr, nrit}wr tht· lTnitl'd veuturi prim'ip!!' was started at this time using
States nor Ureat Britaill had II satisfadory matp- fupl hloekll ttl vaporize volatile materials; however,

7-2
AMCP 7M-1SS

tht's{' de"ic{'s were not fully fNldy for production by the Servj(~es. ljittle information on the manu-
during World War II. flletnre and applieution of colored smoke Si10rlM
The ~mokc-producing materials sHch IL<; WP, WIIS available in th(' United States !it the beginning
F'~, and IH' had disadvantagt's which at times, of World War ~ cluf', mainly, to t.he eur.taiirnent in
Iimitl'd their llsefulness in World Vlar n. All of fireworks ltuUlufaeturc. Investigations were started
the smokps prodllcPcl froUl thest' rnat{'rials ,"'ere by various ei'lilian and military agencies. Various
irritating'. FS smok{' was corrosiv{' in the presence t.ypes of smokf' signai!;--inc·luding both parachute
"f moisture. WP smoke tended to rise rapidly, or and non parae hut<:, rockets, 1 jfle grenades, Very
to pillar, due to thl' heat given off by the burning pistol eartridgrs, hand grenadt~ signals for avi-
phosphorus. He, .'lad similar smoke compositions, ators, submariuf' reeognition signals, and smoke
produeed zinc chlorid;- which was toxic. In spite pots I',)r ground use--were developed in a variety
of tlll' disadva1ltages, thest items wprp useJ, along of polors. Inasmuch as the American Expedition-
with th" Ilt'wly deveiopPfl, mechanical smoke-pro- ary l<'Ol'eps wer(' to opt'mtr in 11 sector held by the
dtwing dt'vii't's, in advancing the strategic and French Army, it was found expedient to adopt the
hwtieal us!' of smoke durinl~ World War II. For t'lltirc Fr('IlCh Army system cf pyrotechnics.
the fil'st time, large areas, including whole cities, The I<'renrh lIsed colore:d smoke sign!l.ls whieh
('()uld be screenrd from aerial obsenr p.tiol1 for rela- eonsiflted of red and yellow smokes in signal para-
tiwly long ppriods of time.4.5 ehutt' rockets, rifle grelHl.des, ?5 mm and 35 mm
Scrt'enin)r smokp again proved to br of vaIu,:, Vf'ry ;listol cartridges, and a messel"ger signal
ill the Korpan actioll in whirh the United Nations' TIll' only }<-'rellch smok(' manufactured in the
:£"orpes o)wra ted without t he benefit of air superi- United States was yellow smoke, since this item
ority for much of the hm('. Hence, lar~l>-area (~oul(l J.ll~ producpd from avaiiablt' ingredients; the
ser('(,lls \wr(' rmployed to protect vital port areas orlwr colored smokes, sueh as re(~, could not be
as well as forward combat areafl. 7 In addition, manufactnrecl because necessary rlyeGtuffs were in
lIIurh of ttl(' I(orpan Ih'1 ion was a st-uggle for dom- short supply at that time. The United States did
inating terrain, and smoke wa'> constantly used in lIot develop mortar or artillery projectiles pro<1uc.
rplativply small·scale operations. t 'olored smoke ing colored smoke durinf-,' World Wlir I.
was also used for screening personnel withdrawal The British Army also recognized the need for
opl'rations heeawH' it persisted IOllger thRn the colort·d smoke signals and developed a number of
whitr ph()sphorns smoke norlllllJly used for this Sttch lllunitiolls early ill Wor.ld 'Val' 1. Red, yel-
pUrp051'.1,6,8
low, hlut" and violet smokes were devdoped for
liS\' ill rille g'renadl's (with or without parachutes),

7·1.2 SIGNAL SMOKES in V pry pistol cartridges, and in 3-inch mortar


'rIle IH'Pel for IllPthods of signalilll1 when neither proje(,tiles. A r~'d and blul' smoke filling for the
hand sigllnl Jlor flag is visibl(, nor thr sound of -!.5·im·h projectile was developed for artillery spot·
\'oie(' or horll is audibl(·, has IOIlg' hrrll recognized. ting alld aviatioll signaling. Dummy drop bombs
:-\li1okt, sigllals hav(' been used for this purpose since or subclIlib('r bombs ('ontaining colored smoke flll-
IIm'iellt tilll('s. IIo\\'('wr, till' thick haze of black ings wert' deYeluprd for training purposes. By the
!l0wd\'1' smoke which pll\'ploped battlefields vir- elose of World War 1, the Allies succeeded in de·
ttlally l'Iilllinatpd slllokP as a sigllaling IIgr;lt for a veloping- eXI>t'rimental colou'd smoke rifle grenades
time. Tilt· illtrodlletioll of Slllohlf'sS powder again as well as roeket.'! and Very cartridges in a variety
matlt' smoke sigllCtis a vaillablt, lllt'tllOd of com· of (·oInTs. They also madt· some use of colored
lll11llil'ation ill military operations. In spite of the smoke for artilil'ry spotting. Virtually no informa·
Il1ClIlY illlproY('lIlents ill ('ommunicatiolls methods, tioll is availabh· I'ollt'erning thl' use of eolored
sigllal smoke (~ontillllt'S to have an important place smoke by tht, Germalls and Italians during World
ill moderll warfare. \Var 1.
Pri.Of to \Vorld \\'ar I, a limitl'd :lUmber of Althouf,th thp rpspareh and development cffort
pyrott'l'}lI1i(~ items, mainly colored fiart's, were used in tht' Ullitl'd Stat~s proceeded at a reduced rate

'7-3
AlrICP 706·185

III the period betwc!:n World War:; I and II, a Hulbct ill Ii tlrcrease in tht' flam~ color and intellRity.
cOl\s\derl\bl(~ l\umber of llluuitiollS for producing Hillel' thl' +I aliI(' tra(~el' W:1S coneidered most im ..
colort!d smokr were dewloped. I.ncluded amor.g f\Jrtllnt, (hI' work was not pursued. After World
these items wprc colore(~ smoke halld and rifle gre- \Vat· II, It requirement for smoke tracers was re-
nades, canisters containing colored smoke fillings rstablishrd, and improved smoke tracerl'. were de-
for val'ious calibers of projectiles, colored &treamer VI'IOPNI based 011 the use of organic dyes,lO the
smoke bombs, colored smoke markers for aerial best d which were of th!' anthraquinone series
delivery containel'd, and colored bursts for the 4.2- producing orange-red smoke. These smok'l tracers
inch chem~cal mortar projectile. All of the~e were WHe developed primarily for training pilots t~
produced in a variety of col.ors. The British Army impnve their gunnery score with wing-mount.ed
also developed ('olc-red smoke rifle and hand gre- guns. D,]e to th~ pilot's extreme forward position
IlRdes, and colored smoke fillings for most (;f their in th!' aircraft, flam(' tr«crrs coming from the wing
artillery projectiles. The German Army limited gnns in the rear were difficult to pick up and fol-
their '!Olored smoL:e signals t,) various small hand low visually a.., they passed. Smoke tracers, on the
signals. other hand, left a lingering trail which was easier
Extensive use of signal smoke in 'World War II to sight and point at. the target. However, since
and the Kore16n Conflict proved that the nsc or they could not be seen readily at night they were
colored smoke fr)r dignaling purposes has an im- not. considered all-purpose tracers and, consequent-
portant place in the communications system of ly, did not brcome standardized.
modern warfa,re. Four colors-red, green, yellow, In 1950, development of spotting bullets as an
and violct--were found to be the most suitable. additional aid for fire control and target acquisi-
SmGkes were a~so of value in marking a specific tion was undrrtakel1. l l 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-
e£ally in the I(or~.an Conflict, the use of pyrotech- ploded to givc flash and smoke. Since the flal:lh was
nic signals, including smoke, was much faster and of extremely short. duration ~ 30 to 50 millisee-
more effe.~ti ve than more modern communications onds), the smoke puff became of greater impor-
methodE when the tactical situation was degen- talwe 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 thr standardization of the caliber .50
7-1.3 TRACKING AND ACQUISITION
M48 eombinatioll spottRr-tracer round and the de-
SMOKES velopment of a Ilrw family of spotting rounds.
Rmoke has been found to definitely complement Another WIt' for the smoke-producing devices
t.he observance of tracer projt'ctiles and, more resultl'd from the illl'reasing sp('ed of air or space
recrntly, has bt'rn used as a space yehiele tracking vehietes which were uewlopcd after World War
aid. Tracer bulll'ts, while dew·loped as a light- J 1. III ()f(h'r to assist t.f·st personnel in the optical
produeing devie!' for improved aim and fire con- tracking of tht'St' vehides, it was Ilecessary to de-
trol for automatil~ w('apons, emit distinct amounts Vt'lop smoke-producing tra('ki~lg aids, somt' of which
of white smokr which is ('om posed essentially of wt'r{' reqnirt'd to fUllctioll at {'xtrl'llwly high alti.
metal oxide particles. Undt'r l'ertain atmospheric tudes.
conditions, snch as firing into bright sllnlight, the
sr..oke trail i>. ('asipr for II. g'Ullllt'r to follow than a
1'1'11 flame tra('rl', a.lt hough t hl' fiaml' tract'r is tht' 7·2 PROPERTIES OF SMOKE
bpst UIld~1' most otill'r l·ollditions. In 192:3, studie:,; 'rlw vultH' of a Illilitary slllokt', wilatever its use,
Wt're Ilndt'rtakplI to dew lop a smokt' tracer. It is r,'latt'd to tilt' seattt'riug', ref\el'tioll, and absorp-
was soon appart'nt that att('mpts to ill~rease the tioll of il!(·idt·nt radiatioll by smllll slIspended 1'8;'-
volume of tht' smukt' trail along the trajt'ctory rl'- t it'!t·;-i. Tllt'sl' propf'rtil's art' assot'illtf'd with the

7-4
1-----------------.---

AJlCP 706·185

[ !r-....... ·. .........

r·' . . . I
!
! , -<,
I
, i
I "·! ,

_-
i 1

.
..... _ACe

i ..-
... ..., I
, [
TV"tCIolM'mc~u I~a~ ~
I
1
'ftOt""'~CIMIlrll;OFW~~ 1",,-
('"'~.i! I
- ~
'-

~ ,
-- 1

I I
.. ~It .. 1ON
I I
i I ..... TliaJC.l[! _.._---_ ...... ",1 '~:r
I
~f~'Mt'd....L ''l''''IIA0'>1«JooII(.-
1"" ,o"~,o" ",'
.,., c' 010-' ",' ~ . 'P.' ,,' ~' , <I'
" ",' ",' ,d'

r=~~~"J
n',
,,' ",' I I
I '"
~ .i' <l
'"
')' 1l.tfrrtC. "fLOCII
( .. /5(0;:
"" -,I ",' ",'

".. 1
.... TlCl I
.~
,*,"i"US~
I
~i ~. I, i
. <,'

-
COI"'ICII'1iIT ~, ~,
I ~,
~.
""I/MC
L-..-~~ ""I
",'
'°'1 ,
""" 0'''''' 0","
'''' 00 00> 0' 0'
'" ~ !CO
""'"
Mln'ICL( tu.Mur"._....

Figure 7-1. Approximate Size Range of Airborne Particles

number, siz(', and naturp of the suspended par- Dusts are particulate clouds made up of solid
tides. 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 of the particles in a
parti('ular munition, and tht, method of release. dllst range from about 0.1 micron to greater than
Thp d('llsity, persistenc.y, and subsequent behavior 100 microns.
of' the smoke eiOllrl also depend on meteorological Mists arl' gaseous snspt'llsions of liquid droplets
eOllditions, such as humidity, wind speed, wind di- produeed by the condensation 01' a vapi>r or atom·
rt'etioll, and air stability. ization of a liquid. Mists, especially those occur-
ring IIlitllrally, ('onsist of relativeiy large particles
7·2.1 PROPERTIES OF PARTICULATE rUIl~ing ill size frcm around 5 microns to larger
CLOUDS3,12 than 10 mi('rons. If the concentration of droplets
The dassitieatioll elf types of suspensions in is grt'at !'Ilough to intt'rfere with vision, it is called
terms of thl'ir nuture, origin, and particle size has a fog.
!lot bpt'll ('olllpl"t!'ly S\ll"l'l'ssful (Iut' to t hl'ir indefi· A S!l1okt' is a suspens;on in a gaseous medium,
!litt' ('haraetl'risti('s awl bl'('lluS(' of tht· differences, slleh liS tlIt' atmosphere, of small partieles which
llut always dl'llr·eut, twtWI'PIi dt'st!riptivt' terms in IIIIVt' h rt·}uli\,t·ly low vapor pressure and whieh
S('it'lltitip 1I11t! ('0111111011 usag,', A gaseolls sllsIKmsion st·ttl!' slowly ullder the infiueJl(!e of gravity. AI-
of liquid or s()lid pllrti(·!t·s t!)(, diallleter of whieh t hOUl!h sllIukl's arl' oftI'll (' haractl'rized by their
is I"ss t hall IOO lIlil'ro/ls is ('ommolily t'alled Ii par- II\O;lt, ot' fllrlllutioll, tilt' main criterion is one of

til'ulll.tt' (·Iowl. 'l'h('l't' art' th1'l't' broad ('lass!'!! of pllrti('\t· siZt', Whilt', at OIH' ti>lll', (lilly clouds
partit'ullllt' ('Iollds: (1) (iusts, (~) mist.", /llld un forllll'd by ('OIl1bllstioll and destr\l('tive distillation
slllokt's. If tht, pIII·tieil'S ill UIIY pllrticu\llt(· cloud wt'rt' l'lassitit'(l as smokes, lit prt'st'ut lU\y gllSl'OWi
urt' It'ss thlln approxillllltt·ly 10 JIlil'rOlls ill di. SllSpt'IISioll of pnrtil'it's rIluging ill size from ap-
IIIl1t'tt'r, tht·), IIrt' t'all"d aerosols. 'I'ht' t.(·rm Ilt'rosol proxilllutt'ly 0.01 t() pt'rhllJls :).0 mi('rom, in diaD}·
\l'IIS illtrudlll"'d to ,'ov,,!' Oldy tille. Ilt'rilll sUlipell- ,'It'r. Ilnd whi('h "lIll11t1t 1)(' ('11,s.o;ifi,'d liS a dust or
siolls. It hilS. hOWt'v!'/", bpt'li applit·d ill r:'t'('ut yt'a~ III i:-;I , is t'ollsitit'rl'd to lit' U SlllOk(,. III many ('ases

to alrllost Hlly III'rial SUSIlt'llsiulI of pln'tieles. hi Ill" slllokt' parti('/t·;; an' aglo(rt'I{lIt,·S of lIIal1Y ex-
SOl/lt· "IIS('S, "spt'("ially ill th,' I 'uit .. d Statt's, thl' t rt'lIlt'ly SIIIII II , pri IlIl1ry purl idt's. ( 'a rl,() II tHuokt's,
It'rm at'rmwl is \IiiI'd iustt'lld of pl1rticullltt' dour.!. for PXlllllplt" lin' l'llUlllOsed of t'xtrl'IlIt'ly "mall,

7-5
AM"P 706-185

6r----r--~r_--,_--_,----~--~----~---r--------------

2.00

c
....
II: C
C ....
II:
....
>
C
j:: ....
::)
3
....uIL II:
t-
IL
....
.
" .50

0
0 O. 0.2 05 0.4 O~ 06 0.7 0.8 0.9 LO 1.1

, 'N M'CRONS (),> 0.~2 M,cnONS)

, 51 0115 0~Z4 0.393 0.3'4 0212 0224 0.196 o 17~ OI~1 0.'43

~ 'N MICltONS !r' 03 IIIICAOHS)

Figure 7-2. ScoHering by Sph.rica' Particl•• With Indicot.d Refractive '"..feu.

7-6
AHCP 706-185

primary particles 0f approximately 0.02 micron in scattering of vehicle light will occur when the
diamlt<>r which coagulate into irregular filaments droplets art' aoout 0.3 micron in diameter.
that may reach a length of several mi(Jron~. In The angular distribution of the scattered light
Figur(' 7-1 is shown ttl!' approximate particle i,,, also a function of rIA. For Rayleigh scattering
sizp range~ for typical airborne particles. by small particles, the forward and backward scat-
te1'ing is the same. With an increase in the pg,rticle
7-2.1.1 Opti~l Properties of Particulate Clouds radius, the forward !'lC8,ttering becomes much
greatPf. For a particle whose radius is equal to or
Particles suspended in a gaseous medium scat-
grf'ater than the wRvplength of light, this f~wtor
ter, rrileet, and absorb radiation in a manner which
may bt' 1000 or morr in favor of the forwar.d IScat-
depends on the nature, size and shape of the
tpring.
particle, and the wcvelength of the incident radia-
f:;moke 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 of a larg-e number of
when used for signaling or similar purposes.
different uniformly sized smokes mixed in varying
Tht' scattering of light by a particle can be
proportions. No completely satisfactory analysis
treated as the interaction bfltween the electro-
of thp 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
marle.
smaller than, its wavelength; reflection and re-
The theoretical treatmeut of the scattering of
fraction, in their normal sensc, no .longer occur.
light by particles which also absorb is a difficult
Interaction between the radiation and particle
problem, especially when absorption is selective.
results in energy being removed from the wave
When the incident light is white, thc scattering
front. Some of this energy is de~rarled to heat but
by each of the particles will remoVl' s.:>me of the
much is re-radiated as scattered radiation. Each
particle be(~omes, in pi'fpet, a self-luminous source. light selectively absorbed so that the light finally
scattered by the cloud will be colored.
The theory of scattering by spberical particles
was developed from Maxwell's equat.ions by 'Jus-
7-2.1.2 Properties of Particulat~ Clouds Affecting
tave Mie. 13 For spherical particle!> which are small
Their Stability
eompared to the wavelength of light, this theory
gives rN,ultf< which are in complete a.greement with Smoke clouds and other particulate clouds are
the results obtained from the ll~ss-general Rayleigh esr,entially unstable and will eventually dis&.ppear
theory which states that the amount of radiation with timr ill)e to: (a) motion of the particles, (b)
scattered is inversely proportional to the fourth evaporation and/or eondensation, and (c) .:Joagu-
power of the wavelength. As the particle radius lation and agglomeration.
ir.f!reases in size to approximat?ly the wavelength
of the light, the scattering becomes a complex func- 7-2.1.2.1 Motion of Smoke Particles
tion f)f the particle radius, the refractive index of Movement of smoke particles under the in-
thl' partiele, and the wavelength of the incident fluen('e of gravity and as a result of nndom bom-
light. Tht' scattering eoefficient, i.e., the scattering bardment by gas molecules (Brownian motion)
indpx, is an ext,.emply complex function of the may cause particles to disappear by sedimentation
parameter r! A, where r is the radius (f the particle or diffusion. Sedimentation effects are important
and)" is the wavelength of the incid.mt light, and for particles one micron and larger, while diffusion
I'xhibHs Olll' or more peak~ l}eforp approaching the effects arr inlportant only for much smaller par-
limiting" vahlt' of 2.0 as is shown in Figur£' 7-2. As ticles.
the refractive index of the partjclt~ increases, the
peak in th('sl' eurv('s moves toward smaller rlldii 7·2.1.2.1.1. Sedimentation
partie It's. For s('reening smokp m&dp from fog oil An individual particle seelillg under the in-
which hus a rl'iradiw illdpx of 1.50, tile maximum fiuencp of gravity will reach a terminal velocity

7-7
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ----- ---- - - - - - - - - - - - - ---------

AMCP 706-185

when the aerouynamic drag on the particle is equal l'ollisil'ns oetween part.icles and r<Jsulting in coagu-
t.o the effective '",eight of the partide. If the par- lation or agglomeration of the particles.
ticle is a rigid sphere which is large with respect
to the mean free path of thc gas, but. not so iarge 7·2.1.2.1.2 Dlliu.sion
that. inertia effects are important, Stokes' I.Jaw is Diffusion of particles due to Brownil\n motion
applicable, and the terminal velocity 11 is given results because the parti~les arc irnp"lcted by the
by: gas molecules of the suspension medium. The ruo·
gd' (I' -- 1")
v = ~---'.!----'c- tion imparted to the smaller particles is greater
(7-1)
181) than that imparted to the larger particles so that
where d is the diameter of the particle, I' is the the amOl:nt of diffusion is inversely proportional
density of the dispersed phase, 1" is the density of to the diameter of the particles. 3 Diffusion eife2ts
the gas, 'IJ is the \'i~cosity of the gas, and g is the ac- arc relatively l111important for most particulate
celeration due to gravity. Particles which are small clouds of military intercst.
with resped to the mean free path of the gag. fali
somewhat more rapidly than this equation indi- 7·2.1.2.2. Evaporation and Condensation
caLes, while large partides settle sOlllewhat more The evaporation rate for a given material o.e-
slowly. pends on thc difference between the vapor pres·
The rat(~ of sedimentation for some particles is sure of the dispeI·sed material and the actual
given in Tablr 7-1. It is to he noted that the sedi- partial preMmre of its vapor present in the air.
At a given temperature. the vapor pressure of a
TABLE 7·1 liquid increases with the degree of curvature of
TERMINAL VELOCITIES AND DIFFUSION its s>urface; this increase becomes marked as the
COEFFICIENTS OF RIGID SPRERES OF droplet size decreas~s. Hence, a critical droplet
UNIT DENSITY IN AIR AT 760 mm lIg exists for any temperature and vapor concentra-
PRESSURE AND 20°C tion. Droplets smaller than the critical size will
cvaporate because their I.ltpor pressure is higher
than the partial pr('ssnre in the vapor phase, while
those larger than tLe critical size will grow as a
result of condensation. The same considerations
apply to the sublimation pressure of a small, solid
particle.

':·2.1.2.3 Coagulation and Agglomeration


The process of continuous and spontaneous for-
mation of larger particles is one of the striking
charact~ristics of any particulate cloud and can
be a major factor in the diminution of a smoke
cloud j liquid particles coalesce while solid par-
tieiel'> agglomerate when they collide. As this
proces..q continues, the smoke becomes coarser and
menta.tion rat!' of a screening smoke which has a finally settles onto It has been found experi-
partieie radim of O.;~ miCf()'l is- abou.t O!le mile per mentally that the !'ate of deerease of the number of
year.
Nonspherical partil'les generally attain a lower
particles, - ( ~~.:...) . is proportional to the square of
trrminal velocity; however, this cffrct is not com- the eoneentration n, or:
pletely pre,lidable. If the <>moke is heterogenef)w;,
thf' particll's will settle at differeut rates ~l1using ( :: ) = Cn 2
(7-2)

7-8
AKCP 706-185

where U is the coagulation constant. In integrated motions of from one to many feet. in diameter are
form: observed. Tht' amount of atmospheric diffusion
is illdica~ed by the angle of riSE and angle of spread
(+) - (-!:-) = Ot (7-3) of the cloud ns it travels downwind from the sour~e.
The initial angles of rise and spread usually will
where no is the number of particles at t =
O. be different than those measured farther away
While it is difficult to calculate the exact de- from the point of generation.
gree of polydisperity, it can be shf)wn that the
probability of collision hetween 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 he'lt
faster than those whicL are monodisperse. More- and turbulence resulting from the process by
over, differential settling also increases the prob- which the particulate cloud is generat~d. the be-
ability of collisions between particles of different havior of the cloud at a distance from 'the gen-
sizes. The coagulation rate of smoke is increased by erator depends on the meteorologilJul conditions
stirring, since eddies and swirls result in particles prevailing. The principal meteorological factors
hav:ng a higher relative velocity which increase affecting travel of this type of cloud are wind speed,
chances of collisions resulting in an increased co- direction, turbulence in the lower atmosphere, and
agulation rate. thermal gradients.
7-2.2 TRAVEL AND PERSISTENCE OF
PAR'fICULATE CLOUDS3,12 7-2.2.1.1 Wind 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 limited number of 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 particles too sirable. Too high a wind iilpeed requires an ex-
slll8.II to fall out appreciably by Stokes' Law and orbitant rate of production in order to maintain
which have~oo Iowa 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. If there
factors which tend to dilute the cloud. Tile form is no wind, good r.?sults 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,
doud has traveled a short distance from the gen- carrying the particulattl cloud into areas where it
erator. Also, the formation of 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 downw·.d wL, the &peed of the wind and
cooler air this effect will be less ohservable unl<.!ss the ax: of the plume is parallel to the wind di-
there is a ...,ery great initial rise in temperatm'e, ap- rection. The density of the cloud at any point
is the case when smoke is produced by the burning downwind will be, in general, approy.imately i .
of white phosphorus. (Se!:' Paragraph 7-3.3.2.1.) "t'rsely proportional to the wind speed.
The process by which smoke is diluted and mixed
with air i9 callen "atmospheric diffusion." This 7-2.2.1.2 Turbulence
process is also termed "eddy diffusior," to djstin- Wind spel.'d and direction are subject to rapid
guish it from molecular diffusion since eddy-like and violent fluctuation. This unsteadiness in wind

7-9
AKCP 706-185

velocity amI direction can be considcled to be due per 100 meters, there win be no tendency for the
to pulsatiolls taking plaee in three directions; air to rise b.'eallsP the air mass carried upward
namely, in the gPl1eral direction of the wind, and will beeOIni' ('older and heavit'r than the surround-
in horizcntal Clnd vertical directions at right angles ing ail'. This <lecrem:e of temperature with alti-
thereto. The total of these pulsations in the dif- tude of 1°C per 100 mete't·s is termed by the meteor-
ferent directions is a measure of the gustiness or ologi'lt the adiabatic lapse rat!' for dry air, and the
turbu!enc(' of the atmosphere. degree of stability or instability of the atmosphere
On!' obvious cause of turbulence is mechanical. will df'pend upon th~ extent to which the tempera-
The higher tlw wind velocity. the greater the tur- tnre gradh'nt departs in one directi.m or the other
bulenel', particularly over rongh terrain. Over a from 1hir-; (~ritical value. Au extremr condition,
smooth surface of water there will be no turbu- when the temperaturp inerea[;('s with altitude, 1S
lene!' produ('cd by mf',:hanical causes at low wind kIlOW}) as inversion, wh ich causes extreme sta-
spf'eds. \Vinci speeds greatpr than 10 to 11 knots, bility ill the I()wrr atmosphere. The meteorological
however, will produce waves wLich, in turn, pro- fa('tors dpscribt'd eOlltrilmte to tlll' degree of sta-
dl!!'p mechanieal turbulenl'e in tIl(' lower air layers. bility of the 'ltmosphere which exerts a consider-
Another important factor in producing turbu- able influence on the performance of a smoke cloud.
knee is thermal instability ill thc lower atmosphere. Extreme conditions of stability or inatability will
During th(' day in bright sunshine, the ground influencc tllP. rffectiveness of the smoke cloud in a
surfal'f' re('eiv('s a gT('at deal of heat frem the sun particular tactical situation.
and, SillC(, the earth is a poor eonduetor, the tem-
pl'ratur(' of the surfnc!' will risf' many degrees. 7-2.2.2 Stability of Aerosol Clouds Under Various
Tlw layer of ilir ill contact with the ground is Meteorological Conditions
IH'ated and, since it becomes lighter by expansion,
the layer rises. Since the warm lower layer of air
7-2.2.2.1 Stable Conditions
('annot rise eVNywhere uniformly, it must break
Hnder inversion (~ollditions over smooth ter-
through thc upper cooler layers somewhat as bub-
rain such as calm water, the otlly tendency shown
bl!'') burst IIPward t;lrough a liquid. The actual
by a smoke cloud to rise and spread is due to the
drivi.lg foree is the weight of the cooler air, which
initial transient effect eaused by the heat and
settles to\\'llf(l thp ground r.isplacing the warmer,
tllrbulcnec produced by the smoke generator. The
!ightel' air. These upward, eOllvertive currents
tllrhnlenec is quickly damped out but the heat
eaus(~ thl' bumpiness of thp air which is noticeable
prr'lun'd may be :mffieient to cause a very pro-
in all airplane The passage of a warm or cold
nounced rise, as is the case with white phosphorus
front lila:.' ('ompldel:v alter the tpmperatul'e rela-
smoke lIlunitions. I Il the case of oil smoke, where
tion bctwe(,ll thp I-!roull(l surfaf'(' and air and pro-
the amount of heat produced is small, the tempera-
(hte(~ stabilit;y or instability regardless of time of
ture of ~he srucke at any dilution is only slightly
day or sky eonditions.
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 presenee of th(' sl.lOke ma-
Stability conditiom; in thl' atmosphere are de- terial. As the smoke! rises, the temperatur~ falls
tpi'min!'tl hy t hI' tf'InIH'ratHre gradient t hpreiu. If becanse of two efl'eets; llamely, further dilution
the temperatnre (le~l'pasc with heigh t is more than with ('001 air, and adiabatic expansiDn due to a de-
1°(' pel' 100 metns, the air will ill' ['lIstable; i.e., ('rease ill baromrtri!' pressure. Since, in an in-
tIl(' 10wl'r laypr of air will tend to eise and COll- version, the tcmprrature of the surrounding air
tinllt' to rise as long as this ('ondition prevails. This increases with illerc'lsing' altitude, an ebvation is
is ,'ausp(] by the rising' Jllass of air, pxpallding and soon I'paehed <\t whiclJ the smoke is stable, possess-
wolillg' 11"; it !'ises, bceolJlill6" warm,~r and lightpr ing a dt'llsity i;jputical with that of the surround-
than the surrounding ai r. :f the dccrease in tem- 1Ilg' all'.
perature with altitud,' is betweeJl zero and 1 DC Oil vapor slllokl is often observed to level off

7-10
AMCP 706·185

at all eleyittioll of approximately 100 feet under wind vrlocity. All instantaneous view of the cloud
stable air conditions. ('e<'tain types of smoke ex- wOllId show that it is furrowed and broken by
hibit an erratic' behavior beeause of ubu{)rmal den- nriatiolls in the Will(1 direction and sudden up-
sity. Exampl('s of these are: (a) the smoke pro- w,'rd t'oIlYt'C'tive currents.
dueed by hurning Jil ill an (/r.~hard heater iL whiel:! Tlw lowl'r air is thermally unstable when the
carbon partielps and carboll dioxid" Iras are pre:;- IH'gatiw' templ'rat;ure dl;creaflr with altitude is
PlIt, and (b) HC smoke in which largo(' particles of more than 1°(, per 100 met(>rs of elevation near
zinc chloride and other heavy materialr-o a~'p formed. ground level. This Ilegative gradient may COll-
'Vhile a substantial amount of :1eat is produced tinue indefinitf'ly upwar(l. Thus, in thunderstorms,
ill til!' formation of thes!' smokes, h1uch ()f it is t'.lll1ulull ('1onds often risr to a height of several.
(tHickly lost by radiation. partielllRrlr at night. milrs; a smok(' cloud would b(' ea"ried to the samp,
8inc(' tl\{, hl'at producf'd in the generation of thr hpight.
smoke will IIsually cause the smoke ('loud to rise {Tmlt-r oth(,1' circumstances, a tmrrent i'f warm-
!,Y('l1 under the most stabJe conditions, it may br (01' air may bl' blowing at an elevation of a few
:-l.nti(·ipate!i that the elond will lift entir(>ly off thl' hnndrC{l feet so that the temperature gradient
g-roull:1 after a short distance of travel. If, how-
Illay bN'omp zero, or r, rn positive, giving an in-
evel', a wincl of ('ol'siderabl(> velocity is blowing,
yprsion at this pll'vation. There is no tl'udency
t his lifting fron: tll(> gronnd will not occur.
for th(' hwpr air to rise through this warmer light-
Although the heat producrd in the smoke gen-
pr layr.!', and a dt'finitr eeilinlr will be established
('rator Pl'OlllOtf'S a risr, it has little {'tcpct upon the
for the eollVt'etivr turbulence. Within this layer
sprrac1 of tlw smoke dou(!. The spread that oc-
tl)(' atmosplH'I'r turns o"l'pr and uver, and the smoke
('IUS is due to initial turbulence and this soon
Illay hE'('ome rliif'lc·;pd thl'oughout tlw layer before
(lamps 011t. COllsequently. if it is desired to pro-
duee l'ontilll~ous clouds of smoh' from a series of it has travf'lf'd wry far, Howcver, eddy diffusion
individual g'('nerators, it is IH'('rssary to place always O('(mrs at tht' boundarirs of the upward
tlJ(' geJierators wry clos(' tog-cthrr; otherwise, the ('onvrctiw ('l1rrl'lI"s, causing· some smoke to diffuse
individual plumrs may lIot merge for H long wa.y throllg-houi: tht' settling layer of cooler air t..:ven
downwind. Thio situation holds fOl' smooth ter- with a hilrh convecti\'r ceiling.
mill. How('Y:~r, if thr terrain is covered with 'fl\(' rate of ris!' of the ('onYectiv(' current in-
shrnblJPry, for (Oxampl!·, thp latf'rai spread of the ('n'asps with tl1p[lI1al instability. The angle of rise
f'loud is grratly ill('l'l'l,Sed as a rpsult of the me- of the smoke eloud. IRS a statistical average) is in-
(·hanieal tnrbnlrll('(' produf'(~c1 by the wind flowing v('rsely proportional to the wind velocity. With
throug;] thp shrubbrl'Y. zpro wind, th(' convectiyc crl'rentr, rise directly
upward. As the wind increases, dIP direction of
tl1P cOll\,petivp (';.rrent is iW'lined increasingly
7-2.2.2.2 Unstable Conditions
away from the vertical.
Whrll thp air f'llrrpnt is turbulrnt urf'ausp of
thrrmal instability, atmoflpheri(' di1fusion takes
pIa!'!' to s11('h all ('x tent that tbp illitial, tranl'lient 7-2,2.2.3 Estimat\on of Atmosph~ric Diffusion3
I)('havior of t hp (,loud, fiu!' to til!' hf'at Hnd turbu- Two ~xpressiolls were drrivi'd which ('nable th('
1(>1]('(' fl'OIll tht' g'PIH'rator, is of littl(' signifieance. (~oll('('ntratioll of (gra~m; Ill'r e ubiI' ('cntimeter) at
'rhr HPI'Oi;OJ ('1011.1 ('olltillll('S to ris(' and spread as a gi\'PII point in II mnokt' cloud to be pr('a.idl'd from
it tra\'('I~ dOWllWi'ld until th(' (·loud bt'('omes so kllm\'l('dge of t he rat!' of (·missioJl of partIculate
t !till that it~ boulldaries ar(' 110 longer distillguish- lIIattpl' awl of ('I'1'tail1 IllP«'orologit'ul pNperties of
ahl(' to tht' ('~'t·. If It tin1/' t'xposnrp WI'I'P to be tht' atmospJlPrp. Till'S!' pqllllti()Jl~ for pl't'dieting the
tahll of tIl!' "Ioud, it wonld app!'ar as a ('ollr with ('olH'PlltrHtioll frolll ('ontillllOllS poillt allli line
its apt'x lit tht' ~('neI'ahr awl it,. axis rising at aJ! seur( e~ at grollnd 1('\'('1 art':
Hllglt' from thp horizontal. the allglt' of rise de- ('oLtimwlls point S(Wl'!'f' PlllittinJ! () gram" per
pt'.lfling- lIjlOIl tilt· d('gre!' of instability and the sP!'oud:

7-11
All.:CP 706·185

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

--~
,
e..p [ -x
n-;! y~
_ _ __z:!)]
( e/+ G~'~
not evaporate, faU out or coagulate rapidly.
-0' C fj ~-Il
,.. tI Z .r d. Be effective at a low eoncentration of ma-
(7.4) terial.
e. Be substanti&lly nontoxic; noncorrosive to
Continuous erosswillcl infinitl' line source emit··
equipment, and, except for control agents,
ting Q grams lwr ~R.cond per centimeter:
nonirritating to t.he ey~s, throat and skin.

.rd:r,z)
2Q
= '7:'he,U.rl-~"· eXJl
[ 1
Clx~- " .
-Z2
(7-5)
f. Be suitable for large-scale manl'faeture,
storage, and transportation, without har..ard
01' deterioration.
w'here the spacp coordinates x, ]I and z (origin at
the oo11r('(') refer t.o thp downwind, crosswind, and
wrtieal dirertions, ff':o,pl'dively; U is thf' mean 7·2.3.1 Screening Smokes
wind velocity; Cy and 0, art' !!:enf'ralized eddy Hereening smokes are usually white and can
diff'usioll t'ol'ffidclIts; and n is a parameter r~fer­ bt· used to:
riJlg to thl' stability of the atmosphere, the llU- a. Conceal movements-, illt6Iltions, cquipment,
mf'rical value of whiph varies bf'twpen zero and and installations of friendly forces from
unity. These equations indicate that t.he concentra- ground observation.
tion varirs dirrctl~' wit.h thp SOllrrl' strength Q and
b, Blanket friendly positions and installations
approximatrly inYl'rf;ely with th£' mf'an wind ve-
in order to cOllceal them from air observa-
laeity fi. Thr distriblltion of eoncentration in the tion and attack.
('rosswind dirl'ptioll and ill the vertieal direction is c'. Prevent aimed fire on approaching friendly
approximatl'ly Gaussian; howpycr, du(' to ground aircraft, i.e., to screen thf' landing of air-
ref\pctioll, thp vcrtical distribution eorresponds to borne troops by parachutc and glider.
only oJl(,-half of the <tallsian (~Ul·\,(,. If the terrain d. Provid(> an extl'llsi\'e, thin haze for conceal-
is level and there is Oldy a small tcmperaturr ment of friendly areas without seriously
gradient, n is approximat{'ly 0.25. Under theS€ impeding close-range vision.
('ollditiollS, tlw peak eOll('entrati:m downwind from P. Establish dummy screens to deceive observ-
a point source will decrease as X--1.76, and for a ers.
line sonr('p as ,r·- 0 .88 , f. Communicate.
g. Form a thermal radiation attenuation '>creen.
7·2.3 SPECIFIC PROPERTIES OF MILITARY
There are three types of smoke screens. A
SMOKES
smoke screell laid over friendly areas to hinder
Rmoktos are us('(1 for four bilSi\' military pur-
('rwmy ael'iul obs{'J'\'ation and visual precision bomb-
poses: (1) for Sl'l'l'l'J1;ng, (:!) for signaling, (:1) for
ing it' culled a blanket screen. Thi:, typ(' screen is
t ra('killg' awl aequisitioll, and (4) for disseminat-
formed by the gradual merging, downwind from
ing (S(',' Para:.rraph 7·:n of ag('nts in riot eontrol the sOllret' of generation, of individual smoke
and nthpr applications. Whih' smoke may be P"()- streams, A smoke "au is normally established in
dtl<'c,l frolil II larg(' lIumhr·r of chemicals in a a battle IIn'a to eOllceal friendly activities from
vtll'it't\, of wavs Ollly a fc'w of these meet thE' spe- ohservation and ground tirt'. It is formed in much
(·ifie 1':.qllil'\'Ill:'I:t~ fc;r a military smoke. '}'h(' ideal tiL' imnw mallllf'r as it blanket. screen. Usually,
miJital',V sn;okl' material will: h()wt'vpr, a Sl\10kf~ ha:lp is h'ss uniformly dense than
a. Ik uyai\ahle ill suftit·icllt qUlllltit.ies for large- a sllloke bhlllkt't. A smokl' cur/din is /I delise,
sell it' prod \letiull of t Iw mixture at a rela- vertical development to C(lneea! objects at ground
tivc'ly low ('ost. It'vpl fr'oJII obst'l"\'t'rs at g-re/llllcl It, "('1.
I l . Hi' easily awl C't)i(·j{'lItly dissPlIlillated with. Onder IllUIlY eircnmstnnces th('se distinctions
out th!' liSt' uf l'laboratp equiplIlI'llt. disappear. For examplp, 11 smoke curtain may in-

7-12
AMCP 706·185

terfere with aerial observation or a blanket screen dissemination, measnrem('nt, ph'., of colored smokes
may settl£> to the ground and become a smoke is {'ontainrcl in Paragraph 7-a.4,
curtain. These distinctions are i:nportant for de-
fensive screening only, inasmuch as offensive use 7-2.3.3 Tracking and Acquistion Smokes
of &moke has the primary objective of blinding
Hmoke-producing (levices such as- generators or
unfriendly forces by enveloping th~m in a dense
traeers are used as 11lI aid in the optical tracking
blankct of smoke at ground level. Due to the re-
of projectiles, high speed aireraft, and missiles
quired subEistenee of smoke screens, large quanti-
hoth at i'wa I('vel Il.nd high altitudes. These devices
ties of near optimum materials must be used.
optimiz(' tll(' 11 bility to locate and track whirles
Of tht:' large number of available smOke-producing
along till' flight path and minimize the possibility
chemicals, only a few have been found suitable for of losing' l;·ignHieant data. Requirements for optical
use in the production of military smoke screens. tracking' aids vary <;onsiderably because of the
wide range of eonditions pncouutered in the track-
7-2.3.2 Signal Smokes inl! of tpst v('hitles operating over a wide range
[t is a prerequisite that smokes used for sig- of altitudes and speeds. No singlt' smoke agent or
naling- and commUlli('ations be clearly distinguish- generating systPllI will satisfy all requirements
able from othl'r smokes (and other clouds) pro- and Ilumerous smoke-produc.ing methods are neces-
duced for diffrrent purposes. Thus, the use of sary. Each is designrd for a particular applica-
tion, I'lUphasizing ('('rtain ideal characteristics.
white, gray, and blanket smoke~ for signaling is
'While thi' valut' of a screening smoke is due
Wi y limi t('(i and colored sn!okes are ~lOrmally used
to its absorbing and light-scattpring power, the
for this purpos£>. In addition, the use of several
visibility of a slUokl' trarking aid is due, chiefly,
differPllt {'olors allows lllort' information to be
to its light-scattering' powrr. The ideal tracking
transmitted and also results ill a elrarer distinc-
and acquisitioll smoke should have the following
tion bctWt't'1l tIl(> smokp signals and It varying back-
(~hara('tpristies :
ground. Effrcti\'!~ methods for the production of
{'olorl'd smokl', including pxplosive dissemination, a. Be t'ffil'ient OJl a wright and volume basis.
invol\'(' tlll' vaporization alld ('ondensatioll of a b, Have the ability to function and perform
dye; tIH'rpfol'c, thp dye must bt' heat-stable so at altitudes where pressure is low, and water
vapor and oxygen conc.entrations are small,
that it {'all hp rapidly vaporizrd at a relatively
e, Have the ability to function through the
high temppratl\l'{' without apprel'iablr thermal
range of temperatures encountered from
(iegl'adatioll. III addition to its color, important
ground temprrature to the minimum high
ehal'aett'risties of a {'olol'rd smokl' include:
altitude trmperaturl'.
a. Visibility (thp conditions under which the d. Require !ittle power for generation and dis-
('loud can be seen and its color recognized). persion.
b. nuratioll (the t.ime period during which e. Bl' as nontoxic, nonexplosive, and noncor-
smoke is rvolved from a munition). rosive as possible with regard to both smoke
c. Persistellce (the total period of time during ehemieals and products.
which a eloud is visible).
d. Volume (thp quantity of s-moke emitted; for
eolol'!'d smokrs, volume has also been de-
7-2.3.4 Smoke for Dissemination of Agents
fillrd as th,' (~ri)ss-sectiollal area of a cloud A~ent smokes for riot control and other pur-

prrselltl'ti to illl observer). POS('s art' producl'll ill much the same way as col-
ored signal smokps. In many cases, a vaporization
1\ Ithough 1101 as iJJlportallt as ill thp ease of prO('eSB is followed by a ('ondensation process in
Sl'('('('IIi 1Ig' sllwkt', tht' smoke (,loud shon ld be as whie)1 till' agent {'ondens('s to form the disperse
Ilontoxi(', nonirritat ing, alld lIoIl('orrosiw' as pos- phas!' of til!' slUokt'. Agent smokes may be dis-
sibil'. IllflJrlllatioll 011 till' ('ompositioll, method of sPlIliltatl'd by {'xp!osiw lIH'all'l a.>; wt'lJ as by some

7-13
AMCP 706·185

of the other methods discussed in Paragraph 7-3, libriUIIl is rpached, The production of a super.
The physiolo~ieal rffeetiveness of materials dis- saturatt'd vapor and formation of a dispersed phase
seminated ill this way depend" strongly on the by \'oJHlensatioll art' eompl(>x procesS>('s and pro-
particle sizt', While visibility of the smokl' may vI' ('('('d essentially simultaneously, Consequently,
lllay not bt' important, tlJ(' volume of smoke and its littlr c1irl'd information has been obtained on the
duration is> important, It is also necessary that the I'lirly stfl~('S of partid!' formation,
vaporization and ('ondensation procrss be efficient Condensation of a vapor iR facilitated by the
alld produ('(' a minimum of nndesired changes in presence of fOl'l'ign particles. InsolUble foreign
the flgent bt'in~ dispersed, particleR can absorb a thin film of vapor on their
;;;urfac('s and bt'havp as liquid droplets of equal size.
7·3 DISSEMINATION TECHNIQUES If t hp foreign pal'ti('le is soluble in th(' condensed
Dissemination refers to the process by which a liquid, thp vapor press nrc of tIle liquid is decreased
\'hemieal agent. is couverted into a cloud consisting and, ('onst'qucntly, the snpC'rsaturation required for
(>ither of vapor or fine particles, suspended in the l'api(l eondensatioll is redw'E,d, Oharged droplets,
aIr, Fo!' agents such as smoke, which are dis- whirh art' fortll('d duC' to tht' prest'JlCP of iOIlS, tend
seminated as a particulate cloud. the process to ha\'(' a larg!'!' surfal'(, and, hence, a lower vapor
usually il1\'o1\'es tht' formation of small particles prpSSllr(' which result in condensation at a lower
of tllP (lisprl'sed plJas(' and the distribution of these sllpl'l'satnratioll, If eondensation, in the absence
partie1es in thr air, of fort'ign partielps, wpre to start from a single
molpculp, tht' theory indieatps that 11 mnch higher
7-3.1 FORMATION OF THE DISPERSED slllWl'saturr.tion wO:lld 11(' required than that {)b-
PHASE SP1'\'(,<1 f'XIH'rilllPntfllly, Therefore, it is postulated
The u.ifilH'rsed phase can be formed in two t hat small agg'r('~atps of mo1pculc>;, of a:)proxi-
ways: (a) h:'o" 1·(lJIdrnsation proeesses in which mat!'ly th!' ('l'iti('al sizt', arC' eontinually produced
moleculp>, of a vapor unitp to form the particles by l'al.tloHl tllli'tulltion in thp vapor. Molecular ag-
of the (lil"persp(l phase, and (b) by dispersion IIl'l'gatps smalJt'l' than tIl!' critieal sizp will disap-
prOf'('ssrs ill whirh thc' particles arr formed by 1)('111', ,,1Iilp Ihost' largt'r than tIle ('ritipal size will

the brpaking up of it solid 01' liquid material. In t'olltitlllP to grow,


the first ('asp, tlll' spprifip surface (the total surface [11 mally ('asl's of military intf'rest. the super-

prr 1lIlit-volllllH' of HIP mat('rial) decreases; while ,;atlll'at,'<1 yapor is produced hy the \,yap0i'atioll of
in the seconr! l·asl'. tIl<' sI)('('ific ~mrfae(' illereases, a sllbstalll'\', followpd by the ll1ixill~ with cooler
ail' of til(' 1'!'latiwly warm vapors produced, Con-
7-3.1.1 Vapor Condensation Processes dl'llsatioll till'lI follows, resulting 1Il the formation
'I'll" disjH'l's('(l phas(' of most particulate clouds of till' disp<'l'I"!'rl pitas(', TIl(' partif'lt's in a smoke
is pro<lw'('cl hy ('OII<iellsatioll fr01ll th(' vapor phasr PI'O(hll·('d as thl' t'('sult of ('()Jnbllf,tiol\ al'p also due
and invol\'('s th,' unitillg of vapor molpf'llirs to form to vapor ('OIl(11'lIsation, Tn this ease, du!' to the
hi~IIt,1' trlllpl'l'atllt'(':' ill\'olved. it is impossible to
largot't' partic'll's, 'I'hc' formatioll of it clispers('d
iIlJaI~"z(' 1flt' IH'OC'('SS ill drtail. Clwmical rractions,
phas" hy this IIIdhor1 il\\'olws two fiteps: (11) pro,
dW'illg' Ihl' \'apot' ill a sllJH'l"satnratt'il statp, alld illl'\lIdillg' s(,\'('I'al for (ll'odul'illg' smokrs of mili-
(h) ('()lIdplI~ill~ tl\(' slIppl"satlll'all'c1 yapol' 'rhl' tary illkl'pst. oft('ll invo1\'!' a ('om})oIlPnt of ttl<' at-
snppl'Satlll'1ltl'd \'apol' is IIsllally obtail\('d by: (a) lIIosphpl'(' (s1\('h /IS wah'!' vapor) as OIl(' of the
1'1'1ll'tallts,
thl' ('()()Iing' of a warlll \'apol', 01' (b) It (·hemieal
,'padillll whit'll I'l'Slllts itt till' fOl"matiol\ of a snper-
sntlll'iltl'd \'lIllOI'. III t'itlll'I' en "I', till' {'X('I'SS vapor 7-3.1.2 Dispersion Processes
will "olld"I1"" 10 fOl'lll 1hI' pa I't il'iI'S of' tlH' dispc'rst'd TIlt' formatioll of a rlispl'rS('d phas(' by di81)('r ..
pha,;", 'I'h,' t'tlll(l('lhalioll of' it snp"I'sallll'all'<l YaIlOt' ,;ioll IIll'liIods ill\'oh('s thl' slIhdivisioll of /I soli<l or
is a'·"ldlqHllli .. tl hy Ih,' Iih,·t'lltioll of hl'at so tllat this liqllicl illto till,' pal'li('ks, Thl' 1Idlla1 1lH'(~hallisms
prOl'I'SS will ,'olltillll" Olll'" illitiatl·d. ulltil ('(Iui- b~' "'hit'li tilt' titl(' pIIl'til'\I'S aI'\' protilll'pd and dis-

7-U
AMCP 706·185

pt'l'st'd ill the ,.;uspending mediulll ar,> intimately t he venturi nozzle type, wher(' the smoke-produc-
rt'luted alld 1I0t always eOlllpletely understood. ing Illatrrial is atomized prior to evaporation.
III the eaSt' of 11 liquid, ('nHgy applied to it causes 'rhert' art' two othpr important types of atom-
tlt(' liquid to (\SSU!lH' an unstable l'onfiguration iZ('rs whil'h arr of sOIllewhat lrsser milit.ary im-
whidl thl'll brraks up into small dropiets. A :;olid portallt'!'. Th!' first of these type,; is· the ceutrifugal
substalll'!' may he dif.>rllpted and dispersed into fine atomizrI' ill whie!: tllr liquid is fed onto the ce r ~r
parti('lrs by appli('ation of t'Bergy, or the solid of a rotating dise, (,Olll" or top and centrifuged
('all bl' preg't'olmd to tht' d!'sired siz!' and then dis- off the ('dgp, producing dl'oplpts of relatively uni-
pPl'srd into til(' sl1spentiing mediulll. form sizr. Tn th!' speond typl', thr hydraulic
In the atomization of liquids, the energy is ex- atolllizPI', liquid is forced throug-h &. nozzle and is
panded mainly in: (a) forming new surfaces, hrokl'lI IIp illto dropletfl. III this latter case, the
(b) ovrrcoming viscous forces in changing the atolllization (lrpellds more Oil tht' physical proper-
shape of thl' liquid, and (c) meeting losses due to tit'S d thp liquid and tlw eonditiol1s of ejeeti()ll
iurfficient application of the energy to the liquid, from the lIozzle t Ilall 011 tl)(> interactions between
Devices commonly used to disperse liquids are of tht, liqni(l and til!' ,'urroulldillg gas.
three main typef>. Dusts can br forml'd by the disruption of solid
One type employs a high velocity gas or air matrrial or by th(, dis/wrs;oJl of a material, finely
.iet to break up II liquid rmerging from a nozzle. ))J'('g'J'UllIHi to a df'sirpd size .
Atomizers of thifl tyP(' produce a very wide range The for('('s l'Pquirrd to disrnpt the solid ma-
of droplet sizes which can be somewhat reduced tprial may he appli!'(1 ratII!'r slowly by milling,
hy trapping the larg('r droplets within the atomizer. l'l'llshillg', or griJl(lillv" 0)' rapidly through ex-
Tht' cleg'ree of atomization obtained by this method plosion or impad. In either ease', tll!' applied forces
IS influi'IH'rd hy the following factorE-i: ,'alls!' disintrg'l'atioll hy "plittinG' or cracking' along
a. TIl(> 1'dativr yeloeity of the air past the plal\('s of W('akll('ss ill the material. The result is
droplets. thr formatiolt of slIlall fragments ana fine particles
b. The physical properties of the liquid, in- n'lpaspd frolll th!, frpshly formpd surfaces by
cluding surface lension, viscosity, and den- !'raeking OJ) a mi!'roseal(' as the material is torn
sity. apart.
(', TIlt' ),l'latjw qllantity of air expressed as tllP
ratio of \'oilll\lp of air to yolume of liquid. 7-3.1.3 Combined Processes
Withill /I limit('d rangp, tll!' ~llkiyama 'ranasawa ~inee mist dispenion methods will not pro-
('quatioll Hpplil's, ('\'1'1\ thollgh it is rlinwllsionally duee pal'tieles "f the correct size, in many casef> the
i 1l('OI'I't'('t. 6 dispersrd phase f(lr smokes of military interest is
obtained hy eOlldf'lIsation from It vapor phase which
is forme(} by (~vaporation of tlw smoke-producing
agent. Howev!'r, ill order to faeilitate the trans·
II'llt')'i' d" is t lit' dillllll'h'l' ill lIIi('l'ol1s of a singlt' drop f!'l' of h(,at to alld the rpm oval 01' thp vapor from
with I\;" sallli' ratio of SlIl'l':W(,-to-yoluIIW as 1\ l'ep1'r'- the slll'faer of til(' agl'llt, it i~ oftrE atomized br-
s('lllati\'(' salllpl(' of til!' atolllizl'd droplets; I' is 1'01'(' it. is ('vllporatrd. Y:1J'tkula1f' clouds ('an be
thl' \'t'1()('it~· of tll\' ail' ill ('('lltilll\'t('I'S 1)('1' st'('OIHI dpyrJopc'!l hy tll(' atomization of II solution con-
)'('Iati\'!' 10 ll1at (If tll(' liquirI: (h I ().t is tl)(' yohlllH'- I aillillg 11 )ll)IJ\'olat i 1(' tH' s\ ightly volatil<' solutr in

flow-I'att' of liquid to tilt' \'ol!lIl1t,-f!o\\,-rilt(, of ail'; a \'olatiJp "nln'lll. Thl' 801\'('lIt ('vapOrall's and leaves
? i.s th!' dt'llsily of th(' liqui(I in g'rallls 1)1'1' (·ubi(· tll(> snilltl' \Vhi..!! ('OlltiPlISl'S to fnl'Hi th,~ disJwrspd
"('1I1illl('I('I': :J, is lht, \· .. Io(·ity of tI)(' liquid ill (lois!'s: phas!' of a parti!'lllal(' doua. TlIt' /·xJ,losiv(' dis-
.11)(1 1 is tIlt' ~ud·a(·t' t"lIsiuII ill dYIl.,,, Pt'!' ('('nli- pt')'sioll of ':olatilp lIlat(,l'ials. ,;uel! as the dyl's used
1111'1(')', This "quatio)) is 11"";] ill ('sliIll1l1illg' 111.' Jlt'I'- fill' ('(dol'('(] slllol,(" is als() it '·IIl!lbilit·d pro('ess. The
forman,·(· of' piIl,ti(·lIlat., ('!olld g','n.'rat())'s slIl'11 as !'xplosi()11 )lIt'l' !11t1J ie'ally d ispl'J'sl'''. \'aporizes, and

7-15
AMCP 706·185

mixes the material with cooler air, resulting in the materials Hll' proper references should be con-
formation of a particulate cloud, >ll1ltrcF4,15,16,l i and if little or no information is
available. pxtrcme caution should be exerted,
Till' rPllJaining' sections of this chapter em-
7·3.2 MILITARY PRODUCTION OF SMOKE
phasizp production of smoke by pyrotechnic means;
Pyrotechnic munitions for producing smoke,
however, thp same principles arp applicable to
whether for screening, signaling, or other purposes,
other methods for produ('ing smokf', some of which
ai:,' usually one of the following general types:
arp briefly discussed.
a, Venturi Thermal Generator Type, The
smoke-producing material and the pyro-
7·3.3 WHITE SMOKES
technic fuel block required to volatilize the
\Vhitp smokps arp widely used for sereening, ac-
smoke material are 1Il separate compart-
quisitioll awl tracking, tirf' control, and signaling
ments. The smoke-producing material is
purposp:-.. 1'he:; ('an bp produced from many chem-
atomized anrl vaporized in t}J.(' venturi noz-
j('als ill a "aridy of ways and, in general, are more
.lIe by the hot gasps formed by the burning
pffit·ient on a weight basis than colored smokes.
of the fuel block.
Helatiwlv fpw of thp nwthods for producing
b Burning Type. Burning-type smoke com-
whitt' smok(: arp of value for production of the
positions are intimate mixtures of chemicals.
largot' amollnt of smoke required for screening
Smoke is produeed from these mixtures by
purposp!o; whil'h is olle or the importallt uses for
either of two methods. In the first method,
whit!' smok(,. HecallsP of the large amount of
a product of comb1\stion forms thf) smoke or
smoke l'C>(juired, it is important that the maximum
the product reacts with (,(Hlstitllents of the
p/f('('t h(, obtail)('(l PPI' IlJlit-wpight of smoke-pro-
atmospherp to form a smoke. In the second
dwillg llIatprial. 'rhis will tlf'pend 011: (a) the
nlPthod, the heat of ('ombustion of th(j pyro-
wpin'ht of tllt' matprial !lvailabh· to forn' smoke
par;;dps. wlwHH'J' this was ori~il1ally pres(lut in
technic spn"?i-l to volatilize a component of
the mixturf' which then l'ondenses to form
the smoKe. tIll' mixtlll'l' 0[' is ('ontriliuted from th(' atmosphcre,
/ll)d (h', t hI' f'tTieif'll('Y of l'OIl wrsion of thf' smoke-
('. J<Jxplosive Disseminatioll Type. The smoke-
Pl'OdlH'illl! nlat('rial into slIlOi{(' partiel!'s having the
IJL'odul'ing matprial if; plllverizf'd or atomized
optinllllll lil!ht-s.. att(·l'ill~ and o:)seuriug' eapability.
and tl](>11 vaporiz,~d, or a prpgronnd solid is
}<'ol'lllatioll of smokf> pal'tieles by ('ondellsation
diRlwrspd by thp ('xplosion of a bursting
(·harge. frolll tli(' vapor phas,· is tht' 0111y practical way to
pI'olb,'!, thl' IUl'I!(' alllOlillt of whitf' SlIlOkp required
It is /0 bi' Ilotpd that smoke is ali-lo produced for for l\lilitltn' St'l'l'l'lIillg PIIl'POS('s. "rhl' hot vapor is
military pm'post'S by othpr than !lyroteehuie means. lIsllally 11I';)(!tH'('d by \'olatilizilt iOIl (\1' by ('hemieal
~'or ('xampl<" ("'J'tain s(,1't'l'ning-slllokp mntprials l'('adiolls II' whi(,1t 0111' r{'aetilllt is [JOrmaIly a COUl-
('a n 1)(' d issf'!lti Ilil t {'(I by 1lH'('halli('al smokc ~t'lll'l'a­ 1'011,'111 of I hI' LlII1()spllt",(>, l~xamplH; of tlw thl'ep
torN allll otltt'['S hy tlw lise of airplalH' spray tanks. [Host \rial'ly itSI'd s"I'I'I'uilll-: SIIlOkf'i-l arr:
Signals and I I'i!!'kill~ aids ('llII i)(' gent'rat('d by
a. Oil smoke. whidl i~ prodn('ed by tlw volatili-
using' Itot ('XIWUSl goas('s frol11 aiJ'('raft or tunk en-
zation H!HI .'owh'usat iOll of oil.
giJIf''; 10 \,ili'ul'iz(' t hI' SlIlokl'-J)J'()(lut'illg materials.
b. White phosphorus smoi.e, which is produced
'I'llI' iIWJ'('(li"lIts u ;1'(1 i/l Sl!lokt'-Jll'odl/('ill~ l'hem-
hv ")wrnit'al l'eadion with th,' atmosphere.
". :~'iJIt, "'!luridt' slliuk,', whieh is produced
i"als alld ('Olllbllstioll Jl['Odll('/S, awl/ol' tlw eOIi·
<I"IISt'<I vapo[' pm'ti"les I'I'OdIH'Pc! ill a Slllok(', should
hy 11 l'owhillllt.iull (If volatilization and dWUl-
I", ,'(lIl~id('I','d to hl' irl'itatillg and/or toxiC'. l'ar('
ieal rNI!'t lOll.
should ht' ('X"l'tt'<1 iii wOl'kiltl-: with slllOkl'-}l,'o<illeillg
millprials alld tht' 1'('slIltill;! ,;Illokps, I'sph,jally 1't'- Oil ~m()kes art' llormull,v l;l'udll('(,d l)y vO'nturi-
gill'dill~ th' i/J},alatioll of high ('OIl"t'lItl'atioIlS alld tyl'" tlll'l'lllal generators, altlJ(lu~h intimate lnix.
IOIlg' ,'XPOSIU·,·' tileI'd\>, \\'h"11 iU\'I'stigatillg' lit'\\' tt:r,' hurnill/-r typt's of llllllJit:OllS ha\'\' been (it'"

7-lti
AMCP 706-185

veloped for dissemination of oil smoke. Zinc A Jll'l'SSIU'(~ tubt' (,Olll!eets' thl' agent ('ompartment
chloride smokp is produced by a burning-type IIlld till' fuel ('ompartrncnt and permits the pres-
munition. 'White phosphorus smoke for screening ~I1I'(' (\\'wlopl'd by the furl bloek to aid in forcing
is normally produced by a bursting-type munition. oil through an orifice into the venturi throat.
IIt're th(' 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 can of tIl£' gasps promotes atomization of the incoming
be produced by t h(' vapol'i7.ation and condensation oil str\'am and the droplpts aI''' quickly vaporized.
of an oil that has a high boiling point and a low The rate of f('eding is goverJH'd by the pressure
volatility. 'I'll(' first successful geIlf~rator for pro- differential bdwe,'ll tilt' agent compartment and
ducing oil smoke was the M1 mechanical smoke tIll' throat. thp size of the f('('(1 orifice, and, to a
generator. In this generato:' the smoke oil was minor ('xtent, the resistance to the flow through
flash evaporated at a relatively high temperature, the fpt'd tube. I"ittle d('('ompositioll of the agent is
with wat!:'r added to prevent coking. Thc equip- ('II1t;;pd by the rplatively high temperatur('s required
ment was heavy and complicated, including gaso- fOl' rapid evaporation due to the short period of ex-
line engines to opcrat(' the necessary pumps and posure. The efficiency of this typP of generator j."
blo'vers, coils for th(' evaporation of oil and high pst w}l\'1\ the agent is heated to a rather high
water, and burners llsing flH'1 oil tu heat the coils. tt'lLlp('rature for the shortest possible time rather
In spite of their many disadvantages, these gen· than a lower temperature for a longer period, 'I'he
prators, along with similar types, were widely used partide sill' of a smoke produced in a venturi
dvring World 'Val' II. thermal-generator type of munition ean be defined
in tl'rm& of: (a) the Nukiyama Tan1\sllwa equation
7-3.3.1.1 Venturi Thermal Generators (Equation 7-li), modified to include the effect of
'rowan! the end of World War II another systt'llI Ill'at upon the aerosol, awl (b) the thermo-
slllokt' g'l'lleratol', tIll' Hpssien, was developed for dYllamit' pl'Opl'rties of both the liquid and the
the ('. :So Navy in which the fog oil was atomized, Jlyrotechlli(~ ('ombustion pro<luds at the point of
mixed with till' hot. gase& produced by the com- mixing, which ,~olltrols the amount of liquiG
IJllstioll of a fllel, and vaporized ill a venturi vaporizP(l. 'l'hllS, thl' smoke formed ean be eon-
throat, 'I'ht' de':elopmel't of wnturi-type th(~rmal· sid('red to hI' llllHIl' up of two parts· the larger
g-('Ilt'l'1ltOI' IlllllJitiollS IIsing pyrotedmie fuel blocks JlHl'1 i('l('s prod ll('pd IH'cdomil!an tly by tl){> atomi.:a-
was also aC('()ll1plisllt'd dll~'ing World War 1I; how- tioll I1I'O('('S';, 111:(1 smaller partidl'g produced by
1'\'P1', t ht's!' items wert' not fully ready fOl' produc- vaporizatioll and l'olltlensation.
tion until after tll<' War. The portioll of till' liquid vaporized depends
Oil till' heat tralls,j't'rrt'd 1'1'0111 Ow hot gases. 'rhe
7-3.3.1.1.1 Operation of Venturi Thermal 1l1ll0lJllt vaporizl·,l is siglliti,'aHtly utfpl'tl'{i by mass
Generators flo", rat PI', meltll SI)('('ifie heat, awl illitial gas tem-
Tilt' ojlt'ratioll of It venturi-tYPI' tilt'rmal gen- pt'rat \l1'('. With propel' dpsign of the V(>uturi,
t'rator to Pl'/lt!IICl' II Siliok(~ iJlvolvl'S thl' atomization tiwl't' is sllftit'it'llt tilt", fot' thl' heut to h(' trans-
oi tht' IIqllid. tltl' vaporization of the droplets f('l'\'l'd frolll tht' /!asl'~ to till' til/llitl. 'rhe oVt>rali
prod\l('t,d, alld th,' displ'rsioll of tlw vapor ill a PI'O\'t'SS ill the v('lItwi (,!III Ill' ,'ollsidt're<l to be
stl'l'lI111 of :Illt g-ases. A typi'.'ai IIlIit, sho\V1l sche- ('~t'lltilllly atiiuhatil',
mati"ally ill Fi/!IIJ'" 7-:1, l'OIlSish of: (1t'IIt'I'ators of d.;" typt' rt'~~:dalt' particle sizp
11. 11 flll'1 bltwk II'hiell, Oil I) II I'll ill g', 11I'otlw:l'S through rapid dilt:lioll of til\' vapor with eool air.
I ht' J 01 gasl'S. i\S 1I1;xi1lg Hnd ,'oolillg tJt't'urs, tilt' slltul'att'll VUpol'

b a "hamlwr l'tJlltaillill/! Ill,· liqllid to 1)1' t'(llltit'llS,'S, For oil ;,lIlukt's, II "t'l'Y rapid ,·"a~1l1a-
\i\"l.Irizt'd illld tlispt'rs('d, alld 1 :iJd \)I""\lI'S for It YI'I'Y short IH·riod "I' till\(' l'll11Sing

t· a high \'l,ltwity Yaptlri!.l'I· tlillt' ill th(' furlll (lj II],' I,itl'ti,·lt·" tu groll', llillltioJl. hOWt'\"'.\ ut'l'llrS so
11 yt'lllul'i, rapidly tl:al tll,' t'uagl!latiul\ i~ dlt,('kpd dh'l' u few

7-17
AMCP 706·185

d, Supply the carrier gas to remove the oil


VAPOR GAS EXIT vapor,

'c= Ammonium nitrate-charlloal compositions have


proved to be a satisfactory fuel block for the
volatilization of fog oil.
'l'he reaction bet.wren ammonium nitrate and
carbon can he written:

if it is assumed that all the carbon is oxidized to


AGENT carbon monoxide. If all the earbon is assumed to
1)(' oxidized to carbon dioxide the reaction is:

AGENT
FEED HOLE 'l'he volume of gas, measured at O°C and 760 mm

"¥fi~~
\ C .,......TrR
.....c.....~L WIRE
Hg, is about 0,97 liter per gram of mixture for the
first reaction and 0.92 liter per gram for the second
reaction.
~--------~F~U~E~L~______
~------.-~---;
Analysis of the gases produced by the burning
of a typical ammonium nitrate fuel block (11
parts charcoal, 3 parts linseed oil, and 83 parts
Figure 7·3. Typical Venturi Thermal Gel/erator ammonium nitrate) gave the following:
48.8% 13.5%
thousandths· of a s('colld, and a rl'nul.l'kably nur·
0.6% 5.2%
row rang(' of partich' sizl's results. If the generator
26.1% 5.8%
is working well, it i~; possible to obtam a reugh
('h('( k Oil the parti(·lp·sizl' rang'(' by a simple color \\ hi<'h correspollds, approximately, to the reaction:
t('st. If t hI' slln's dist' or allY other bright light
SOllr('l', W)lPll almost obsl'ul'('(l, appears re~l, the
tiNH 4 N0 3 .+. 4C ~l1H20 + CO + aco ll

purtiel(' sizl' is sOIlH'what smaller than d('sir<,d; if


-+- tiN~ + II:.!
it lIppt'ars IIlHgt'llta, ttH' Jlur-tiel\' siZt' is satiNfae· As illllstniit'd ill Chaptt'r ;{, this l'('aetioll should
tory; if it apJw!lrs hllll', tilt' particl!' sill' is yit'lrl l\(,lIrly Oll( litt'r of gas, measured at O°C and
larg!'I' thall dt,;.;ir'!'d f(;)' maxilllllll' ,wl'PP'lillg dfe(:. 7f;0 mill Ilg, Il('r g:null of mixturl' burned, Ap·
li\'t'IIt'ss. If tll(' slllol{(' Pl'otil1!'t'(l is llot of a uniform proxillllltt'iy (Ui>,;; kl'/llori('s pl'r gram of mixture is
partil'l(' siz(', j ht' SIIIl'S dis(' will IlpJlt'llr whitt' aud ('\,ol\'(,t! wlwll tllt' mixtnl't' is burllt'd.
110 i'()I)(,ltlsioll ('1111 h(' drawl\ as to parti,'h~ ';izl' be· }<'\l(.J bloeks niH bt' !lrl'sst·d using II binder, or
illg' i1l'o(lilt'pd by tht' gl'llt·ratol's. thl'Y ('1111 Li' ('/1St. III ('it/wI' ('lise, thl' burning rate,
whi\,1t dt'tl'rmill('s tIll' Iwat and gas evolut.ion raws,
is I'oll~hly Pl'(lpol'tiOlllll to tll!' urea of thl' burning
7·3.3,1.1.2 Fuel Blocks4 • 1H
sllrfal'l'. 1"01' 1\ fixed burJlillg III ('a, tl~t' rate of
The heat lind product gases produccd by the
hlll'llilll! i'lIll be ,'hllllgt'd by:
burning of 1\ JlYI'ott'('hnif' fuel bloek tnm:t:
it.VaI',villl! th,' siz(' of th\' ('hurl'oal.
II, HllitH' t Itt' tl'lllperature of tht· oil to the h. :'lodifyilll! lilt' slIl'fllt,t' of tllt' I'hal'l'oal, and/
vnporimt iOIl t!'lupcl'llture. \)1"
h. Ruppiy tIlt' lat"1l1 heat of ('vaporhtiOlI to tllt' ,', ('halll!iug' t h,' ('ompw,itiull of till' fUt'1 bloek.
oil.
\'. Supply th\, }It'a~ Inst as sensiblt' heat ill tht' ('urDoll i~ JllJ!'llIally tht' It'/ist,ullif,lrlll ingrl'(l·
hot )!IlSt's anti hot l'olltlliw'r. ii'lI! all.I, tlll'l'\'1'o/'t', "!lUSt'S lIloSt of th,' \'arilltiOIl

71 i'i
,-------------------------------------------------------------------- - ----- -----

AMCP 706-185

TABLE 7-2
CHARACTERISTICS OF TYPICAL OIL SMOKE POTS

rharacteristic l' !Jpe Devic('

Floa.ting (Fig. 7-3) Training (Fig. 7-4)

Size, in. ]:3 high by 1:3 dia. 5.7 high (including


fuze) by 2.5 dia.
l'(,1!tllri Onlicc
/)iameter, in. (l.0890 0.076
H' eight, lb I·U) (oil) 0.24 (oil)
12.0 (fuel) 0,22 (fuel)
() it :lund S{-}P No.1 or 2 SGF' Xo, 1 or 2
Fuel Brock Composition Fast-BlI rnillg Top Jlli.rt1lrc
8()~{ NH 4 N0 3 H2% NH 4N0 3
11 ';{, Charcoal 11 % Charcoal
;~y, IJinseed Oil -1% KNOa
;~% TJinseed Oil
.'-IloII'-Burl/ill!7 Basl~ Mixture
K2~!(, ~I:l4~()3

H% NB 4 CI
'i~) ('hareoal
:1% IJillsl'ed Oil
1!l1I /t il) II BOl1choll fllz\, (:\1208) BOll('hOI\ fnz!' (l\T20lAl)
"spits" through (similal' to
wutnri igniting floating' tYIW)
quiekmatdl & start!.'r
UIII'I'/II!! Tilll I' , mill 12 ± 1,5 1,2 :::±: 0,25
.1 Pillil'otio" SCI'l't'llillg', llsrd singly Urt'lI1HiP type,
01' ill Illlllt ipl!' Oil t1st'd for trainilll!
land 01' water pili' JlOses
()IISC/I"ill!! /'OWIT Sing-It· pot 1iIl~
a 1:~.O\l() l'll ft
1'''0111 allti lolally
'1I'sl'ul','S objt·,·ts
I-ti ft','1 away

111 1)[ll'lIill~ 1',,1' stlJlPo,t,dly id"lIlit'al fllt'l 1d,'t·\0;, \\'ith ,'hal't'DIII. .)11 th,' IIth,'1' halld, IIddiug' Hill
Tn'allll"II! of Ill" ,'al'lHlII with ,'h"lliit'lds (slidl as 1Il"lIillli' dIIOl'id,' Il/' Sllb,tillilillg' IIHphtirnlnlt' (01'
potus,sillHI ,·/Il'hOllUI.· ,.1' silililal' alkali dlt'lll!(,IlI!'.) . ,tal',')1 ill a ,'/lsI I'll"! hltH'k I fo/' l'lIHI't'(l1tl will I'l.'-

III,'I"'<I,,'S th,· IlIlrllillg !'a/" ",'hil" t 1"'/1/1111'111 witll dill'" th,' hUl'lIillg' I'alt',
Itll ilt'id will d",·n'It,.,,· tIll' hlll'llilll! rail', TIlt' suh- ,\11 illl'l"'lI'" il! ,·jlll,'!' 1111' illiliul 1,·lIlllt'rallll't·
,lilllli"l1 "I' l'"tassillill lIilJ'Il!t', ,.;odillill lIitl'lIl,', 01' III' tIlt' jll'l'SSIII'" ill Ih,' 1'\11,1 hlo"" "llIl/llh"I' will Hlso
HII111I(;',illl:! <"Id(l/'III.' fill' part of III!' allllllllllillill illt'I"'ilS" tIlt' hlll'l,illg' I'll!" ~111'!:ill!: (II rapid bllr:l-
lIill'at" will "1l11S" all ilj('I"'HS" ill hlll'ni,,!: I'lltt·, A lUg' with H high I'll!,· of KIIS "\'tdlltioll t'.dlowt·t! by
1"'It'''llabl., .'xplllllatll'll 1'(11' th,' ill!'!','II";t· is Ihat ,,/0\\1'1' hlll'l,illg' will, a lo\\' I'II!t' of gas ,';'ollltiull) is
th"st' "tllIlJIt'lIll1ls fol'lll "I!l'hollat"s \\ Iit'll bUl'lIt·.! ~1I11ll'! i III"S oh~"I'\"'d Th i~ IIhj"t'l ionahl,· ('Yl'lil' bl'-

7-19
AMCP 706-185

OIL VENTURI
VAPORIZER
figure 7-4. Typical Oil Smoke Pot (Floating)
/'"
/
havior is pl'obably due to variatiOl;s in the charcoal
Ilst'd inasmuch as surging is favored when a blend
of slow- and fast-hurning charcoal is used to
make thr flu'l block.
Recaust' charcoal may cause undesirable varia-
t.ions in the burning l'haraderistics of a fuel block,
attempt" have brrll madt' to develop a fuel block
FUEL
which does not cOlltai!! eharcoal. A mixture of
g'uanidirlt' lIitratl" ammonium Illtrate, linseed oil,
IUHf IImmollnilllll dil'hromate WHS found to bp only
part.ially satist'aetoI'Y. Hrasonablt- SUCCt'SS was ob·
tained using polysnlfidt' ammonium perchlorate
as a hilldt'r' allil a suh"t.itutt' for all or part of tllt' Figure 7-5. Typica.l Oil SMoke Pot (Training)
('arbon ill 1\ ('Ilstabll' I'm'l blul'k, This reduced or
1'lilllinaft>,1 tIll' SWt,lIillg lind ('I'Il('killg observ('(l in pots similar ttl those \hwd in orulIg'{' groves in the
standard 1lllll11OIliuIIl lIitratt' I'arboll fu('l blocks. lfllijt'tl Statl's, /llld tht- HIlSll'l' gl'!ll'ratol' developed
alltl l\sl'd by tIll' British ill til(' Battle of Britain.
7-3.3.1.1.3 Typical Venturi Thennai Generators Iii 1111 "/lSI'S, t hI' SlIlt)kt' PI'o(itl('l'Cl wus brownish-
('har'lIdt'ristil'S of lypi(,111 vt'lIturi·tYPI' thl'rmal g'rll)' til blll('k itt ,'ulur bt't:ltllS(' till' 0;1 'NUS partially
gt'llt'ratorsal'l' gil'l'lI ill 'l'abll' 7·'.!.. l<'igul'l's 7-4 !llld dl'I'OIll}lost'd I hilS yit·ldillg' frt·!' ea!'lJOlI. III gene:ral,
7·;' illustrate s,'hl'llllllil'ally two typt'S of oil frd th" SlIIukt, pl'lldll,'Ni had poor sl~rN'l1illg propertil'~'
SlilOkl' pots. ami lilllilt'd Jll'r.sist I'll ('{'.
Two oil lillltJkt' gt'lh'nd.or mixp:-> which wert'
7-3,3.1.2 Other Methods t'or Producing Oil Smoke J'I'lI>illllllhly ~;lIti,.;fad(Jry w,'!'!' ,\t'wlo[lt'd during
HI,fllrt· lilt., dl'\'I'!O]llllt'll! of Iht, \11 smok!' ~t'll­ \\'01'1,1 \\'111' II. Thl' lir:.! was it 1IlIXt.l,i'" of saw-
ITalor. Illdhuds fiJI' prot/Hl·jllg' ni!·blHwd
,'DIlIIJIIIIl ,iust alld 1'i:1l 1'1'/111 I imprt'g'lIl1tl'd I\ith II soilltiull of
thl' J't'dul'lioll lIf air supply
SlIlllk!' ";1'rl','lIs ill..tlldl'd plltassilllll I'hlUl'II\t' hilt! l\ 1 ig-h bllilill~ POil,t oil
to t.hl' hoikr,.; ,)f lIaval ships, Ih,' IISI' ,d' slIllltlgl' '. Diul) willdl had bl't'll jt'lit'li by tht' addition of

7-20
AMCP 706·185

a small pel'{~entage of soap. '1'he other mixture smoke is formed. Phosphorus penloxide and phos-
cOllsisted of jellied oil and black powdtr. Tn each pho.!":,c acid art' not toxic in small concentrations,
car>e, the ideal mixturr was one in which aJl of the although they may be irritating to the eyes, res·
fuel bllt none of the oil was oxidized, and in which piratory traet, and skin. Phosphorus smokes have
the amount of heat produced was sufficient to relatively little effect on metals.
vaporize all of the oil. '1'he smoke exit orifice was
important in controHi::1g t!1c flaming tendency of 7·3.3.2.1 White Phosphorus
t;J.e Inixture, tlw particle size cf the smoke pro. White phosphorm; is widely used in bursting·
duced, and the pressure within the smoke pot. type munitions to produce smoke screens for
Considerable eifort 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 hellt in exhaust gases from vehicle and air· white phosphorus, produced and spr.ead by an
crfie engin!?s 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 bUl'ns which art' slow to heal, it is an excellent
scre~ning purposes but was adequate for signa.l-
harassing agent.
illg. In an attempt to increase the amount of White phosphorus is the most efficient smoke
smoke produced, til!' exhaust gases were h~rned in producer on a weight basis; however, the screen·
an aftrruurner, thl'reby increasing their tc..npera- ing effectiveness of white phosphorus in bursting-
t mes and heat content. 'With this modification, type munitions is slight. Most of the charge burns
sati!;faetory slUoke ~creens were produced by air- within seconds following the burst, resulting in a
l~raft using intrrual combustion ('ngin('s.
smoke concentration llIany times that required for
7·3.3.2 Phos}Jhorus Smokes t~ff('etive screening. In addition, the temperatll:'e

White sllIokr ('ollsisting of small droplets of rise 1Il the cloud immediately surrounding the
phosphorie aei<l haw' been wid2ly used for mili- bU:'st is suffieient to produee a strong thermal up·
tary purposrs. 'l'hcs(~ droplets result from the :lraft 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 :or sigruding purposes but generRlly reduces
l'ompounds in th(' air, and the water vapor in the the ,·ifectiveness of white phosphorus as a screen-
air, or: ing smoke.
Two general ways to improve smOke-producing
+
P4 502 -~ 2Pa0 5
rffieiency are possible. The first involves reduction
P205+ 3H 2 0 ~ 2H aP0 4
of the heat of combnsti')n, which can be accom-
+
H aP0 4 nH 2 0 ~ H SP0 4 (dilute)
plished only by using different phosphorus com·
Till' <'onecntration of phosphoric a('id in the drop- pounds. The second method, which is more attrac-
lets is rh.. tprmined by tlll' relativp humidity. Meth-
tivc, involves eon trolling the rate of combustion
ods whi('h have bt'ell used to form phosphorus pent- by rl'ducillg the fragmentation of the phosphorus.
oxide for military srnokt's utili..ing phosphorus in- Several methods for eOlltrolling the fragmentation
('huh' :
of' phosphorus h·~ve beelJ tried, including the addi·
It. burning in air of whit!· phosphorus (which tion of ll}('chanical reinforcement such as steel
is spontaneously flammable), woo1,10 asbrstm;, plastic tubes, wire screens, and
h. burning' ill air of tIw phosphorus vapor (pro- oj hpr deviees, (·/tusing cjedion of the phosphorus
dlll'ell by the (~va:)oratioll of red phosphorus in pieeps of pr(>lleterminrd size. Other mllthods
in a furl-oxidant mixture), and attpJllpted invol\'(' the alteration of the physical
t', burning in air of phosphint' (produced by prop£'rties of phosphorus so as to prodUCE: a plas·
the ad ion of It Jllt'tal phosphide with water). ti(~ Illass with low shatt(~l'ing eharacteristics.
Phosphorll," vapor is I'xtren1('ly toxic' and causes Plasti('iz£'d white phosphorus,20 PWP, was
bOI!!' liPl·It/"; howpver, it is not pres('nt after the fouud to be the most promising develOpment for

7·21
AMCP 706-185
This page is reproduced at the
back of the report by Il different

.~
reproduction method to provide
better detail. aOCaS04 + 191\ --. 6Ca(POs h + 12Ca2P207
+ lOP~Ss
The h"at "-oduced by this reaction vaporizes the
.t!mailling red phosphorus contained in the smoke
mixture. Thl' phosphorus vapor burns on contact
~ '. - to
with air-. Some sulphur dioxide is formed when
the P 18:1, produced in the above reaction, burns
along with th~! phosphorus vapor:
+ 80 + 2P201S
'~)f1(JK['
P 4S3 2 ---~ 3802
111 the presence of moisture, there is a tendency
.\'~ P.· '
illlRsTu-in r:(l'r .
for 1'('1\ phosphorus to slowly oxidize due to the
presence of small quantities of copper and iron.
_"iiiIIl!f Thil'l may result in ignition diFeulty and an over-
~
.. . ' - ..
all decreased perforruanee of the smoke item.
• '" 4
Stable I'd phosplwtUS has been produced by de·
creasing or eliminating these, impurities. 21 ,22,2S
..
~i. .
7-3.3.2.3 Metal Phosphides
Metal phosphides, esp~cially calcium phosphide,
which was first produced commerci'll1y in 1920,
Figure 7-6. Typical WP-filled Device (M15 WP Smoke have been l.:sed. in sea markers. In these markers
Hand Grenade) the metal ptosphide :reacts with water to form
phosphine, which then burns in air to produce
control of the fragmentation of phosphorus and phosphorus pentoxirle and wat.er. For calcium
pillaring of the slUoke. This consists of an intimate phosphide:
mixture of granulated white phosphorus in a vis-
COUf> rubber solutioll. The; material burns more CaaP:! + 6H 0 ~ 3Ca(OHh + 2PHs
2

slowly and the particles do not disintegrate by 2PH 3 + 40 ~ P 0 + 3H 0


2 2 11 2

melting. As a result, pillaring is reduced and the Thl! rate of reaction is governed by the access of
effective s<-oreening time is greatly prolongeil. Test thl! water and by the baek pressure of the gas
results have indieated that plasticized white phos- produel'd. Calcium phosphide has been the most
phorus produces distinctly better smoke screens satisfactury for this purpuse. Aluminum ph06-
than similar phosphorus-filled rounds. The auti- phid:~ is difficult to react and is slow-burning,
personnel incf'ud:ary action of PWP 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
Phosphor as Containi.ng Phosphorus
Red phosphorus, the eomparative~y inert aHo- Other methods for producing phosphorus-con.
tropie form of phosphorus, is used in burning-type taining smokes include:
munitions mainly for signaling purposes. Compo- a. The dispersion of phosphorus in a solven\;
sitions '~()J}sistill~ of red phosphorus and certain such as carbon tetrachloride or carbon di.
oxidants or fncl>; an relatively slow-burning ar!d sulfide. The solvent evaporates and the fine-
are sometimes used in sea markert:. The chemical ly divided phosphorus burns in the available
reactions may be (Iuite involved. Fo ... example, the oxygen and produces a druse white smoke.
main reaetiull for a burning mixture of calcium b. 'l'he rI,ftctioll of phosphorus trichloride with
sulfate awl red phosphorus appf'ars to be: ba.ses sllch as ammonia and amines. The

7-22
,----------------------------~-------~----

AMCP 706·185

0.33 LB. STABILIZED RED PHOSPHORUS 1M EACH


OF TWO ALUMINUM SUPf'LEMEN'fARY CHARGE
CON·r,.INERS. TOTAL SMOKE CHARGE: 0.66 LB.

figute 7-7. Typical Red Pho$phorus-Filled Device

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


followillg' l's,lIuple: The characteristics of typieal smoke-producing
d('vicf's contai!ling phosphorus are summarized in
PCb + XU: -.~ P( ~bNH2 + HCI
1
Tahle 7-3. Illustrations of such devices are shown
PC1~ );H~ + ~HJ--O> PCI(~H:d2 + HOI in I<'i~ures 7·(j and 7-7.
PCI("'H2>~ + NlIa~ P(NH2).~ + HOI
lH ~I + NH3 --) NH Cl 4
7-3.3.3 Metal Chloride Smokes
Tht' SlllOkl' is composrd of a mixture of A iarg(' IIllmber of metal chlorides have been
<lllIillopitolphorus chlorides aIlll NH 4CI; the IIs\,d to produce white smoke. All of the metal
slIIokp produ('pd is I~ollsiderecl irritating but chlori(lps react with water to varying degrees and
llot tuxi(,; phosphorlls trichloride is not ex-
t his charaeteristi(~ dpt ermin(,s, to a large ext.cnt,
('('ssin'ly (~ol'ros.iv!' to allY llll'tal affeded by t1\('il' l'flicieney as smok(' agents, While th(- methods
hydJll(whloril' acid; ('ither wet or dry it is by whieh they are disseminated depend on the
'Illite ('ol'rosiw to flesh. partiC'ulal' metal ehloride, OH(,C disseminated the
". 'fIll' displ'l'sioll of phosphorus sulfides in Illetal chloride reacts with the watcr vapor in air
,'arhon bisllltidl'. The sol\'('lIt (waporates and resulting ill ihe formation of hydraterl oxides, or
th(, tin('l~' tiivid('d particles of phosphorus Ilydroxicips and hydrochloric acid.
'iulfid,' hurn readily ;1j air; total combustion
of th('s(' sulfides yi!'lds phoRphol'ns p!'ntoxiue
7-3.3,3,1 Liquid Metal Chlorides
lind sulphlir dioxide:
The liquid metal chlorides can be disseminated
1'48;1 + bU~ --0> 2P20r. + :jS02 by thermal vaporization followed by cond!'nsation,
21'~S;, + 150 2 -~ 2P~Oi; + 1080 2 or by atomization, FM, a commercial fDrm of
Both produeis react with water to produce titallium t!'traehloriill', has probably becn the mDst
slIlf:II'OW; ac-it! an<l phosphorie acid; the wid('I," llsed li(l'li<1 metal ehloride smoke agenL
slIlfhlps of phosphorus ar(' harmleRs to both
metals al)(l Hf'sh. 'rile smoke prO'll1('('d is also 7-3.3.3.1.1 FM Smokes
l't,lati\'('ly hal'mlt's:, to mdals itud pprRonllci F~I SllIok(, a~ellt, 'riCa., i~ extremely reactive
lIlllIl'r nOl'mal ('oJl(litiolls; howe\,!'I', pro- r\'sulting ill the formation of hydrated oxides, (r
1()\I~ed ('XpOSUl'l' to high eoneentrations wit it atmospht'ril' moisture alld, when Ilscd for
,,/ion hl 1)(' avoiul·(l. s(~n'(,lIiJlg, is oftl'n dissl'milJatpd from aircraft

7-23
AMCP 706·185

TABLE 7·3
CHARACTERISTICS OF TYPICAL DEVICES USING
PHOSPHORUS FILLING

() h(~ract eristic Device

WP Smokc Ha.nd Projectile


Grenade (M15) (T91 HE Water Ma.rker)
Size, in. 41;2 high 12% long
2% dia. 1% dia.
()harge U; 07. PWP 2.6 lb Comp B.
Weight 0.66 Ib Stabilized
Red Phosphorus
Ign-ition M206Al fuze M500A1 fuze
HE bur!1ter Compo B
Screening S~atters WP Explodes on
Oapability over a 20 yd impact-50 ft
radius high; 50 ft dia;
cloud duration
3 min---25 mph wind
Application 'l'hrown, bursting Used in 90 mm
charge explodes, munition
4-5 sec delay. (white marker)

spray tanks.24 Its reaction with water yapor is when dissolv!>d in dichloroethane and similar ma-
relatively complcx. First, the titanium tetrachlo- terials. The solvent evaporates and ~he titanium
ride is hydrated. This reaction is followed by tetrachloride reacts with the water vapor in the
further hydrolysis yielding, finally, titanium hy- air to produce smokt'.
droxide and hydrochloric acid. The smoke consists
of a mixturc of fin? particles of solid titanium hy-
droxidc, Ti (OIl) 4; the hydrated oxide, Ti0 2 •
7·3.3.3.1.2 Silicon Tetrachloride
H 2 0; intermediatt' hydroxychlorides of titanium; Silicon tetraehloride is another liquid metal
and dilutc HCI droplcts. The sequence of reaction chloride which has been used to produce smoke.
is: Silicon tetrachloridc is, howe vcr, less re'lctiv~ than
titanium tetrachloride and, unless considerable
TiCl., + fiH 2 0 - 4 'riCl 4 ·5H2 0 moistlll'c is present, little smoke is produced. The
TiCl 4 • 5JI:!O --~ TiCI:,(OH) . 4H 2 0 +
HCl. smoke particles produced from tha l"eaetion of sili-
TiCl:!(OIl) . 4II 2 0 -_.-) 'riCh(OHh . 3H2 0 con tetrachloride with watcr vapor are dilute hy-
+
HOI drochloride acid droplets and hydrated silicon
'l'iCI 2 (OHh . aII2()--~ Ti(OH)4' H 2 0
oxide. 'rhe teaction between silicon tetrachloride
+
2HCI and water ,'apor is similar to that for titanium
fJi')uid FM is excessiwly corrosive to metal if trtraehloride.
moisture is prt'sent. With nnisturc, FM forms a Silieon tetraehloride is less corrosive to meta1s
solid, gummy deposit that clogs equipment. .d.. 0.2 than titanium tctra(!hloride. If dry, it can be
perl~cnt phosphorus.mlution in CS z and CCI 4 , storcd in aluminum or steel containers. With
added to the FM, allcviates this problem. moisture, sili('on tetrachloride forn;s It. b'llmmy
'l'italli II III tetrachloride can also bf' disseminated (ieposit which clogs equipment. Flesh blll'IlS f::-om

7-24
AMCP 706-185

silicon tetrachloriue are similar to hydrochloric gnhr. The last two ingredients served to absorb
acid burns. the carbon i.:ltrachloridc and to slow down the rIlte
of rel-'ction. .As tbe smoke produced contabed
7-3.3.3.1.3 St.'innic Chloride some carbon in addition to the zinc chloride, it was
Stannic chloride will prod ace a good smoke somewhat gray in color. An American improve-
(rom rcll1.tively small amounts of rr.aterial. The ment, thf' addition of an oxidizing agent, resulted
11\ a whiter bmoke. Othet· changes were made lead-
reactions of stannie chloride with water vapor
J.re similar to thost' of titanium tetradtlorid". The ing to the development of the smoke mixture,
Rmoke is eomposed of HCI droplets and a mixture available at the start of World Wfl.r II, known in
of four shnnic hydroxy chlorides. L1 the presence the United States as HC. 'l'~is mixt.ure contained
of moisture tney arc nearly as corrosive as titan- hpxachlol'oethane as the chlorinating agent, zinc as
ium tetrachloricle. A gummy d<3posit on metals dIP fuel, a perchlorate as an oxidizing agent, and
is formed by stannic ehiOl'ide w~len moisture is ammonium chloride as a retard~r. The British
present. 'fhp smo\;.p is corrosive to anything af- hud a sim.ilar mixture containing bexachloroethane,
fected by hyd:rochloi.·ic acid. Stann ic chloridE; pro- zinc oxide, and calcium smcidc as a leducing agent.
(hH'es burns similar tll strong acid curns. Since neither of these mixtu.res 'Vas completely
satisfactory early in World Wa~ II, the Britisn
mixtuTi' was modified h:v replacing the reducing
7-3,:;.3.2 Solid M'}tai Chlo~ides
agent, calcium silicide, with alumin~u'..
Solid mptal chlorides are normally dis~'~lliinated
by thermal vaporization followed by condensation.
In mo,;;t ca~;es, the energy required to vaporize these 7-3.3.3.2.2 Chemistry of HC Smoke Kixturesll5 •26
agent~ is provid0d by a pyrotechnic heat source. The basic reaction between a completely chlori-
Thc hy<h olyses rpactions for the metal chlori.des nated carbon compound and metallic zinc can be
which have been used as smoke agents are: represented by the reaction:

CuCl 2 + 2H 2 0 .~ Cu (OR) 2 + 2RCl CxCly + y /2Zn ~ xC + y /2ZnC12


~"'eCI2 -r 2H 0 ~ Fe(OH)2 + '>.HCI
2 Thie reaction is highly exothermic with the evolu-
FeCl a + 8H',!O Fe(OH)s + 3HCl
-i>
tion of 165.3 kilogram-calories or 581 gram-calories
AICI a + 3H 0 -~ Al(OH)a + 3HCI
2 per gram of mixture if carbon tetrachloride is
ZnCl z + 2E 0 ~ Zn(OHh + 2HCl
2
used, and 244.6 kilogram-calories or 565 gra.m-
CdCI + 2H~O __ Cd(OHh + 2HCl
2 calories per gram vI mixture if hexachloroethalle
HgCl + 2H 0 -~ HgO . H 0 + 2RCI
2 2 2 i& used as the chlorinating agent. If zinc oxide is
3nCl2 + 2II 2 0 -.~ Sn(OH)2 + 2HCI added, the mixture will burn more slowly. The
smoke produced \1'1 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+Zn
solid :netal chlorides used as a smoke ageut. Al-
though toxic, zinc chloride produced as the result which remOves the carbon from the smoke. The
of a pyrotf'ehJlit' reaetiolJ. is widely used for screen- zinc produced by this reactiun then reacts with
iJlg and signaling pttrposesY I nasmuch as hydro- additional amounts of the chlorinating agent. .A2,
ehlorie aLid is produced by the reaction between the reaction between zinc oxide and carbon is
zinl' lhloridp and water valJOr ill air, UlP smoke is endothermic, ear1r attempts to use zinc oxide in
irritating to })f'l"sonnel 'llld will react with any He-type smokes .vere only partially successful
materials afi'el'ted hy hydrochloric acid. since the temperature reached was not high enough
The French, during World War I, were the first to cause complete :reduction of the zinc oxide.
to produef' a smoke mixturi' of this type. The mix- .As the result of modifications made during the
ture known as the Berger mixtufP consisted of early part of WorlJ War II, He smok.) :mixtures
zinc, c8.rbon tetrachloride, zinc oxide, and k.iesel- --as nl)rmally compounded for sereening yurposes

7-25
AMCP 7()6..185

- -uow consist of. approxiraa~dy equal amounts by ThE amount of aluminum in the foregoing reac·
weight of zinc oxide and a chlorinating agent 3uch tion ca~ vftry from 3.6 to 10." percent by weight.
as hexachloroethane or carbon tetrachloride, and 3. With the lowc! aluminum content, only carbon
few percent (\£ aluminum. The reactioI'. might pro- monoxide ifl formed; and, as the aluminum con-
ce~d through the following stflPS, when hexachloro- tent ifl in(,l'eased, free carbon begins> to appcar
ethan.e is the chlorinating flg-ent ; along with the ('arbon monoxide until at the
2Al +
O-lOla -.-~ 2AlCIa 20 + upper limit ali the carbon is in the form of smoke.
If less than 3.6 percent of alumim1 ffi is used, both
This reaction is exothermic, libcrating around 280
earbon dioxidc and ca'I'bon monoxide are produced;
kilogram-calories of energy. The aluminum chloride
and, U8 the p{'rcentagc of aluminum is still further
formed then reacts with the zinc oxide:
l'C'ducc'.1, tllp ratio of carbon dioxide to carbon
2AlCla +
3ZnO ~ 3ZnCl 2 Al2 0 s + lllOlloxidt' inereast's The heat evolved varies from
This reaction is al;;o exothermic, libcrating 103 0 356 grum-ca!orit's per gram of a smoke mixtu:ce
kilogram-calori('s. The overall reaction obtained ('Olll!lillillg :3.6 IJel'cent of aluminum to 717 gram-
by combiuing' thc above reactiolls is: ealories per gram of mixture containing 10.1 per.
2Al+ C2 0l 6 +
3ZnO ~ 3ZnOh --l-AhOa 2C + cent aluminum (,ontent. If carbon tetrachloride is
This readioll is highly ('"«othermic, libcrating 383.5 tIlYed (Typr.E He mixture) illsten..l of the hexa-
kilogram-calories or 717 gram-calories per gram dllol'orthalH', tht> amount of aluminum for similar
of smokc mixture. A second r~action sequence rpuetiolls to take place ranges from 5.37 percent
\('ading to tIll' samp overall readion is possible. to 10.2 percent. The Variation in burning time
This sequence, which to somc im'estigators bE:tter with aluminulJl content, for mixturp containing
reprcsents thc actual (;om',,(' of thc reaetion, is; lwxachloroethane (Type-C HC mixture), is illus-
2Al + :~ZllO 3Z11 + A1 0
--'> 2 3
tl'ati'o by till' data pl'Psented ill Table 7-4.
:~Zll + C:!Cl n ~ 3ZnOl2 + 20
Both of thes(' rt'uctions are C'xt'thrrmic, the first TABLE 7-4
to the f!xtent of 1:16.6 kilogtam·ealories, and the V ARIATION OF BURNING TIME OF TYPE-C
second to the extent of 219.H kilogram-cal odes. HC SMOKE MIXTURE WITH
The overall l'!'aetioll with aluminum is similar to ALUMINUM CONTENT
the reaction:
(AN,·l\I8, He SMOKE GRENADE)
:ICaSh + 15ZlIO -+ fjC 2 CJ O ~ 15Zn012
Aillminum Cuntcnt, Burning Time,
+3CaO sec
%
+ 6Si0 2
+ 10C 9.0 55
for tltf' parlier smoke mixture cOlltaining ~alcium 8.4 64
silicirl(' as f hl' I'PflucilJg" agcnt. "'.0 65
'rhl' t'""tPl1t of the reaction betw('en zinc oxide 7.;; 71
and e«rhull ('an b,' varied b~' changing' the propor- 7.0 84
tion of aluminulIl ill the RInoke mixture. If the' 6.5 96
aluminum (~ontcllt ill the smoke mixture is re- 6.0 107
ducf'd, whil(> thr' pr()portiolls of hexachloroethane 5.5 147
and zille oxide· art' let'pt "ollstant, tht' amount of 5.5 200
free "arbon ill thp smok(' is I'edu(~ed. This results
ill It whiter smoke and also l'l'dUl'f'S"he burning Tlw character of the zinc oxide also has an in-
ratf'. Thp oVt'rall n'a(·tiolJ wh?l'f' no ('arbon is pro- fluence em the burning rate of the smoke mixture.
d llcl'(l is;
He smoke grenades which were loadd wi.th a
2A! -+ [IZnO + 3C 2 CI II -~ A hOa -+ 9ZnCl 2 smoke mixtul'l' containing 6.25 percent aluminum,
+ 6CO 46.9 percent hexachloroethane, and 46.9 perceni,

7-26
AMCP 706-185

zinc oxide were found to have a wide range of Impurities such as chlorides, sulfates Ilnd nitrates
burning times depending on the moibture, car- a('(~elerate
th(' reaetion.
bonate and sulfate content, and the particle size
of the zinc oxide used, Very fine and very coarse 7-3.3.3.3 Modified He Smokes28
zinc oxides form slower-burning 'mixtures than When a shortage of chlorine appeared imminent
those of intermediate size. Fast-burning smoke during World War II, attention was focused on
mixtures result when moderately large-sized pa.r- the possibility of developing inorganic chlorine
ticles of zinc oxide with a low moisture and car- carriers derived from hydrorhloric 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 chlorid!l smoke
of zinc oxide, or those having a high carbonate mixtures. The following reactions involving alu-
content, are usect A blend of a coarse and a fine minum, ft'rric ehloride, and zinc oxide are t.hought
zinc oxide results in a faster-burning mixture than to occur at high temperatures:
would be predicted from the burning time of the
indi vidual oxides.
2Al + 6FeCIa + 9ZnO ~ Al 0 a + 6FeO
2

The apparent density of the zinc oxide has no


+ 9ZnCl2
2AI + 2FeCh + 3ZnO --..+ Al 0 a + 2Fe
2
direct effect on the burning time of the Type-C He
smoke mixture containing zinc oxide, For Type-E
+ 3ZnCb
He smoke mixtures, the consistency of the filling '1'he heats of rea~tion 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 burniug of the mixture also decreases nature of ferrie chloride, compositions containing
as the relative density of the zinc oxide decreases. this ingredient are difficult to prepare in moist
If 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 KFeCl4 has
result, other means must be employed to further been proposed.
retard the burning rate. The substitution of basic In recent. work,29 hexachlorobenzene and
zinc carbonate for zinc oxide, in a q'Iantity not Dechlorane (perchloropentacyclodecane, C10 01 12 )
exceeding sewn percent of the zinc oxide, is one have heen used instead of the more volatile hexa-
method. The ,;toichiometric ratio of zinc to hexa- chloroethane. The smoh volume and burning
chloroethane, however, must be maintained. Other tim(' art' comparable to the normal HC composi-
retarders which lengther:. the burning time of tions; its stability during storage is better. No
the lIe smoke mixture include urea and Monostral significant difference in relative toxicity was found;
blne dye. Naphthalene was found to have a re- both smokes are toxic and product' degeneration of
tarding action on the fast-burning mixtures but tissues in the respiratory system 011 long exposure.
110 definite effed on the slow-burning mixtures. Plastic bonding agents SO Wf:re also successfully
~u('rost', Vinsol :resin, and anthracene were tried tried allowing the smoke compositions to be loaded
but were not satisfaetory. into ul1ui-lual-shaped eontainers. The filling and
lIe smoke mixtures are relatively stable ex- blt'nding operations have been improved with im-
eept whm there art' soluble chlorides in the ziIlc provement in uniformity of the mixtures. Storag,~
oxide or when water contacts the hexachloroethane. eharacteristics of plastic bonded white smoke muni-
Although til(' sl'qllcnce of events when water gains tions were also better, although corrosion has not
access to all IIC smoke mixture containing hexa- bet'll ('ornpletely rlimillated.
('hloroethan(' has not been established conclusively,
it is reportpd~7 that in the presencc of zinc dust 7·3.3,3.4 Zinc Hexachlorobenzene-PDtassium
and moisture C~Cltl is redueed and tetrachloro· Perchlorate System
ethylellP is onl' of the reaction products. Zinc Zinc hrxal' h 10robeIlzene-potassium perchlorate
dust is oxidizul to zinc oxide and zillc chloride. systems have been used in some cases for signaling

7-27
AMCF 7(.1'6·185

[,.,.',I",',!~i!,:,,;,I:;'x~:a;;liJl·i\'. ~ "

-
Figure 7·9. M5 HC Floating Smoke Pot

temperature above the transition point of potas-


sium perchlorate, reacts with the latter at the
boiling point of hexachlorobenzene, according to
reaction 2. The latter reaction, together with reac-
tion 1 to a limited extent, raises the system to 11
Figure 7-8. AN-M8 HC Smoke Hand Grenade temperature above 500°0. At temperatures above
the melting point of zinc (4]9°0), 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°0. Therefore,
three chemical rcactions 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
of this t.ernary system. 31 These reactions are: to thermal ignition.
1. 3Zn +OgUl6 -----+ 3ZnOb 60 +
2. 4C +
KOI0 4 -----+ KOl +
400 (and (0 2 ) 7-3.3.3.5 Typical Devices
3. 4Zn + KC10 4 ~ KGI +1ZnO Typical devices using He type smoke mixtures
'fhe agrcement between the measured and calcu- are shown in Figures 7-8 and 7-9. Details and
lated heats of eomGustion based on these reactions specificd tions 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 of hexachlorobenzene to Several white smokes are made up, at least
produee carbon. Carbon, which is produced at a in part, of droplets of dilute sulfuric acid result-

7-28
AlICP 706-185

TABLE 7-5
CHARACTERISTICS OF TYPICAL DEVICES USING HC MIXTURE

Chamctcristic Device

He Smoke Hand He Floating


Gt'enade (AN-MS) Smoke Pot (M4A2)
Size, in. 5.7 high 13 high
2.5 dia 12 dia
Four smoke emission Three vent
holes in top holes in top
Charge 19 oz Typc-C 23.5 to 27.5 lb
Wdght HC Mixture HC Mixture
Ignition M201Al fuze plus M207 Al fuze plus
ignition mix and first fire charge
starter mix and delay charge
Burning 105-150 sec 10-15 min
Time
Application Thro,"TI, 1.2-2 sec Screening
delay-may be
launched from
rifle or carbine for
screening 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, uEcause of the presence of chlorine comes in contact with the skin, sulfur trioxide
atoms in the original compound or mixture, dilute causes burns that heal slowly. If 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 (lor-
foniC' a('id and ~ulfur trioxide, which is used for rosive to anything affected by sulfuric acid.
screening, is probably the most important. Pro-
longed exposure to this type smoke can be in- 7-3.3.4.2 Oleum
jnriom; and should be avoided. Oll'ul1l is a solution of sulfur trioxide in sul-
furic acid. 'fhe agent is dispersed iu the same
7-3.3.4.1 Sufide Trioxide manner a~ sulfur trioxide. The sulfur trioxide
This agent is usually dispersed into the at- reacts with water vapor ill the air; the sulfuric
mosphere in fine particles either by mechanical acid tho;, formed and the sulfuric acid solvent ab-
atomization or thermal vaporization. The dis· sorb water to give smoke droplets of dilute sulfuric
persed sulfur trioxide combines with water vapor acid.
in the atmosphere, resulting in the formatif)l1 of
tiny droplets of sulfuric acid: 7 ·3.3.4.3 Chlorosulfonic Acid
This acid reacts with water similar to 80s.
SOa + IhO ---+ H 2 S0 4
Smokt is produced by uispersion of the aeid into
'rhe acid tht'u t.akes 011 more water vapor to pro- tlte atmosphere by mechallieal atomizatinll or
duce partieb, of diluted acid which constitute thl'l'mai vaporization. Whell tilt' di3persed acid
the smokp cloud. Dry sulfur trioxide does not mingles wit h waft-!" vapor, sulfuric a(·id and hydro-
attack metals at ordinary temperatures. At. red (,hIOl·ie lleid are produced:

7-29
AMep 706-185

HOlS0 3 + IhO ~ H S0 + HOI


2 4 7-3.3.5.1 Ammonium and AmiDe 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
sueh as HOI can be vaporized by heating. For
acid. The smoke produced, theref{lre, is eorrosive
ammoniUIlI chloride the reaction is:
to allY thing affected by sulfuric acid or hydro-
chbric acid and is irritating to the respiratory
~y!'item, eyes, and skin of exposed personnel.
On cooling, recombination occm:s. Amine salts,
such as aniline l".ydrochloride, mllY be used sim-
7-3.3AA Sulfuryl Chloride ilarly. Ammonium or amine salts n:we no effect on
Sulfuryl chloride is dispersed in the same man- metals when dry j however, the presence of water
ner as sulfur trioxide by mechanical atomization may reRult. in some ('orros-ion. These salts can be
or thermal vaporization. It reacts with water hand It'd 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 ilS corrosive to metal and flesh monia or amines to produce smoke. The base must
as is sulfuric aeid. Dry sulfuryl chloride is (lor- combine WIth the metal chloride just after dispel'-
rosive to those materials affected by sulfuric or ~i()n. Other bases such as hydrazine may be used
hydrochloric acid and will cause burns to the flesh in place of ammonia.
similar to those or sulfuric acid,
7-3.3.5.2.1 Hydrogen Chloride and Ammonia
7-3.3.4.5 FS Smoke The reaction of hydroJen chlorice with Itmmonia
FS smoke agent consists of a mixture of 45 per- is similar to the reaction of a metal chloride with
cent chlorosnlfonie acid 811d 55 percent sulfur ammonia. This two-gas system produces fine par-
trioxide, and is slightly more reactive with 'Vater ticles of solid ammonium chloride. The smoke
than FM smoke agent (Paragraph 7-3.3.3.1.1). formed is consideled very visible. Gaseous hydro-
Thc material can bl:' dispersed by mechanical gen chloride is not very corrosive to metal con-
atomization or thermal vaporization. For ploduc- tainers when dry; however, when moisture is pres-
ing smoke S('r(,£'118, it is often disseminated from ('nt, it is quite corrosive. Ammonium chloride
spray tallks earripd by aircraft. As the smoke smoke is not eorrosive to metals. Hydrogen chlo-
eonsist,; of droplets of dilute sulfuric and hydro. ride gas is very irri.tating I'.nd, in moderate quanti-
ehloril' arid, HI<' smoke is lwrrosive to anything ties, it is toxic. Ammonia gas is also toxic in mod-
affedrd by thesp compounds. Thp smoke is very erate qnantities; however, ammonium chloride
irritating to thl' nose and lungs and exposnre ,;moka is hannless.
should hi> avoided. If moisture is prcsent, FS
smoke ageut is ('xl'cssivply corrosivr, aud it will 7-3.3.5.2.2 Titanium Tetrachloride and Ammonia
('ause skin burns. The reaction between titanium tetrachloride
and ammcnia is somewhat c{)mplex. First, an am~
7-3.3.5 Smoke-Producing Reacti(>Qs Involving moniate is formed. This ammoniate is hydrolyzed
Ammonia or Amines by water vapor from the atmosphere. Ammonia
Mm;t of tIll' rt'adiolls dpsl~ribed ill this sub- reads with the hydrochloric acid gas reJeased dnr-
paragraph wprt' at one time UseLl to produce ing hydrolysis of TiCI. to give NH.Cl. Therefore,
scrPI'uillg ,;mokt'. POI' many rt'Rsons tllt'y are not the system withC.lt water vapor is less e:l'fectiv('.
prt'sclltly so used. Some of these systems do not The reactions for this prOl~ess are as follows:
rt'(JlIirp atlllosplwrt, "o:!~tituent:; (sueh as watt'r +
TiCI.j 4Nil3 ----+ TiCl. : 4NIIa
vapor) to 1H' Pifl'diyt' SmUKl' prodlH~t'rs and, thele- TiCI •. 4NlIa + 5H 2 0 ----+ Ti(OH) •. H 2 0
fore, may be lI&Cflll at high altitudes. + 4NH.Cl

7-30
AHCP 706-185

The smoke is a mixture ('If Ti(OH)4 . H 2 0, jnter- trioxide; other bases such as hydrazine, hydrox-
mediate hy(.~roxy chbrides of titanium, and am- ylamine, etc., probably could be substituted. The
monimr. chloride particles. basic reaction is as follows:

7-3.3.5.2.3 Silico!! Tetrachloride, Ammonia,


IWISO~ + 3NHs ~ S02(NH h 2 . NH"Cl
and Waror + H 20
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 silicoll tetrachloride is formed 7-3.3.5.3.3 Sulfuryl Chloride and Ammonia
while at the same time hydrolysis of the silicon Of Amines
tptrachloride occurs to give SiOl1 , 2II 2 0, and HCl; Sulfuryl chloride will react with bases such as
and finally, NH3 combines with the Hel to give ammonia and amines to give a better smoke than is
NII 4 Cl. The reaction sequence is: formed with water vapor. The fOllowing reactions
SiCl~ + 4NHa ~ SiCl 4NHa 4 •
are for sulfuryl chloride and ammonia:
SiCl 1 + 4H 0 --) Si0 ·2H 0 + 4HCl
2 2 2 S02Cb + 4NIIa ~ S02(NH b + 2NH Cl2 4
SiCl4 .4NH3 + <lH20·~ Si0 2H 0 2 • 2 2802 Cl 2+ 7NH3 ~ 4NH4Cl
+ 4NH4 Cl + NH (S02NH2 h
3S0 2 Cl 2 + 9NH~ ~ 6NH CI + (NH)a(S02)s
4

7-3.3.5.3 Sulfur Compounds and Ammonia The first reaction give~ sulfamide; t.he second,
amillosulfamidl' ; and the third, trisulfamide.
Sulfur compounds will also react with bases in-
Whether the smoke particles are those products
('luding ammonia and amines. 'fhese smoke-pro-
or further reaption products is 1I0t known.
thlCing sy&tems do not requirp atmospheric con-
stituents to form the smoke particles and, there-
fore, lllay be useful at high altitudes. 7-3.3.6 Sulfur Smokes
Sulfur smokes ~onsist of small particles of ele-
7-3.3.5.3.1 Sulfur Trioxide and Ammonia Ilwntal sulfur suspended in the air. Sulfur smokes
Of Amines l~aJl be prOdlH'rd by methods similar to those used
TIl(> smoke is formed by supplying a reactive for th(' productiou of oil smokes. In addition,
gas to sulfur trioxide at the timl' of dispersion. sulfur smokes can be made by intimately mixing
Ammonia and :uIlilles have proved successful, and sulfur and a suitable fuel. Mixtures which have
other basil' .'>Llbst anc('s, such as hydrazine, hy- lwen used include sulfur, sodium nitrate, and char-
(iroxylamill<.', etc., might bl' satisfactory. In the eoal; sulfur, potassium nitratE' and charcoal; and
('a~e uf sulfur trioxidl' alld ammonia, the reactions sulfur, ammonium nitrate, aud charcoal. The sul-
are: fur is present ill much larger quantities than in
SOJ + 2NlI:! _ S02(Nlh):: + H 2 0 blaek powder; the latent heat of vaporization and
SOa + NIIa~ HS0 NH z 3
fusion of tht' sulfur absorbs thp heat produced by
S03 t- 2NlI a _ NH 2 SOaNH4 nit' J't'action and, hence, s!')ws the burning rate.
Th(' burning rate for this type of mixture depends
All tlirt'P r('adiolls Ot'cur mon' or less simulta-
011 the pereelltage of sulfur.
Ilpollsly. As far as (~all bj~ determillt'd, the smoke
('ollsists of pu rtielt's of thl'se product&.
7-3.3.7 Orgaaic Metallic Compounds
7-3.3.5.3.2 Chlorosulfonic Acid and Ammorua Ct'rtuill orgllTlIl' Illt'tallil' ('ompoullds eaIl be usen
or Amines fur tht, protiudioll of slIloke. Thesl' ('olllpounds are
Am1llonia and til(' amines rl'lI('t readily witli rt'adi\'t' awl will burn spolltunl'ouflly ill moist air.
I iCIRO:! ill lIIueh th!' SUIlIt' manlier as w!th sulfur T1H' [WI! w'n"!' of rl'adion hpt W('('ll 1111 organic metal-

7··31
--------------------- ---------------------------------- ----------------------

AKCP 706-185

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


thermic reaction between the organic metallic com- TOTAL OBSCURING POWER OF
pound and water vapor, yielding a hydrocarbon WHITE SMOKES
and metal hydroxide; the heat of this reaetion re-
sults in the hydrocarbon's burning to form carbon ChemioaZ TOP, ft 2 /lb
dioy.ide and water. This reaction for dimethyl
White Phosphorus 4600
zinc is:
TiCl 4 + NHs 3030
(CHahZn +
2H 2 0 ~ 2CH 4 + Zn(OHh SOa 3000
CH 4+202 ~ CO 2 2H2 0 + FS 2550
In this case the white particles consist of solid HCI+ NHs 2500
zinc hydroxide particles. HC Mixture 2100
SiCl.I + NU a 1960
7-3.3.8 Comparison of White Smokes FM 1900
Oleum 1890
The total obscuring power, TOP,32 of a smoke
SnCl4 1860
is ob 1;ailled by mUltiplying the product of volume,
in cubic feet of smoke produced per pound of ma-
PCb + NH3 1600
terial, and the reciprocal of the smoke layer, in
+
PCl 3 NHs 1800

feet, necessary to obscure the filament of a 40-watt


+
HClSO a NH:i 1600
SiCl4 1500
Me.zda lamp. The TOP for some white smoke HCISO:J 1400
agents, at low altitudes where atmospherie con- BM ~lfixture 1400
sbtuents are plentifiul, is given in Table 7-6. Berger l~::'CtUl'e 1250
The so-called "standard smoke" is a smoke of
such a density that a 25.candlepower l-ight is .iust
FM +1,2-Dictliv:;-~pt.\}an(' 1235
Cl
S02 2 l~UU
invisible when observed through a layer 100 feet
thick. A comparison of some white gmoke agents at
Ch +NH3 750
AsCl a 460
low altitude, where atmospheric constituents are Type-S Mixture 460
plentiful, ill terms of the amount of smoke agent Crude Oil 200
required to produce 1000 cubie feet of standard
3moke, is given in Table 7-7.
All of the 'fOP and standard smoke measure-
ments were made at low altitude, where atmo-
spheric constitw~llts aVd.ilable for reaction with the TABLE 7-7
primary smoke particles were plentiful. The im- AMOUNT OF SMOKE AGENTS REQUIRED TO
portance of atmospht'rit' eonsiitncnts is illustrated PRODUCE 1,000 CUBIC FEET OF
ill Tabl!' 7-H wher(' the Humber of graIlls of smoke STANDARD SMOKE
formed pf'r gram of ~:moke agent w,ed is tabulated.
It is evident, for thl' agents compared, that WP Compound Amount Required, oz
yields the gn-atest weight of aqueolH; solution in -------_._-----
equilibrium with air at 7fi per('PH! relativc humidity Phosphorus 0.060
per unit-wl~ight of the sl1lok!' agf'ut. 'I'hl' ratio for 1<'M + NIls 0.090
fog oil is ullity (1.0) sill('(' tilt' fog oil is lIot hygrn- Sf):! 0.094
scopie alld only tlit' tll!Cllt is availablt, tl) fonn the Ii'S 0.110
smoke partidf-s. TIll' yahlL's do not tak\' into ac- He l\lixtllJ't' 0.120
('Olint illgn'dients whit'h rt:lllai'l : ~i.n(r as residues I~1M 0.150
or otherwisl' t'on/rilm!!' littll' ,: .. ~Ilt' obscuring' Uit'lllll O.I.!';}
power. 'I'hl' ubsoiut\· \,11111(';; will vary with till' ('rudt' Uil 2.000
rt'latlw hUlIlidity, but I'hal\ge \'('I'y Iittll' with air

7-32
AMCP 706·185 AMCP 706-185

TABLE 7·8 the requisite purity of color when disseminated


AMOlJNT OF SMOKE PRODUCED PER UNIT as a smoke. 'rhese properties are closely related
WEIGHT OF SMOKE AGENT AT to tIl(' ehemical constitution of the dye. No dye
75% RELATIVE HUMIDITY was ever sl)('cifically developed for smoke appli-
cation; only those available were considered and
Agent Amount tested. In an early investigation of the thermal
stabiJity and volatility of dyes, it was concluded
Fog Oil 1.0 (does not produce that dyef containing amino or substitated amino
aqueous solution) groups, but not sulfonic groups, were suitable for
Zinc Chloride 2.5 (water vapor absorbed) the production of colored ;:;mokes. These conclu-
Ferric Chloride 3.1 (water vapor absorbf)d) 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 eonstitutiollal characteristics which
render a dyestuff suitable for the production of
temperature at anyone vahe of the relative colored smoke were found to be as follows:
humidity. Also, the relative results are not Il. The molecular weight of the dye should pre-
changed. It is important to note that these measure" ferably be less than 400, but iL no case
ments chiefly concern the obscuring or screening greater than 450.
power of the smoke and no consideration is given b. The dye should be a member of one of the
to other factors which might be important for a following series: anthraquinone, azine, azo,
signal smoke, tracking aid, or tracking and ac· qninoline, xanthene, or anthrone.
quisition smoke. c. The following groups must be absent: sul-
fonic, hydrochloride, nitro, nitrose, quar-
7-3.4 COLORED SMOKES33 ternary ammonium, and oxonium.
Colored smoke~, like other ~mokes, can be pro. d. The following gruups may be present:
duced by four basie methods: amino and substituted amino, alkyl, aryl,
a. Dispersion of finely powdered, colored rna· chloro, bromo, hydroxy, and alkoxy.
terials e. The dye must not tend t() undergo auto-con-
b. Chemical reactions resulting in the forma· densation.
tion of eolored particles
Not all dyes whieh have the above characteristics
e. Detonation of an explosive, thereby scat·
will produee satisfadory colored smokes, but some
teri ug colored material, or
of the mlluy dyes which have been evaluated will
d. Volatizatioll and eond(-l1satioll of a eolored
product, "{'XCt,lil'nt" colOl'ed smoke clouds. Some
material.
of the more satisfactory dyes are listed in Tables
'rhe first two methods have been found to give 7-9 and 7-10.
slIlokt's of only small volume and dull eolor. The In g-elH'ral, the anthraquinone dyes have proved
last two methods, both of' whieh involve the vapori- to ht' sll}ll'rior to all otiwrs ill produeing colored
zation and ('olldrllsation of It l'olorrd material, have smok(' douds. 'Pitt' azo derivatives have furnished
bel'lI fOlllJ{i fpIlsiblt, ouly wl1l'1I volatilt' organie ollly It f('w f;uitablt' dyes, despite the fact that
dYl'S art' lH-wd It,; tilt' eolorillg' matt'rial. As It result, th!'y constitutt' tilt' largest class investigated. In
all ('olol't'd Slllokl' sigllals (t'XI'l'pt bllwk) ar(' based, 110 t'IISt' ha\'l' t hI' It.W dyes bet'll superior to the
at pn'st'lll, IIpOIl Ib, use of !Ill orgallit' dyt·. Itllthl"l1qllillOllt' tlyt's Till' undesirable qualities of
tilt' IlZO dyt's /II't' thl'il' tt·lldt·!lt'Y to flame and their
7-3.4.1 Dyesa4 trullSpUl't'lley. Amolll~ tht· IIzillt' dyrs, I"osindont' and
Sill\'p (·(,jured smokes illvolv(' vaporizlltio)l !Llld its tlt'rl\'ati VI'S ~d\'t' t·xl·pll('llt. bright smok t• douds
t'olltll'llsatioll, eOll'ititul'llt ,lyf's art· I"l'tjuirt'd to be without flawing, 1'ht'ir t·nlor rllllg!', however, is
tht·rlllully stahlt· alid fairly "t.!atil,·, IIlId to Jlosst's~) lilliitt'd to n'd allti UrllIIgt·_ This ("lass of dYl's otrCnl

'7·33
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -- - ---- - - - - --- - - - - ----

AMCP 706·185

TABLE 7·9
SOME DYES WHICH HAVE BEEN USED IN BURNING· TYPE
COLORED SMOKE MUNITIONS

Red Smoke: Dyc(s)

9-diethylamino-7 -phenyl-5-henw (a) phell3zinone.


Also known as 9-diethylamino rosindone
1-methylaminoanthraquillone
1- (2-methoxyphenylazo) -2-11aphthol
2-quinolyl-2-indandiolle-1,:3 (Rhodamine B) plus
1- (4-phenylazo) -2-naphthol
2-aminoan t hraqll i nOlle plus I-JllPthy laminoan thraquinolle
O-tolylal:()-o-tolylazo·~-Ilaphthol (Sudan IV); plus
2-quinolyl.2-indRudiolle-l,8 (Rhodamine B) ;
plus auramine hydrochloride
1- (tolylazoxylylazo) -2-naphthol

Green Smoke:
1,8-di-p-toi.uidinoullthraquinone
1,4-di-p-tol uidilloa n th raq ninone
1-methylamino-4-p-toluid inoan thraquinone plus
au~amille hyd!'oehloride
1,4-rli-p-toluidinoull thruq uinolle plus
dimethylaminoazobcnzelle
1,4-di-p-toluidil101tllthrll(!uillOlll:' pI us
am'amine hydroehluridt'
I,4-di-p-toluitlinoallthraquinolli' with quinophthalone
(quinoline yellow)
----------------_.
0l'an[lc Smoke:
I-ami IlOIl n th raq ui IIOlll'
1·amillo.8·(, hloroaJlth I'llq UillOllt' pIns q lIillizurin
1- ( 4-pht'lIY llizo ).~.lIa pl.t hoi
H, lO·d iallilinoa II t h rat't'llt' pIlls \lht hnlopprillultl'
1- ( 4· P h'llY luzu ) .:2.11111' htlwl plus !I .1O-dinl1i Iinoan thru('('IH'

()ra1lg(!-Rcd f:!mokt :
1- (4-lIitropbfJllylnw) .~llapl!thol
-----------
r ('/low s'rrwkc:
AUralnill!' hydrtll·hl,lridt·
1· (4·dimethylumiuophl'llyll!zu) .~- JlI!phtlio\
1-\ 1.phl'llylazul-:2-lllljlhtho! (~Ildan II plus l'itlH'r Illlrllmiut'
hytir(l('hluJ'idt' ur tjlllllophthlll<"llt' (qUiIlOlillt' yt'llu\l' I
~.'!': ·dimt't hy I· p- pht,lt,\' !aZ()1l11 ilillt'
AXCP 706·185

TABLE 7·9 (cont'd)

Blue Smoke: Dye(s)

I-hydroxy-4-p-toluidinoanthraquinonc
Indigo
l-amino-2-bromo-4 .. p-toluidilloallthraquinone
l-amino-2-methyl-4-p-toluidinoanthraquinone
(Alizarin Sapphire, Blue R. Base)
1,4-dimethylaminoan thraquinone
I-hydroxy-4-p-t<,.luidinoanthraquinonc
I-methylamino-4-p-toluiui'1oanthraquinon<:'
N - (p-dim('thylaminophellyl ) -1 ,4-naph tholquilloniminc

Violet Smoke:
1,4-diaminoanthraquinone
1,4-diamino-2,3 dihydroanthraquinol1(
1,5-di-p-toluidinoanthraquiuone
I-methyl&mino-4-p-toluidinoanthraquinone plus
2-quinolyl-2-indandione-l,3 (Rhodamine B)
l-methylamino-4-p-tollllri.inoallthl'aquinone plus
1,5-di-p-toluidinoanthraquinone
--------------------------------------------------------------------

TABLE 7·10
SOME DYES WHICH HAVE BEEN USEr> IN EXPLOSIVE·TYPE
COLORED SMOKE MUNITIONS

Red Smoke: Dyers)


1- (2-methoxyphenylazo) -2-naphthol
l-me+.hylaminoanthnquinone ~ Celanthrene Red)
----------------_._._------
~ cllow Smoke:
2,4-dj(.. l1iuoazobenzt'lw ({,hrys(lidillf' a, base)
Auramine Hydrochloride

are,en Smol,e:
1,4-oi-p-tnluidillounthraquillOIl(' (Quillizarin Oreen)
p!us IJuillophthaiolh' (QUil:olinc Yellow, base)
in the ratio of 6ri /35
] -4-oi-p-toluidinoltllthraquiIJfJl](> plus Iluraminc hyrlrochloride

7-35
AMCP 706·185

cP g
01.)

~
ILl

~
.... 0 c-

~
t- ~
.., ~ ~
i ..,l-z
III
..,II: ..,
II:

t:
0
~
0

50 -

L
100
I
300
l
SAW'LE TEMPERATURE. °c
I
500
NOTE:
'--~-c4Jobl--'""'"--'riJAo..--
SAMPLE TEWPERATURE, °c
aAo
x- AX~ TEWPERATUAE REPRESENTS SAWPLE
TEWPEAATUAE FOR THE DTA CURVE AND
FURNACE TEWPERATUR£ FOR-THE-TGA CURVE

Figure 7-11. Differential Thermal Analysis and Thermo-


gravimetric Analysis Curve For J,4-di-p-to/uidinoanthra-
NOrE: ~-AX~ TE~TURF. REPRESENTS SAMPLE quinone
~~rw~ O~R CAftl:E"a:>CURVE
Figure 7-W. Differential Thermal Analysis and Thermo- ture and decrease the quantity of smoke available.
gravimetric Analysis Curve for J,B-dihydroxyanthra- Although organic dyes have been widely used
quinane in burning. and burst-tJ pe colored smoke markers
and signals, very little is known about their (,hem-
the most promif" for future investigation. Several ical, physical, and thermodynamic properties at
dyes '~nntaining 'lUlfonic groups have been tested elevated temperatures. In making a choice of
and, rith 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) -l-naphthalenesul- SUblimation, decomposition, equilibrium vapor pres-
fonic acid which gives a fair red smoke. Lakes and sures, rlltes of vaporization, and the temperatures
otht'r pigments have Jeen found to give no smoke at which these phenomena occur--art: important.
wheil used in pyrot~chnic mixtures. For satisfac- !<'or 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
tene t.o give a muddy.~olored smoke. Inorg~nic vaporization, the fuel-oxidant to dye ratio required
imprtrities ar£' generally either sodium chloride for optimum vaporization of the dye will not allow
or s(,dium sulfate and, while they in themselves the munition to contain the amount of dye necea-
do ll'.t change the color of the smoke, large quanti- sarJ to produce an acceptable volume of colored
ti~s "low down the bur.ning rate of the smoke mi.:;:· smoke. If the dye can be vaporized at a low tern-

7-36
AMCP 706·185

perature but the differential between the tempera- 30 percent initial weight 10s.1 during which a point
ture for vaporizll.tion and the temperature for of i.nfleetion occurs. It is p03tulated that th:is ma-
decomposition is not largc, the dye to fucl ratio terial reacts to form all effective c"lor pl'llduct in
inereases but the po~sibility of decomposition of the temperature region (\f 350 D C to 440°0. If,
the dye is also greatly increased. In general, there- however, the t8mp~rature of the dye is not care-
fore, the dyes utilized must be thermally stable and tully controlled, it decomposes further to form a
vaporize without decomposition at intermediate voJlltile red product. Tn geMral, the Jyes in
temperatures. Groups 2 and 3 do not perform satisfactorily.
The volatilization properties of organic dyes They fail to vaporize app~·eei&l.;ly and the irNgu.
proposed for use in pyrotechnic smoke mixtures larities in the differential thermal analysis curves
were studied by differential thermal analysis indicate the occurrence of reactions and/or de-
(DT A) and thermogavimetric techniques.35,~6 The composition. '{'he temperature produced by the
dyes evaluated by these techniques l3an be classi- reaction must be mfficiently high to rapidly
fied into three groups. vaporize the dye but not excessive so as to cause
The materials in Group 1 exhibit an inir.ial decomposi.tion of the dye, or flaming. A conling
weight loss, the rate of which inureases as a fun(;- agent such as sodil'm or potasl'ium bican..onate
tion of temperature. They do not nave an inflec- may be added to t}le fuel n::.bc. to regulate the burn-
tion in their thermogravimetlic C".ll'ves until they iJl!~ rate. Bindercl are s&ffletimes 'Used to produ~e
have undergone a weight loss of 65 tv 100 perc:.e:ut. a composition that is easier to hJ.ndll.' and process.
An examination of the DT A curves for these ma·· The propertIes and structures of .lertain se-
terials generally indicates an endothermal reac- lected dyes are as follows:
tion followed by an exothermal trend, and, finally,
an endothermul region. Over t.hese temperature
Dyes Selected by the British as the Be:'lt Agents
rangl~s the fol!owing phenomena were ohserved:
Available for the Produetion of Colored Smokes
fusion, the evolution nf small quantities of vapor,
by Explosion, Using PETN (pentratrythritol
and boiling.
tetranitrate) for the Explosive:
Compounds in Group 2 show an initial wcigln
loss of froUl 30 to 50 perpimt, fonowed by a sharp Red: o-methoxybenzene-azo-~-naphthol (BriIliant
break in the therm-..gravimetric curve, after which Fat Scarl€'t)
Molf:l:ular Weight: 278
the tate of ~'eight loss is- gflIlcrally slower. The
Components: o-Anisidine ....,. ~-nllphthol
thermogravimetric curves for Group 3 materials
Cl1 H 14N 2 0 2
indicat.e an initial weight 108.'1 of only 2 to 20 per-
cent prior to an inflection.
In general, the materials in Group 1 possess
the thermal properties of :,tability und volatility
required fOI" :S1'.l.tisfl'_ct::>ry func1.ioning in pyrotech- =
nic smoke items. For most of these ~aterials, as
shown in Figure 7-10 for 1,8-ilihydroxyanthra-
quinone, no 'Neight 10s3 occurs befo<'~ LIsion; once
the Loilin~r point is approaclled. the rate of weight
Properties, Descriptirn: Red paste; separates from
loss inerea",es unifl)l'mly.vith temperature The
glaeial ace~ic aeid in red erystalliue powder,
absence ()f a break or point of inflection in the
m.p. 180 D C. HzO---insoluble. Alcohol--red 30-
thermogravimetric curves for the Group 1 ma-
lution on boilillg. Ih80 4 -bluish-l'cd s.)lution,
terials, is indicative in this cas:), of vaporizu.:;il)u.
red precipitate on dilution.
GrOd!) 2 materials do not vaporize appreciably.
Commercial Names: Oil Vermilion (W), Sudan R
A& sLLw'l in Pigure 7-11, 1,4-di-p-toluidinoan.
( A); BriLiant Fat Scarlet B I)~(;i), Pigmen·
thraquinone. a ~taI1rlard. dyi) used for the pro-
Pmple (MTJB).
duction of blue ~r>10ke, e1~hibits ,-,pproximatdy a

7-37
AKCP 706·185

Yellow: 2,4-Diaminoazobenzene (Chrysoidine G, and paste (By), Alizarin Brilliant Green EF,
base) G cone. (LBH), Solway Green E, EF, GM
M oleclllar lV eigh t: 212 (SDC), formerly Kymric Green E, G extra
Components: Aniline-m-Phenylenediamine (SDC).
C1. 2 H 13N4 CI A mixture of 55% 1,4-dimethylaminoan-
thraquill{llle (Brilliant Blue G, M.W. 266) and

C=>-N = 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 8.
Properties, Description: Reddish-brown crystalline color approaching the green of the spectrum.
powder o. large black shining crystals with a ---._._-----
green lnstl'r (latter IJOutahl the homologs from Quinoline Yellow: Mixture of symmetrical quin-
0- and p-toluidine). H 2 0--orange-brown solu- ophthalone or 2-quinolylindandione, with small
~i()l1. Alcohol-orange-brown solution. Bther- quantities of iso-quinophthalonc, or unsym-
insoluble. HCI to Aqueous sohltion: brown-yel- metri.cal quillophthalone or 2-quinaldyleneph-
low gelatinons precipitate C0:1.31sting of ha.il'-li~{e thalide.
needles. NaOH-red-brown precipitate of chrys- Molecular Weight: 273
oide base, m.p. 117°C, spari:l~ly soluble in H 20, Components: Quinaldine and phthalic auhydride.
soluble in ether, alcohol, or benzene. H 2 S0 4- C1s H l1 N0 2
brown-yellow solution, cherry-red to orange so-
luLen on dilution.
Commercial Names: Chrysoidiutl G (CAC), (DuP),
(Gy), (SCI), (MIlY), (By), (GrE), Chrys-
oinine Base (C1JC), (OV), (JWL), (LBH),
(W), (NAC).
Quinophthalone iso-Quinaphthalone
Green: Mixture> of 1,4 di-pi-toluidinoamino-an-
thraquinone (Qu;nzarin Green) ann quin- Properties, Description: Yellow powder, crystal-
oph thalolle (Qumoliiw YeHow, base) in the lizes from boiling alcohol in thin golden-yellow
mtio of 65/35. needles, m.p. 240°C; iso-quinophthalone is more
;l/olecll1ar lVr;ight: 418 (Quhlzarin Ureen) soluble in alcohol and crystaIlizcl,1 in orange-
romponvnts: lrucu-Quillzarin (or 1,4-Dichloroal1.- yellow prisms, m.p. 187°C. H 2 0-Insoluble.
thraquinone) and p-Toluidine. Alcohol-sparingly soluble with a yellow color.
H 2S04 -yellowish-red solution, yellow Boceulent

({On" -.- Co==> CH3 precipitate on dilution.


(Jommercwl Names: Quinoiine Yellow spirit-soluble
(II), (S), (RF), (A), (B), (By), (K), Bril-

l 'COA).H (=~ CH,


Properfies, Description: Bluish-gr~en powder.
liant }i'at Yellow C (SCI). Quinophthalone

Dyes Selected by the U.S. as Satisfactory Agents


II 2 0-·_I;luish-green solution. HCI---dark soluble for Producing Burning Type Smokes:
preeiJ,itatr. NaOH-dark sult;blr precipitate. Yello w: A uramine-Hydrochloride of tetramethyl-
H 2 S0 4 - dull reddi.i;h-blue solution, bluish-green diamino-diphenyl-ketonimine.
solution on dilution. Molecular Weight: 267
f!ommercial Names: Alizurol 8yaninc Green E, G ('omponcnts: Tetramethyldiamino-diphenyl meth-
l:xtra, K (BAC), Alizarm C~'anine Green F ane, ammonium chloride, and sulfur.
paste lind powder, EF, G extra, 3G, K powder CJ7II22NaCI +
H 20

7-38
AMCP 106·185

Yellow: Bd&.naphthalenc.azo-dimethylaniline and


Auramine C1sH!7NII
Jrfole~ular Weight .. 275

7-3.4.2 Fuels38 •87


The numher of combustibles t.hat are satisfac-
Propert,:es, Description:Sulfur-ydlow powder. tvry in colored smoke mixtures is very limited and
H~O-"oright yellow solution, readily decom- ~ncludes sulfur, thiourea, and sugars such as
posed on boiling. Alcohol-yellow 'iolution. lactose, sucrose, and dextrose. Dextrin, starch, and
NaOH--white precipitate of Auramine base, lampblack can be used, in part, to replace the
m.p. 130°C, soluble in ether. E 2 S0 4-colorless abov~ materiRIs but resuits have not always been
solution, pale yellow color on dilution. satisfactory. Among the sugara, lactose has be~n
Oornmcrcial Names: Auramine (If), (Gy), (S), found to be the most de!1irable. 8m'rose and dex-
(SCI), (BtD), (.A), (B), (By), (C), (II), trose (corn sugar) have the disadvantage of being
(MLB), (tM) j somewhat hygroscopic, and a small percentage of
Auramine 0 (BDC), (DuP), (Gy), (8), starch is u3ually add~d to enabb their handling
(BCI), (8tD), (B) under .condit.ions of high humidity. Potassium
o conc. (LBH), DuP) NO(CN) chlorate and sugar are usually mixed in IlLout
II (BDC), (LBH), (B), equal parts. Although wch a fuel mixture con-
(A), (B) 2 (BtD) tains an excess of sugar, the eXCeSS ha~ been found
NAC (NAC) m~j (B) necessary to secure proper action of the smoke
no extra conc. (SCI), (Bt.D) extra conc. ingredients. For slow-burnhg colored smoke mix-
(MI.JB) turts, a fuei composed of sulfur and potassium
chlorat,e, in stoichiometric proportions, has been
Fat Yellow A (SCI)
four.d to be highly satisfactory.
CaD'lry YeHow (Gr E)
With either sucrose or lactose as fuel, the
gaseous produets forMed are carbon dioxide and
(Jrcen: 1,4-di-p-toluidinoanthraquhlOne with aura-
wat.er vapor:
mine hydrochloride
CI2H:?2011 + 8KClOa ~ 8KCl + 12C0 2

Red: 1-Methylam inoanthraquinonc «(;elanthrone + llH 0 2

Red) Lactose wOl.ld yield an additional mole of water


M o~c('.1l1ar Weight: 237 when oxidized by potassium chlurate.

7·3.4.3 Oxidants88 •87


A large nllll'_ber of fUel-ol(idant mi1:tures have
been investigated. The mtidizin6' agents btudied in-
clude chlol'ates, per6blorates, perruanganates, lli-
trates, nitrites, peroxides, and oxides. However,
C{)mmerrial Name: Dut'anoI Red BeBDC) the only satisfactory oxidizing agent f'lUnd thus
--------_. far, despite its friction-sensitivi.ty, he& b'3er. po-
Products Currently Used for Colored Smoke Com- ta&sium chlorate. Po~assium nitrate might be used
positions: to replace potassium chlorate in ~oIOl'ed smoke
Gr(!er.: 1-4·di n-toluidinoanthraquinone and Aura- mixtures if a very stable dy~ sucit as I-methyl-
mine amin,xllltbraquinone is used. Even with this dye,
on!y slow-burniug arenades have be(>n produced
------_._---------------_. uoing potassium nitrate. With most dyvs, 8. n.i-
fled .. I-M(~hylamiuo anthraquinolle
trate is always le8S desirable thana chl('lrate, and

7-39
nitrates have been found unsatisfactory with aura- ('asily handled, (5) it is available at low cost and
mine hydrochloride and indigo. Nitrates, there- ill quantity, aIld (6) it eliminates the necessity for
fore, should not be substituted for the cblorates consolidation under pressure. Other plastics which
in colored smoke munitions unless a special condi- hav(' been cOlisidered include various monomers
tion, such as a shortage of chlorate, makes it neclls- and polymers of acrylic and vinyl plastics, poly-
sary. amines, and epoxy-type resins.

7-3.4.4 Cooling AgentsS3•1I7 7-3.4.6 Evaluation of Colo,,"ed 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 decolnposition able. These colors were most perceptible against
of the dye with resultant decolorization or strong the various backgrounds and displayed optimum
flaming. '1'he best cooling agents have been found visib';iity at a con!>oiderable distance. Further, they
to be sodium bicarbonate or potassium bicarbonate. were least aiff;cted by the light-scattering proper-
Potassium bicarbonab'l 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 meru.urp. the quality of a colored smoke. In
Other cooling agents which have been investigated many cases, they were merely observed at va.rious
are the ammonium salts such liS the chloride, distances. More quantitative methods involve the
bromide, oxalate, carbonate, sulfate, 'Sulfite, thio- use of Munsell color eharts 40 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. 41 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 kaolin- data were converted to the internationally accepted
have often been added to smoke mixtures to retard C.l.E. system of color rf'presentation for evalua-
the burning- rate and reduce flaming. tion.

7-3.4.5 Binders
Graphite, zine oxide, and linseed oil have been 7-3.4. 7 Sensitivity of Colored Smoke Mixtures42
used for oorne application:-. but in most cases no Most of the colored smoke mixtures whif.lh have
binder has been used and the composition has been been used, with the exception of the yellc w smoke
eonsolidated under iJressure. Because of the prob- mixture containing auramine, may be r,)Jlsidered
if'ms associated with the loading of smoke mix- satisfactorily insensitive to friction and impact
tures, some work has heen directed toward the de- under the conditions encountered in normal load-
velopm('nt of a plastic-bondf'd smoke mixture. 3s ing operations. Yellow smoke mixtures containing
None of the plas-tic-bonded smokes haV(~ 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-
:wetate3 1> would be advantageous be~ause: (1) it t.aining 1- (4-dimethylaminophenylazo) -2-naphthol
eOlltributes few undesirable qualities to the smoke, are lIlarkedly less sensitive to impact and friction
(2) it binds smoke mixtures into a hard, tough, than mixtures eontailling auramine. Ignition LJst
nonbrittle mass having excellent water and shock results show that colored smoke compositions can
resistaDc(', (3) it produces a formulation which be ignited by hot surfaces--and lIO doubt by open
withstands high and low temperature surveillance flames and othcr (lired heat SQurces-of compara.-
with negligible change, (4) it is safe, nontoxic, and tively low temperature. Following ignition, dust

7-40
AM'CP 706-185

SMOKE CIlNISTERS

Figure 7-12. 105 mm M84 Colored 5mbke Pro;edile

douds or dispersions of these powders are capable Diethylamino Rosindone might undergo metabolic
of producing dust explosions. reduction in the body to yield carcinogenic 13-
naphthylamine. Green smoke dye 1,4-di-p-toluidino-
7-3.4.8 Toxicity of Colored Smoke Mixture anthraquinone is on the current approved list for
As standardized, the colored smoke clouds are drugs and cosmetics (Food and Drug Admi.nistra-
nontoxic in ordinary field concentrations. In gen- tion)0

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
[t has been reported43 that certain dyes exhibit information pertaining to the potential hazards in.
carcinogenic characteristics which should be volved ic 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 /lnd artillery projec-
for carcinogenic activity even though the original
tiles, float signals, rockets, smoke bombs, and similar
dye may be harml~ss. The hazards involved in
munitions. As flhown 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 th& fuze func-
posure no matter how small the dosage.
tions. The ejeation charge ignites the starter mix,
One of the smoke dyes of great interest to the
ture which, in turn, ignites the smoke mixtu."re.
Army, Indanthrene Golden Yellow GK, bas been
This device contains three canisters which are
tested and f01'lld to be not carcinogenic but it is
ejected from the base of the projectile on air burst.
closely related to 3,4,8,9-dibenzpyrene <Idanthrene
Each canister contains from 380 to 410 grams of
Golden Yellow wit.h,)Ut the two oxygcns) which is
either yellow, red, green, or violet smoke mixture.
known to be a very potent carcinogen. If this com-
Many other smoke-producing items, such as gre-
pound should he pret~.;nL 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 of these
as .01 % it would present a considerable hazard.
devices are given in Tables 7-11 and 7-12.
Red dye, I-meth~'lamill'lanthraquinone, has not
been tested for earcinogenicity but has the possi-
bility of beiug '1 pot,ntial liver carcinogen. Two 7-3.4.10 Direct Volatilization of Dye
other smoke dyes, Sudan Orange R (l-phellylazo- Colored smoke clouds are also produced by
2-naphthol) and 1- (2-methoxyphenylazo) -2-na!)h- direct volatilization of dye in the thermal genera-
tho} are reported as carcinogenic. Blue dye, 1,4-dia- tor-type munitions (separate dye and fuel com-
mino-2,3-dihydroanthraquinone, has not been tested partments). The dye should preferably bc a
but is expected to be relatively safe by its structure. crystalline eompound and have a melting point

7-41
Allep 706·185

TABLE 7·11
CHARACTERISTICS OF TYPICAL EJECTION.TYPE COLORED SMOKE DEVICES

Characteristic 4.2-in. Colored M18 Colored Smoke


Smoke Projectile Hand 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 SQ M201A1
1.2 to 2 sec delay
Propellant M6
Loading Pressure 18000 Ib/in. 2
Smoke Duration 50-90 sec
Applications Time-fuzed for air-burst sig· Grenade is thrown or
naling and/or base-ejected for launched from a rifle or car-
marking ground positions. bine by using a M2Al gre-
!Jses red, yellow, green or nade projection adapter.
violet colored smoKe for sig- Hses red, yello",", green, or
naling, spotting, or outlining violet colored smoke for sig-
a position naling
Visibility Very good Easily identified at altitude
of 10,000 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°0, when Yellow N (N, N-dimethyl-p-phenylazoaniline) gives
mixed with a ~mall proportion of a melting-point a satisfactory color. 'l'he dye duPont Oil Yellow
depressant such as diphenylamine (less than 25 N produces a brilliant yellow colored smoke. Mix-
percent is necesssry). The dye should be stable tures of blue and orange dyes, such as Galco Oil
for three to four minutes at temperatures of 50°C Orange Y·29~ and Ga!ea Oil Blue NA (1,4-di-
to 100°(: above its melting point. The dye 1-(4- amylaminoanthraquinone), give a brown-orange or
phenylazo) -2-naphthol--(~alled commercially by a brown-rose cloud. Blue smoke results from using
variety of names, i.e., duPont Oil Orange, Sudan only 25 percent Galeo Oil Orange Y -293. With a
Orange, Federal Smoke Orange-E, and 1-(0- 75 percent mixture of National Oil Scarlet 6-G
tolylazo)-2-naphthol (C&.lco Oil Orange Y-293)- and Caleo Oil Blue NA, the color has the appear-
protluces good orange smoke clouds but var;es in ance of a mixture of orange and violet or tan and
quality depending UP<JIl the commercial source. violet. IJarger percentages of scarlet result in a
The dye l-xylylazo-2-naphthol (Oalco Oil Scarlet rose-colored cloud and smaller percentages result
II, National Oil ~carlet 6-G) gives a much redder in blue smoke. A mixture of the dye 1-(2-methoxy-
cloud but the addition of 20 percent duPont Oil phenylazo) -2-naphthol (Federal Signal Red A)

7-42
AMCP 706-185

with Calco Oil Blue NA gives a blue-gray cloud


for all proportions tried. The dye Monoazo Red
(duPont) gives I!luch 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 uye 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-Green
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 ear bon tetrachloride to four pal ts of SAE-10
oil is not satisfactory due to congealing of the so-
lutioll. The use of hexachlorobutadiene as solvent,
however, is considered succes:ful in that 4;he result-
ing mixture of dyestuff and solvent is extremely
fluid and has no tendency to congeal. Azo dyes are
founu to be the most satisfactory. These are Oil
Yellow (4- (O-tolylazo) -2-methylaniline), Oil Seariet
6-G (1-xylylazo-2-naphthol), Oil Red 0, and Oil
Gt'eell Q-261.
Further tests indicate that solutions of dye in
hexachlorobutadiene, diluted with SAE-IO 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 galluns of trichlorvbenzene, and three gal-
lons of SAE-lO oil are found til be satisfactory.
No gelling of the solution is noted after six to eight
days.
Oil slllokr is also produced in a wide variety of
colors and shades Ilsing thr following oil-soluble
dyrs either as such or in admixture:
Oil n Iue
N A (1,4-diamylamilloanthraquinone)
This page is reprodu0ed at the Oil Blue RA ! N- (p-dimethylaminophenyl) -1,4-
back of +!'e report by a different
reproduLoIl metlwd to provide naphthOl! lIillonimine]
hetter detail. Oil Red N-1700 [1-(tolylazoxylylazo)-2-naph-
Fig;Jre 7-J3. MJ8 Colored Smoke Hand Grenade tho) J

7-43
AMCP 706·185

SMOICE MIX
PRESSED AT 11,000 PSI

EJECTION CHARGE
25 G. GRAOE A4 ILACt( POWDER
35 G. INFALLIBLE ~OWDER

..." .....' ; •• :-. ::." . o· • :': '.. .' " :


.0, ,,00::::_
. .. . '0 '0:'-
. .. :.,. .....

'. .." .
. . .. .. "..
.. '... ."
..
. : . '.
• '0
t. ".'
••
.. •

TRAWIOARD WASHER
CANISTER

FIBER WASHER

Figure 7·J4. 4.2·;n. Co'ored Marker Projedile, Colored Smoke, E7S

Oil Orange Y-293 [1-(0-tolylazo-2-naphthol] basic smoke, All t.he 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 ana 700°C.
Gas Green CG (l,4-di-p-toluidinoanthraquiu. Oil Blue RA is used successfully at 400°0 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°0 and 625°C. Water solutions of Auramine
, of dye' is obtained by adding about five percent
and Red Y Supra Conc. (Safranine) are used dec-
of 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 "le oil cloud does not appear to have any
dye is added at a point in the oil smoke exhaust
injurious effect. Water solutions of Blue FFB,
where the temperature can be varied l;letween 400°C
New Blue N (Methylene Blue), and Magenta XX
and 800°C. By controlling the temperature within
fail to produce color under the conditions of these
approximately 50°C limits, a fairly constant shade
experiments.
is obtained with each dye. By using different tem-
perature bands, variations are obtained in the
shade of smoke produced from a given dye. The 7-3.4.12 Black Smoke"'"
. 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 of temperature are produced by burning of hydrocarbons such as
due, at least in part, to the changes in color of the phenanthrene or anthracene. The, addition of an-

7-44
,
~----------------------------------------------- - -- - - -- - - - - - - ------ - - --------- ---------------

AMCP 706-185

CHARGE

Figura 7-JS. 105 mm Ml Colored Marker Pro;ectile

TABLE 7-12
BASIC DIFFERENCES BETWEEN THE COLORED MARKER AND
BASE-EJECTION SMOKE PROJECTILES FOR 105 mm. GUN
--------------------------------------------------------------
lIE Oolored Marker Base-Ejection Oolored Smoke
--------.-------------------------------
Build-up period vi Effective instantaneolls Over a period of from 1-2 min
colored cloud
Density of cloud Highly saturated Wispy
Duratifhl of cloud Average 6.3 -85 sec 75-120 sec
Size of cloud Approx. 40 X liD it Streamer approx. 4 ft across
Lethality of round May be lethal (iragments) Nonleth<tl
Fuzing of round .M1'SQ & V'l' fuzing MTSQ fuzing (: nly
'Vcight of round Equal to 105 mm HE round Lighter than J.05 mm HE
round
Ranging of ro~md Similar to 1()5 nnn HE round Canister impacts up to 1;;0
ft away from impact point of
projectile body
---_..__._---_._-----
thrl'''fOne naphthalene to He smokt~ mixtures also
'.II' with an appropriate detonator or booster charge,
TJl.}(juI',ps "laek smoke. The oxidizin~ agent gen- the resulting exploaion giving a !arge puff of
(~!'al\y used is poiassilll¥l p\~rchloratt'. c0!ored smoke. Colored smoke clouds are also ob-
tained from a mixture of a salt and It dye dis-
7·3.t. ,13 Explo~lve- Type Colored seminated by a central high-explo8iv~ burster of
Smake Bursts45 •46 bal atol. amatol, 60 mm igmtion powder, Composi-
In addition to the \~()l()n:d smoke dissemination tion B, or other:.;. '{'he use of a salt dilutent is one
md.hod;.; dis('uss('J in the previous Pal ag-raphs, PrlH'Puu:"e fo!' pr'ndueing tontrulled nuclei on which
I here i~~ tll'~ hiPthod that produces its ,·,fled through the dye may condense. Cll<;t or pressed dye, along
HI(' ad-bn ,)f an explosive hurst<~r. Both propellailts with a ~entral burster, is also used to produce eol-
ami high explosives j;,re u~ed for thh, PUrIY1S{·. F(,( ored douds. 'rhe basic performance differences
examp"', li eclored smoke llflrst ean b\~ obtained hy b~tw('en uissemination of eolort'd smoke fly all
IIsiug a mixtltrt, Df (tpproximatel:: equal parts of itf'1l\ using an ('Xploslve burster and by a munition
tlye and EC i:ilwd(,l'. 'l'hi" rnixhtt't" is detonated using burning-type smol{e mixtures are tabulated

7-45
AMep 706·185

m 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 tne
7-15. weight of a burster used in colored ma.rker pro-
The dyes that are satisfactory for dissemination jeetiles was derived by a.r;;suming 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 by EO pow- weight of burster required is given by the empirical
der. Among the best dyes for explosive munitions formula:
are 1- (2-methoxyphenylazo) -2-naphthol for red,
1- (4-nitrophenylazo) -2-naphthol and 1- (4-phcnyl-
We = KW(Y + U)eK' (7.7)
aZ(l )-2-naphthol for orange, and 4-phenylazo-m- where
phenylenediamine for yellow.
Wv = weight of explosive required (including
initiator), g
7·3.4.13.1 Propellant Bursters41 K= a constant, 11.4 X 10- 6 to 11.4 X 10- 11 ,
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 Ee powder and dye in a projectile !lave been W = weight of steel components of projectile
tried as follows: (excluding fuze and base), Ib
a. Mixing the dye and Ee propellant powder Y = yield stress of projectile steel, psi
intimately before loading the projectile, e= strain elongation at fracture, %
b. Coating the projectile wall with meltec. dye U= ultimate strength of projectile steel, psi
and placing the EO powder in the central K' = ratio of caloric ';alue of a standard ex·
cavity, plosive to explosive to be used. For in-
(~. eilling 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 EO powder in We = KW(Y + U)e(11/9)
alternate layers. Burster charges designed by this method have
The last method, in which alternate layers of dye functioned favorably. The quantity (Y +
U)e is
and EO powder are used, was found to be the best. roughly equal to twice the strain energy absorbed
The alternate-layer method of loading with EO by one cubic iIlch of steel.
powder was found to be superior to bursters of
either TNT or tetryl. The burster ex~losive used 7·3.4.14 Typical Mixtures
is a mixture similar to amatol loadings, consisting 1'ypieal colored smoke mixtures, including a
of 27.8 percent ammonium picrate and 72.2 percent fcw 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 tha.t when it is detonated, it will of the dissemination of agent aerosols is beyond the
break the projectile apart without causing exces- seope of this handbook. In genera.l, the principl~l!
sive di!lpersion uud/or burning of the filler. The and Illrthods applicable to the disseminatioll ef a
products of explosion must be ~ompatible with the ('olorrd smoke agent are applj('~ble i;(> t.he dis-
dye used. The color of many dyes is influenced by semination of an ag'er,t aerosol

7-4(;
AMCP 706·185

TABLE 7·13
TYPICAL SMOKE COMPOSITIONS

Typical
Type Composition, % Application Devices

WHITE:
HC-Type C Hexachloroethane 45.5 Screening Smoke pots
Zinz Oxide 47.5 and Smoke bombs
Aluminum (grained) 7.0 Signaling Grenades
Modified He H exachloro benzene 34.4 Screening- Smoke
Zinc Oxide 27.6 and projectiles
NH4 CIO. 24.0 Signaling
Zinc Dus! 6.2
Laminac v/catalyst 7.8
Modified He Dechloral e 33.9 Screening Smoke
Zinc Ox;de 37.4 and projectiles
NH 4 ClO 4 20.5 Signaling
IJamina·· w / (' !talyst 8.2
Plasticizf'd Whit.e White J'hosr lOms 65.0 Screening Chemical
Phosphorus (PWP) Plafticizer 35.0 (antipersonnel) mortar projectiles
(Necprel' , 100 parts)
(Carbon 75 parts)
(Z'--!ene 44 parts)
(I itha!'l e 15 parts)

BLACK:
KC;')a (200 mesh) 52.0 Screening }renades, etc.
Allthra~e"le (40 mesh) 48.0

COLORED:
l{ed Dye-MIL D-3718 40.0 Signaling Navy floating
KC10 3 24.0 drift signal
Naf-CO s 17.0
Sulfur 5.0
P()lyt'~ter resin 14.0
lied I-Tllethyll!mino (AQ)· 45.0 ~ignaling Rocket type
1,4.di-p·-toluidino (AQ)· 3.0 parachute
KelO s (2~) 3&.0 ground
Sugar, nn{,' (1]\-1.) 17.0 signals
1. (methoxyphenylazo)· Air marker 90 mmRed
~!-nlipht,hol 80.0 Marking marker
NaCl 20 (j ground targets projectile
• (AQ)--A ntilrH.quillot,(1

7-47
TABLE 7-13 (cont'd)

Typical
Type Co'mposition, % Application Devices

Red Dye (R) 40.0


KClO a 28.0 Signaling Improved
(plastic) NaHCO a 23.0 grenade
Sulfur 5.0 fillings

Polyvinyl acetate in
ethyl acetate 3.0

Yellow Benzanthrene 32.0 Signaling Rocket type


Indanthrene GK 15.0 parachute
KClO s (23\10) 30.0 ground
Sugar, fine (1l1J.) 20.0 signals
NaHCO a (201J.) 3.0
Yellow Auramine Hydrochloride 40.0 Air marker, etc. 90 mm yellow
NaUl 60.0 marker projectile
Yellow Dye (Y) 40.0 Signaling Improved
(plasti3 ) KClO s 29.8 grenade
NaHC0 3 23.2 fillin~
Polyvinyl acetate in
ethyl acetate 7.0
Green 1,4-di-p-toluidino (AQ)· 28.0 Signaling Rocket type
Indanthrene GK parach1lte
(golden yellow) 12.0 ground
1(;10 3 (23\L) 35.0 signals
Sugar, fine (1liJ.) 23.0
NaHC0 3 (20iJ,) 2.0
GrcPll Dye (G) 40.0 Signaling' Improved
(J.llastic) KClO a 26.0 grenade
NaHCO a 24.0 fillings
Sulfur 6.0
Polyvinyl acetate
w / ethyl aeetute 4.0
Violet Violt't (!ye, ~j!-\Ilalin!-{ Hoeket type
~pec. MIL-D-:i6!l1 47.5 llaradlUt{'
KCIO a (25)1.) 28.0 gro, lid
Sugllr. fiue (HlJJ.) 18.0 signals
NaIll '0:1 (2D\J.) 4.5
Asb"stns 2.0
Orllllg't' H-ddoro-l-ulllillO (A~)· 39.0 ~iglll\lillg Urelllidt's
Auramilll' 6.0
KClO a 22.3
~\llfllr H.7
NallC0 3 24.0
• (AQ! AutllTlt4Uinolll'

7·48
A)(CP 706-185

REFERENCES
1. A. M. Prentiss, Cllemicals in War, McGraw- Bureau of K.wal Weapons, WashingtoJl., D. C.,
am Book Co., Inc., N. Y., 1037. Ma~' 1959.
2. K. F. Sawyer, "Screening Smokes," 7'horpe's 16. N. Irving Sax, Dangerous Properli,e, of In-
Dictionary of Applied Chem.i..~tr~f. Vol. X, 4th dustrial M,..te,'iaJ,s . .2nd Ed., Reinhold, 1963,
Ed., Longmans, Green, London, 1950, p. 781. L,ibral") of Congress Catalog Card No. 63-
3. H. L. Green and W. R. J.lane, l'tlrii~date 20370.
Cloupt: Dusts, Smokes and Mists, D. V8.Il N0S- 17. David W. Fassett, lJon D. Irish, Eds., I.,.,..
du~rlrial Hygien-e Gud Toxicology, Vol II,
trand Co., London, 1957.
4. History of Res.tlrch and Development of the Interscience Publications, 1963.
Chemil~l War/.we Sc,·vi.ce in World War II
W. AN-M7 F'ile; Bwck Program, Report 0-2148U,
·'i.einbold, N. Y., 19'.!:8. ' Olin Mathies('>n Chemical Corpora.tion, New
Haven, C<>nnecticut, April 15, 1961 (DDC-
5. L. P. Brophy, D. M. SYlldham, R. C. CochrallE,
AD 271 (878).
Thf., CJ.emiooJ. W (J.rfare Set m'ce: From .Labora-
19. L. F. Young, W. M. Conway, The T36E1 81e~
tory ta ji'i,eld, Department of Army, Wash-
Wool White Phosphonu (SWP) Smoke Gre-
:ngton, D. C., 1959.
nade, Picatinny Arsenal Technie.a.l Report
6. W. A. Noyes, Jr., Ed., Chemistry, Srlience in
2618, Pica4;.inny Arsenal, Dover, N. J., Novem-
World War 1.1 Series, Little, Brown and Cll.,
ber 1959.
1948.
20. R. D. Kracke, Improved Pho.piwnu Smoke,
7. John A. Ma.rtin, "Combat Smoke in Korea,"
TCR-13, Techni~al Command, Anny Chemical
Armed Ji'orces Ohemic(1l Journal, 7 October
19i):? Cl'mtcr, Edgewood Arsenal, M.aryland, March
1949.
8. B. E. Klebt:r and E. I. Byrnes, "Make
21. H. Zislin, StfAbiZization of Red. Phorplwnu,
Smoke," Armed Forces Chemical Journal. 6
A~nHO. . Frankford Arsenal Report 660, Frankford
Arsenal, Philadelphia, Pa., October 1945.
9. S. L. A. Mar'!haH, Infantry OperaHom and
WeapVn& Usage;n ICorea During Ihe Winter
22. M. S. Si!verstein, G. Nordblom, Stabilwation
of Oommercial Red Pho6phorus, Frankford
of 1950.. 51, Report ORO.R-13, Department of
Anhlnal Re.,ort 206, Frankford Arsenal, Phila-
Army, Washillgton, D. C.• 2'~ October 1953.
delphia, Pa., April 1943.
10. W. W. Cl.'velJ, T. Stevensoll, 8mokf l'rtUer.,
23. M. S. Silverstein, G. F. Nordblom, C. Vl. Dit-
Cill-i.ber .50, F'rankford Al"St'ne.!, Philadelphia,
trich, and J. J. Jacbbein, "Stable Red Phos-
Pa., Nov~mber 1951.
H . .BAT Antilan~ Weapon a'lI.l Ammuflitiota, phorus, " Industrial and Engineering Chem-
Frankford Arsenal Report ]080, Frankford istry 40, 301 (19/t8).
Arsenll.l , PbHade11)hia, Pil. 24. D. L. Elbt.edt, Laborf1,lory aM Pligl!.t Tut.
'2. W. A. Noy~, .Jr., Military Pf'obu"" toill!. A.ero- of Chemical Tracking Aid., AFMDC-TR-58-2,
,..ols and N otl-Per,ident Oases, Summary Teeh- Air Force Missile Development Center, Hollo-
ni(~al Report of Division lO, DepArtment (if mon Air Force Base, New Mexico, July 1958
Arm)', Washington, n. C., 1946. (DDe-AD 23 7:16).
13. U. Mif', A un d~r Pbys. ~3, :177 (1908). 25. 3. B. Elkins, HC Smoke: ProfHJrt~s of Zi,fIC
14. M. H. P. P. YC\'lck, The Texicity or CombtU- Oxide Alecti"g tltp Burnifl{i Characteri.~t\u
Iwn Product6 oj' P'I.Imte.dinics, CWlJ-TM.26- of HO Smcke Mixtures, TDMR.729, Edgewood
12, Army Chemica! Warl'are Laboratories, Arsenal, Jlr{d.
r<:d,ewtlOd At·UNI&.l, Maryland, MI\~r 1960. 26. I... Finkt>lfltein, Thl (,hemuiry of HC Smoke
IS. To:w.' Tl fUm-ds A.H(Jciottii. "./lit:1 PYf'oteckml" Mixttlrel, A.rmy ChemiclL) Lllboratories, Edge-
Items. np 2793, Naval vnh.llttlce I..nOOratory, wood Arsenal, Md.

7-49
AIICP '106-185

REFERENCES (cont'd)
27. G. Vfeingarten, .Long Range Research on. Py- metric AMlysis of Organic Dyes, Piclltin..'1Y
rotechnics Devektpme1.t of an Improved Smoke Arsenal Technical Note 25, Picatinny Arse.lJl.l,
CompoHtio'1'8 {(lr Acf~t·~dor, Practioe, M·1, Pica- Dover, N. J., 1958.
tinny Arsenal '1'eclmical Report 1799, Pica- 37. ORDWES Quarterly Report 1948-8, Wes-
tinny Arsenal, Dover, N. J., November 1950. leyan University, Middletown, Connecticut,
28. Jack DeMent, Compoditivn for Smoke Produc- May 1948.
tian., U.S. Patent 2,995,526, August 1961. 38. W. W. Reaves, J. H. Hassmann, Investiga-
29. J. E. AndTews, Jr., B. Werbel, Smokes, Pica- tion of a Long Burning Plastic-Bonded, Col-
tinny Arsenal, Dover, N. J., May 1962. ored Smoke Mixture, CWLR 2339, Army
30. J. E. Andrews, Jr., K. G. Carlon, W. W. Chemical Laboratories, Englewood Arsenal,
Reaves, EvaLuation of a Plastic·Bonded HC Maryland, .January 1960 (DDC-AD 233 750).
Smoke Oomposition for the M8 Grenade, 39. N' J. Wilkaitis, Researc/>. and Development of
CRDLR.3065, Army Chemical Laboratories, Flammable Plastic for Colored Smoke U.8,
Edgewood Arsenal, Maryland, April 1961. Army Chemical Laboratories, EdgeWOOd Ar-
senal, Maryland, October 1956 (DDC-AD 137
:U. S. Gordon and C. Campbell, "Preignition and
748).
Ignition Reactions of the Pyrotechnic System
40. Munsell Book of Color, Munsell Color Co., 10
Zn-CeCle-KCI0 4 , " Fiftn. Symposium on Com-
East Franklin St., Baltimore, Maryland.
bustion, Reinhold Publishing Co., N. Y.,
41. Chemical and Radiatioll Laborat,)ries Report
1955. thO, Edgewood Arsenal, Maryland.
~2. S. Grundemeier, Survey of Li.terature of
42. S. J. Magram, S{'nsitivity of Colored Smoke
Ohemical Tracking Aids, HADC-TR-57-7, Air Mixtures; TDMR-547, EdgeWOOd Arsenal,
Force Missile Development Center, Holloman Maryland.
Air Force Base, New Mexico, August 1957 43. A. F. 'l'aiyrek, The Toxicity of Certain Dyes in.
(DDC-AD 135 001). Current Use, PieatinllY Arsenal, Dover, N. J.,
:j:l L. Finkelstein, Colored Smokes, Vol. 12 of His- May 1964.
tory of Research and Development of the 44. Development of a Black Sm'Jke Candle for
Uhemicat Warfare Service in World War Il, Signal Purposes, EACD-376, Edgewood Ar-
Army Chemical Center, Edgewood Arsenal, s~nal, Maryland, March 1926.
Maryland. 31 December 1945 (DDC-ATI 207 45. T. Advokat, Colored Marker Shell M10'l (155
451). mm), Picatinny Arsenal Technical NotE: 140,
:H. G. D. Heath, Formation of Coloured Smoke Picatinny Arsenal, Dover, N. J., September
Clouds, Part 1 of Review of Suitable Organic 1956 (DDC-AD 108 297).
Dye Stuff, PR 2547, Ol'eat Britain, April 1943. 46, T. Advokat, HE Colot'ed Marker Sheli for
:J5. D. Anderson, S. Gordon, D. Edelman, Thermo- M29 and T72 Mortars (81 mm M.'f62), Pica-
gravimetric Determination of the Energies of tinny ~4.rsenal Techniral Report 2664, Pica.-
Activation V olatil.1·zati01l, Picatinny Arsenal tinny Arsenal, Dover, N.•J., January 1960
Technical Note 16, Picatinny Arsenal, Dover, (DDe-AD 314 621).
N. J., 1948. 47. G. D. Heath, Production of Colored Smoku
:J6 D. Andel'SOll, S. Gordon, D. Edelman, Dif- by Explosive Dispersion, PTP-147, Great
ferential Thermal Analysis and TherfIWgrcwi- Britain, January 1950.

i-riO
THE FOLLOWING PAGES ARE DUPLICATES OF

ILLUSTRATIONS APPEARING ELSEWHERE IN THIS

REPORT. THEY HAVE BEEN REPRODUCED HERE BY

A DIFFERENT METHOD TO PROVIDE BETTER DETAIL


ENGINEERING DESIGN HANDBCK)K SERIES
listed below are the Handbooks whic.h have been publishe\! 0" aN! cur~t1y b6'inq prl"IJ!C'. Hatldb\ll)i:a wtth put.l!c(ltion
dates prior to 1 August 1962 were publisned 65 2U·sfirles Ordnance COI~S pemphllts ~: Cir~ullr 31~-Ja, l~ J~~y 1963.
,-edesignated those publlcations'as 706-serles AM( pamphh!ts (I,e .• OROP ?O-llt wa~ re!lf!'s19na~d ,~Cl' 706·13P), All nflii'.
reprinted. or revised Handbooks are being published 15 706-serles ~C par.lphlets,

~.El.llilli_IftS8 i ll1 $a.d_~_!J!1!..'!E..i.:l.~)


No. iitle ~2.:. l.LtJ.!.
lu6 Elements of Annament En91 neeri ng. Part One. 263 ilerl)dynarl C~
Sources of Energy 284(C) Trt.Jector1<!5 'IUI
107 Elements of Armament Engineering. Pdrt Two. 286 StructUrtlS
Ba 11 1st I cs
108 Elements of Armament Engineering. Part Three.
~eapon Systems and Components
110 Experimental Statistics. Sectlon I, Basic Con- 14U irlject·)riel'. (Ii fferellt jill £11.ct5, lind Data
cepts and Analysis of Measurement Oatl for Projecti les
111 Experil.1ental Sta~istlcs, Section 2. Analysts 150 I llterl (II" eli 11 15 tics of GUhS
of Enumerative and Cl~s~lficato~y Data 160(5) Elemer.ts of T~rm;r.ll bbll1~tics. Part One,
112 Experimental Statistics, Section 3, Planning i II trc dl,l'.: (.\ on, Kl1) Mechanums and
and Analysis of Comparative Experiment- VullH!,'abill ty (Ii)
161(5) El~nents of Te~lnal 8~1115t'cS, Part Two,
113 Experimental Statistics, Section 4, Special Coilflction and Anelysis of Data ::pncemlnl
Topics Targ'!ts I U)
114 Experimental Statistics, Section 5, Tables 162(5-RD) Elements of T!rminc; BAllistics, P'Irt ThrlH.
121 Packaging and Pack Engineering Application to M1s51141 Ilid SDI~ Tir9f't~ (U)
134 Maintainability Guide for Design
135 Inventions, Patents. and Related ~atter;
(Revised) C:u'l'iages and ..~oW1t!.~erie8
136 Servomechanisms. Section I, Theory 340 CarriJges and Mo"nt~,·E:e!1!!r!.1
137 Servomechanisms. S&ctlon 2. Measurement and 3~ 1 Crad1fls
Signal Converters 342 Reco-; I ')yst'!!l!l'.
138 Servomechanisms. Section 3, Amplification 343 Top C.trriaQ'!!s
139 Servomechanisms. Section 4, Power Elements 344 Bot >"00'1 ::: .. rri age~
and System Design 345 (c~lllbrators
170(C) Armor and Its Appllcatl~n to Vehicles (U) 345 Eievatlnl! Hl!ch~njsms
270 Propellant Actuated Oevlces 347 Tr4vers ing 1!\!c;'lft,lisns
290(C) Warheadt--G.neral (U)
331 Compensating Elements (Fire Control Series) GIlM SI1.Mef!.

A"1m<ni ti~ E:r:p1.osivet1 Series


250 Guns" ·<;,-mera 1
252 (jun T'It;,.u
175 Solid Propellants. Part Olle
176(C) Solid Propellant>, Part Two (U) NiZits£!7i i)l'OteahniC's Se-t'c/J
177 Propert i es of Exp los I ves of Mil itr ry lnter-.s t. 186 Part Two, Safety. Procedur@$ aou Glos~a~
Sectlon 1 187 Part Three, P;'opertles of Materials Uud in
178(C) Properties of Explosives of' Military Interest. Pyro~echnic CC1IIJPOSl ~jons
Section 2 (Ii)
J.79 Explosive Trains leg Part Five, Bi~;iogr~vny
210 Fuzes. General and Mechanical
211 (C) Fuzes, Proximity, Electrical, Part Ont (U)
212(5) Fuzes, Proximity, Electrical, Pllrt Two (tl) Z91 Part One. Sjst~ Integration
213(5) Fuzes, Proximity, Electrical, P&rt Three (U) ~92 Part TW(l, Weapon Control
214(5) Fuzes, Proximity, Electrical, Part Four (U) 293 Part Three. Computers
21S(C) Fuzes, Proximity. Ele~trical, P!rt Five (U) 294(S) Plrt Four, Missile Anaament (U)
242 Design for Control of Projectile Flight 295(5) Pilrt FivlI. COl;ntermeawres (U)
Characteristics .:96 Part Six, St.rucwre~ and Power Sources
244 Section 1, Artillery Ammunition--General, ~9 7:S) Part Seven. Sllrnple Probletll (U)
with Table of Contents, Glos5a,'y and
Index for ~erles ~l'ia?!_ SI1l'ies"
24S(C) Section 2. Design for Terminal Effects (U) 149 Rubb,r and Rubber-Li\e Materials
246 Section 3, Desig~1 for Control of Flight 212 Gasket Materhls (Non,oota111c)
Characteris ti cs (out of print) 691 Adlles j yes
24' Section 4, Design for Projection 692 Guide to Selection of Rubber O-~jng$
248 Section 5. Inspection Aspects of Artille~
Ammunition Design 693 Magnesium and MagneSium All~y5
249 Section S. Mlnufaeturf of Metallic Com~onents 694 A1UllinUll\ and Aioolnl. Alloy~
of Artillery Ammunition 697 Titanium and Titan~um Alloj5
698 Cc~ptr end Copp.r Alloys
699 GUicM t{'l Spec!flcatlOlls for Flexible Rubher
Products
355 The Aut~tive Assembly 700 Plastics
356 Automotive SuspenSions 721
722
~orrosion and Corrosion Protection
G11lss
Metals 0'
~'llliGti~ NioBiZ4 ~·il'l-i • •

281(S-RD) Weapon Syst~ Eff.ctlvenes. (U)


282 Prop~lslon and Propellants
I
'The Mlterlals Series is being publilhed a~ MIlit.ry H.ndbooks (MIL-HooK-) ~hjch are ay~j\able to ~pirtment of Dtt~t
Agenci,s from the N,vel Su~ly Depot, 5801 Tabor Avenut, Philadelphia, Pennsyl<.ni~ 191Z0,

1-5\

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