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AMC PAMPHLET AMCP 706-175

ENGINEERING DESIGN HANDBOOK

EXPLOSIVE SERIES

SOLID PROPELLANTS PART ONE

HEADQUARTERS, U.S. ARMY MATERIEL COMMAND SEPTEMBER 1 964


HEADQUARTERS
UNITED STA TES ARMY MA TE RIEL COMMAND
WASHINGTON, D. C. 20315

30 September 1964

AMCP 70 6- 175, Solid Propellants, Part One, forming part of


the Explosives Series of the Army Materiel Command Engineering
Design Handbook Series, is published for the information and guid-
ance of all concerned.

(AMCRD)

FOR THE COMMANDER :

SELWYN D. SMITH, JR.


Major General, USA
OFFICIAL: Chief of Staff

Chief, Administrative Office

DISTRIBUTION: Special
EXPLOSIVE SERIES
SOLID PROPELLANTS
PART ONE

By A. M. Ball

CONSISTING OF
CHAPTERS 1-10
PREFACE

This handbook has been prepared as one of a series on Explosives.


It is part of a group of handbooks covering the engineering principles
and fundamental data needed in the development of Army materiel,
which (as a group) constitutes the Engineering Design Handbook Series
of the Army Materiel Command.

This handbook presents information on the design, functioning and


manufacture of solid propellants for use in propelling charges for guns
and rockets.

The text and illustrations for this handbook were prepared by


Hercules Powder Company under subcontract to the Engineering Hand-
book Office of Duke University, prime contractor to the Army Research
Office-Durham for the Engineering Design Handbook Series.

Agencies of the Department of Defense, having need for Handbooks,


may submit requisitions or official requests directly to Publications
and Reproduction Agency, Letterkenny Army Depot, Chambersburg,
Pennsylvania l 7 201. Contractors should submit such requisitions or
requests to their contracting officers.

Comments and suggestions on this handbook are welcome and


should be addressed to Army Research Office-Durham, Box CM, Duke
Station, Dur ham, North Carolina 27 7 0 6.

'

ii
TABLE OF CONTENTS

Paragraph Page
PREFACE............. . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
UST OF ILLUSTRATIONS. . . . . . .......... .. ...... .. . . .. .. vm
LIST OF TABLES... . . . . . . .. .. . .... . . .......... . .. .. .... . . x
LIST OF SYMBOLS... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi
CHAPTER. 1
INTRODUCTION
I PURPOSE .... . .. . .. .. ....... ..... ... . .... . .. .. ........... .
2 DEFINITIONS .... .. .. ....... ... .. . ... . .................. . I
3 PLAN . . . ........... . .. ........ I
REFERENCES ... ..... . ... . .. ...... ... . .................. . 2
CHAPTER 2
EVOLUTION OF GASES BY PROPELLANTS
4 GENERAL.................. . . . .. .. ....................... 3
5 EQUATION OF STATE......... .. . . . ... ... . .... ........... 3
6 BALLISTIC PARAMETERS ... , ...... . .. . ........... ,...... 3
6-1 Specific Force.................... . ... ... ... . . .. . ... .. . . . . 4
6-2 Characteristic Velocity....... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
6-3 Reduced Characteristic Velocity. . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
6-4 Specific Impulse......... ......... .. . . ..... ............... 4
6-5 Reduced Specific Impulse . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
6-6 Volume Specific Impulse .... . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
6-7 Gas Horsepower. . ... . .. ... ... . .... . ..... .. .... ... . . . . .... 5
7 THERMOCHEMISTRY... .. ................. .... ...... . . . . 5
7-J Specific Gas Volume............... . . . . . . . . . . . . . . . . . . . . . . . 5
7-2 Flame Temperature at .Constant Volume. . . . . . . . . . . . . . . . . . . . . 6
7-3 Flame Temperature at Constant Pressure..... . . . .. ... .. . ..... 6
7-4 Ratio of Specific Heats.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
7-5 Exact Calculation of Flame Temperature and Product
Composition .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
7-6 Hirschfelder-Sherman Calculation........... . .... ........... 7
7-7 Example Calculation ofF, c!. I,~ by the Hirschfelder-Sherman
Method....... . .. .... . . . . ............... .. ....... . . .... 9
7-8 ABL Short Calculation for Specific Impulse. ... .. . . . .. .... .. . 10
8 MEASUREMENT OF BALLISTIC PARAMETERS .. .... .. . .. 10
8-J Measurement of Heat of Explosion. . . . . . . . . . . . . . . . . . . . . . . . . . I0
8-2 Measurement of Specific Force. . .................. . ..... . .. IO
8-3 Measurement of Characteristic Velocity... .. . . . . . . . . . . . . . . . . . 11
8-4 Measurement of Specific Impulse . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
8-5 Example Calculation of I,,, from Measured I,,, (de\) at Non-
standard Conditions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
9 BURNING OF PROPELLANTS . . . . ... . . .. . ................. 12
9-1 Effect of Pressure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
9-2 Effect of Temperature............. . ..... . ... .. .. .. .. . .. ... 14
9-J Effect of Gas Velocity. Erosive Durning . ...... . . . . . . . . . . . . . . 15
9-4 Effect of Composition. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

iii
TABLE OF CONTENTS (Continued)

Paragraph Page
9-5 Burning Rate of Composite Propellants .... . . . .............. . 16
9-6 Problem of Unstable Burning .................... . ......... . 17
9-7 Transition from Deftagration to Detonation ................. . !7
10 PROPELLANT GRAIN ................................... . 17
11 SCHEDULING OF MASS RATE ........................... . !9
11-1 Gun ...................................... . ............. . 19
11-2 Catapult ......... . ...................................... . 20
11-3 Rocket Motor .................................. . ........ . 22
11-4 Calculation of a Rocket Propellant Charge .................. . 22
11-5 Gas Generator .......................................... . 24
11-6 Calculation of a Gas Generator Propellant Charge ........... . 24
REFERENCES ........................................... . 24

CHAPTER 3
PHYSICAL PROPERTIES REQUIREMENTS

12 GENERAL................................................ 27
13 DENSITY...................... . .......................... 27
14 GRAVIMETRIC DENSITY....... . ...................... . .. 27
15 HYGROSCOPICITY....................................... 27
!6 COEFFICIENT OF THERMAL EXPANSION................ 28
17 THERMAL CONDUCTIVITY................... .. .. . ...... 28
18 MECHANICAL PROPERTIES.............................. 28
18-1 Ultimate Tensile Strength........ . .... . .... . . .. .. ... . ...... 28
18-2 Elongation in Tension.... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
18-3 Modulus in Tension. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
18-4 Stress Relaxation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
18-5 Creep. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
18-6 Compressive Strength. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
18-7 Deformation at Rupture in Compression.... . . . .. .. .. .. . 31
l 8-8 Modulus in Compression. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
18-9 Shear Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
18-10 Brittle Temperature............................... . ....... 31
REFERENCES ................ . .......... , . . . . . . . . . . . . . . . . 31

CHAPTER 4
BLACK POWDER

19 GENERAL........... . .................. . ................. 33


20 APPEARANCE...... .. .............. . ......... . ........... JJ
21 COMPOSITION.................................... . ...... 33
22 GRANULATION..................... . .................... 33
23 THERMOCHEMJSTRY.................... . ............... 33
24 HYGROSCOPICITY....................................... 36
25 SHELF LIFE............................... . .. . ........... 36
26 MANUFACTURING PROCESS ...................... , .... . . 36
27 USES. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
REFERENCES............................................ 41

JV
TABLE OF CONTENTS (Continued)

Paragraph Page
CHAPTER S

CRYSTALLINE MONOPROPELLANTS

28 GENERAL. ................... . .......................... 42


29 NITROGUANIDINE...... . . ........ . ................... 42
30 RDX.. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
31 HMX ..... . ......... . .... . ..................... . .......... 43
32 PETN ..................................................... 43
33 AMMONIUM NITRATE............ . ........... . ... . . ..... 44
34 AMMONIUM PERCHLORATE............. .. .............. 44
REFERENCES.................................. .. ..... 44

CHAPTER 6

PLASTIC MONOPROPELLANTS

35 GENERAL. ............................. . ................ . 45


36 FORMULATION ... .. ............ .. .............. . 45
36-1 Polymer. ......................................... , . . . . . . 45
36-1.1 Nitrocellulose ......................................... . 46
36-1. 1.1 Nitrogen Content. .. . .. .. .. . . . ... .. .................. . 46
36-1.J.2 Solubility ........................................... . 46
36 .J. J.3 Hygroscopicity ... .. .. .. .... .. .... .. ................. . 46
36-1.1.4 Viscosity ........... . ........ . ............. . ..... ... . 48
36-1.2 Other Polymers .... . . .. . . ...... . ....................... . 48
36-2 Stabilizer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . 48
36 .2.1 Diphenylarnine ........... . . ... . .. ..................... . 49
36-2.2 2-Nitrodiphenylamine ........................ . ......... . 49
36-2.3 Ethyl Centralite ............ . .... . .. . . . . ................ . 49
36-3 Oxidant-Type Plasticizers ................................. . 49
36-4 Fuel-Type Plasticizers ....... .. ..... . ........... . ......... . 49
36-5 Additives ......................... . ..................... . 50
37 BALLISTIC CHARACTERISTICS .......................... . 50
38 PHYSICAL PROPERTIES ........... . ... . ............ . ... . . 51
38-1 Ultimate Strength. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
38-2 Deformation at Rupture...... . . . . . . . . . . . . . . . . . . . . . . . . 52
38-3 Cold Flow... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
38-4 Hygroscopicity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
38-5 Density.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
38-6 Vapor Pressure..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
38-7 Coefficient of Thermal Expansion...... . . . . . . . . . . . . . . . . . . . . . 52
38-8 Plasticity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
39 THERMAL PROPERTIES........................... 52
40 USES...................... . .............................. 53
40--1 Gun Propellants... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
40-1. J Propellants for Cannon. . . . . . . . . . . . . . . . . . . . . ..... , . . . . . . 54
40--1.2 Propellants for Small Arms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
40--1.J Propellants for Mortars............ . ............ . ........ 54

v
TABLE OF CONTENTS (Continued)

Paragraph Page
40-2 Rocket and Gas Generator Propellants ..................... . 54
40-2.! Propellants for Rockets .................. . . .. .. . . . . .. .. . . 56
40-2.2 Propellants for Gas Generators .......................... . 56
REFERENCES ...................... .. .. ... . .. ... ... .. .. . . 56

CHAPTER 7
COMPOSITES COMPRISING CRYSTALLINE MONOPROPELLANTS
IN PLASTIC MONOPROPELLANT BINDERS

41 GENERAL............ .. . ... .. .. .... . . . . . ... . ..... . ....... 58


42 FORMULATIONS....................................... . .. 58
43 BALUSTtC CHARACTERISTICS.......... . ... .. . .......... 58
43-1 Non flashing N itroguanidine Propellants. . . . . . . . . . . . . . . . . . . . . 58
43-2 High Force Nitroguanidine Propellants..... .. . .. ... . .... . .. 59
44 PHYSrCAL PROPERTIES.................................. 59
45 THERMAL PROPERTIES........ . ... . . .. .. ...... .. .. . . .. .. 61
46 MANUFACTURING PROCESS................ . ............ 61
REFERENCES................... . .. . . .. . . . ... .. .. .. .. .. .. 61

CHAPTER 8
MANUFACTURING PROCESSES FOR SMOKELESS POWDER

47 GENERAL ......................... , .... . ........ ,.... . . .. 62


48 NITROCELLULOSE... .. .. .. . . .. . .... . ... . ... . ............ 62
48-1 Nitrogen Content...... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
48-2 Solubility. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
48-3 Viscosity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
48-4 Significance of Nitrocellulose Properties...... . .... . .. .. .. . . .. 66
49 SOLVENT EXTRUSION................................... 66
49-1 Mixing...................... .. .. .. ... . .... . .. . ... . .... . . 67
49-1.l Premixing Operations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
49-1.2 Post-Sigma Blade Mixing Operations........ . . . . . . . . . . . . . . 68
49-2 Forming ...... , ....................... . . , .. , . . . . . . . . . . . . . 72
49-3 Removal of Solvent. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
49-4 Finishing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
49-5 Blending...... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
49-6 Propellants Made by Solvent Extrusion ... , . . . . . . . . . . . . . . . . . . 72
50 SOLVENT EMULSION (BALL POWDER) PROCESS......... 74
50-I Forming Operations......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
50-2 Incorporation of Plasticizers................... . . . . . . . . . . . . . 75
50-3 Finishing Operations..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
51 ROLLED SHEET PROCESS.... . .. ... . . . .. .. .. .. . . . . ....... 77
51-1 Mixing .............................................. ,... 77
51-2 Rolling.... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
5!-3 Finishing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80

vi
TABLE OF CONTENTS (Continued)

Paragraph Page
52 SOLVENTLESS EXTRUSION PROCESS . . . ....... .. .. .. . ... . 80
52-l Extrusion .. . ... ... .. ....... ... ... .... . ........ ... ... . _. . . 80
52-2 Finishing. . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
52-3 Flaws ... ............. . . ...... .. ... . .... . ... .. .... .. .. . . . 84
53 CAST DOUBLE-BASE PROCESS... .... .. ........ . .... ... .. 84
53-l Casting .... .... . ....... ... ............ . . .... ... .. ........ 85
53-2 Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
53-3 Physical Strength . .. .. . . ... . . . ......... . ............ _.... . 88
53-4 Uses of Propellants Made by Cast Double-Base Process ........ 88
54 SLURRY CASTING PROCESS.. . ... .......... .. ........... 88
REFERENCES .. .. . .... .. ..... . . . .... ........ . ......... ... 88
CHAPTER 9
FUEL BINDER COMPOSITES
55 GENERAL. ................... . ......... . ... . ... _.. . ...... 89
56 CHOICE OF OXIDIZER... . ... . ........................... 89
56-1 Potassium Perchlorate........... . ...... . ...... . ... . ....... 90
56-2 Ammonium Perchlorate .. , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
56-3 Lithium Perchlorate ..... _.. , ..... _........... . . _.. . ...... 93
56-4 Ammonium Nitrate... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
56-5 Mixed Oxidizers ..... , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
57 VOLUMETRIC RELATION OF OXIDIZER TO BINDER ..... 94
58 CHOICE OF BINDER...................................... 94
58-l Asphalt. .......... _. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
58-2 Polyisobutene. _....... , .... , _. . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
58-3 Elastomeric Binders ......... _. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
58-3.J Polysulfide Rubber.................................... . . 95
58-3.2 Polyurethane Rubber. , ... , . . . ................. , . . . . . . . . 98
58-3.3 Butadiene-Acrylic Acid Copolymer Rubber, PBAA... . ...... 99
58-3.4 Poly(vinyl Chloride) . . ... . ,........................... ... 99
58-3.5 Elastomeric Binders for Cartridge-Loaded Grains ..... . .. ... IOI
58-4 Thermoplastic Synthetic Polymer Binders for Cartridge-Loaded
Grains .. . ... . .. . .. .. , ... , ... . , ..... ... . ..... ...... ... .. 102
58-5 Cellulose Acetate .. . .... . ..... . ..... . ............... . ..... J02
58-6 Other Binder Systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I 02
REFERENCES ... ... . _.. . . ...... .... ................ Jl l
CHAPTER 10
INERT SIMULANTS FOR PROPELLANTS
59 GENERAL ... . . ..................... . .... .... ...... ... ... _ 112
60 MOCK-UPS . . . .. . .... _.. .. ........ . .... _.. _. . . .. . .. .. . ... . 112
61 SIMULANTS TO REPRODUCE PHYSICAL PROPERTIES .. _ J 12
62 SIMULANTS TO REPRODUCE MANUFACTURING PROP-
ERTIES .. . .. .. ..... _............................ .. ... .. . 112
63 SEMlllVE ....... __ .................. . . ... . ... .. .... . .. . . . J 13
REFERENCES .. .. ........ .......... . ...... . .. . .. ........ . 113
GLOSSARY.......... . ........................... .. . 114
INDEX ..................... . JJ7

vii
LIST OF ILLUSTRATIONS
Figure Title Page
l Reduced specific impulse versus area ratio and gamma......... . . 5
2 Burning of solid monopropel\ant.............................. 12
3 Rate-pressure relationship of propellants for which r = bP"...... 13
4 Rate-pressure relationship of plateau propellants. . . . . . . . . . . . . . . . 13
5 Rate-pressure relationship of mesa propellants. . . . . . . . . . . . . . . . . . I4
6 Burning of composite prope!lants-fi\1er rate faster than binder... 16
7 Burning of composite propellant-filler rate slower than binder.. . 16
8 Neutral geometry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
9 Rod and shell grain.,,., , , . , .. , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
I0 Star-perforated grain.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Jl Slotted-tu be grain. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
12 Progressive geometry........................................ 18
13 Multiple-perforated cylinder. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
14 Degressive geometry................. . .... . .... . ............. 19
15 Gun cycle....... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
16 Closed bomb assembly.. . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . . . . 21
17 Closed bomb record....................... . ................. 21
18 Catapult cycle...... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
19 Rocket motor cycle..................... . ................... 22
20 Tensile test setup. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
21 Tensile test record showing derivation of ultimate strength, elonga-
tion, and modulus........................................ 30
22 Black powder, grade FFFFG, 8X magnification................. 34
23 Black powder manufacturing process. . . . . . . . . . . . . . . . . . . . . . . . . . 37
24 Black powder wheel mill. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
25 Black powder press . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
26 Nitrocellulose monopropellant system. . . . . . . . . . . . . . . . . . . . . 45
27 Cross section of grain of IM R smokeless powder for small arms,
photographed in ultraviolet light, I l 2X magnification.. . . . . . . . 47
28 Physical properties versus polymer concentration. . . . . . . . . . . . . . . . 51
29 Relationships among T~. F, and Q for gun propellants........ . . 53
30 Specific impulse of dou hie-base rocket propellants as a function
ofTp .................................................... 54
31 Burning rates of double-base rocket and gas generator prope1iants 55
32 Cross section of triple-base gun propellant grain, crossed nicols,
32X magnification. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
33 Nitrocellulose manufacture........... . ....................... 62
34 Cellulose nitrator. ........... . . . .... . . . , . . . . . . . .. . . . . . . . . . . 63
35 Nitrocellulose wringers ...... . ............ . ........ _.... . . . . . 64
36 Nitrocellulose boiling tubs..... . ..... . .... . . . . . . . . . . . . . . . . . . . 65
37 Solvent extrusion process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
38 Sigma blade mixer ................................ _. . . . . . . . . 68
39 Schraeder mixer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
40 Macera tor. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
41 Macaroni and blocking presses. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
42 Cutting machine. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
43 Sweetie barrel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74

viii
LIST OF ILLUSTRATIONS (Continued)

Figure Title Page


44 Solvent emulsion process. __ ........................ . ..... . 75
45 Ball powder .... _ .......... . ... ... ... .. .. .. ........ .. ... . 76
46 Still. ....... _.......................................... . .. . 77
47 Rolled sheet process .... . . . .. .. .. . . .. .. . . .. .. . .... . .. - . .... . . 78
48 Roll mill_ ................................................. . 78
49 Slitter .............. _....... . ............... .. .. . ... .. ... . . 79
50 Trench mortar increments ................................... . 81
51 Solventless extrusion process .... . .. ... .... . ... . ... ... ... .. .. . 81
52 Sol ventless extruded shapes ................................. . 82
53 Carpet rolling ............... . . . . . . . .. .. .... .. ... . .... . .... . 83
54 Solventless extrusion press .......................... . ....... . 84
55 Cast double-base process ...... . . . . .. .. .... . ... .. .. .... . . ... . . 85
56 Mold parts ....................................... _........ . 85
57 Casting setup .... . . . .. . . .. . . .. .. .. ... . . . .. . ... ...... .. ..... . 86
58 Cast grain ........................................... . 87
59 Specific impulse, l.,p, and flame temperature, Tp, of NH 4C l 0 4 -fuel
binder composites ........................................ . 91
60 Burning rate, r, at lOOO psi, ambient temperature or NH.iCI 0 4 -fuel
binder composites .................... _ ................... . 92
61 Specific impulses, /P and flame temperatures, T1,, of NH 4 N0 3-fuel
binder composites ........................................ . 93
62 Slurry casting process .... _ ........ . ....... _ . . ......... . .... . 95
63 Sigma blade mixer (200 gallon) ................... .. . _ . . .. . . . 96
64 Vertical mixer (300 gallon) .......... _...... . . . _.. . .. . ....... . 97
65 Mandrel for medium size rocket motor. ............. _........ . 98
66 Medium size case-bonded grain with a 5-point star configuration .. 99
67 \-inch extruder for poly (vinyl chloride) propellant. ............ . 100
68 Extrusion of wired grain .......... __ .......... _......... . ... . 101
69 Extrusion process for fuel binder composites .. _.. . . ..... .. .... . 102
70 Blocking press_ ................................. . ... . ...... . 103
71 Extrusion press ........................................... . . 104
72 Compression molding process for fuel binder composites .... _.. . . 104
73 Compressing stacked disks ................. __ . _ ........ . . ... . 105
74 Machining outside diameter of grain ...................... . .. . 106
75 Jato grains .................................. . .... . ... .. ... . 107
76 Finished jatos ..... _ .......................... __ .. _........ . 108
77 Individual segment (50 pounds) of !000-pound segmented grain .. 109
78 Segmented grain ( 1000 pounds) ... _.......................... . 110

ix
LIST OF TABLES

~k Thk p~
l Reduced characteristic velocity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2 The rmochemical constants fo r Hirschfelder-Sherman calculation . . 8
3 Nominal compositions of black powder available in the United
States. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
4 Granulations of potassium nitrate black powders ... . .. . . . . . . . . . . 35
S Granulations of sodium nitrate black powders .. .. . . . . . . . . . . . . . . 36
6 Consumption of black blasting powder (all types) in the United
States. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
7 Physical and ballistic parameters of crystalline monopropellants . . 42
8 Hygroscopicity of nitrocellulose....... . . . . .. . . . . . . . . . . . . . . . . . . 48
9 Nonflashing propellants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
10 High force propel lants. ... .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
11 Oxidizers for fuel binder composites. . .. ... .... . ..... . . . . . . . . . . 89
12 Hypothetical fuel binder CHu . .. . . .. . . ... . ............. .. . . . 90
13 Hypothetical propellants..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
14 Oxidizer loading versus binder density pe r unit volume.... . . . . . . 94

x
LIST OF SYMBOLS

a == a COi1Stant I = ingredient in propellant composition


a = acceleration 1 = total impulse
a = time rate of acceleration = specific impulse
a (subscript) = atmospheric = calculated thermodynamic specific im-
av (subscript) = average pulse
Ab = area of burning surface S= 1,11 (del) = measured specific impulse at nonstand-
A. = area of no22le exit ard conditions
j (subscript) = partial value contributed by product
A,, = port area
A1 = nozzle throat area
J = product gas constituent
k = erosion constant
b = a constant
K = a constant
b' = a constant K = Kelvin (temperature)
b" = a constant K = ratio of initial propellant burning surface
c (subscript) = chamber Ab
c* = characteristic velocity to nozzle throat area = A,
c: = calculated thermodynamic characteristic K1 = eros1v1ty constant
velocity I (subscript) = liquid state
C = concentration of polymer in solution L = distance downstream from the stagna-
l tion point
C0 = mass flow factor == --;
c L = grain length
CF = thrust coefficient M = molecular weight of combustion gases
= number of weight atoms of carbon in 1
== specific gas volume
unit weight of ingredient I in propellant M
composition M1 P = average molecular weight of combustion
c" = molar heat capacity at constant pressure gases at isobaric adiabatic flame tem-
Cv = molar heat capacity at constant volume perature
d = grain diameter MT" = average molecular weight of combustion
D. = diameter of nozzle exit gases at isochoric adiabatic flame tem-
D, = diameter of nozzle throat perature
e = base of natural logarithms n = exponent in de Saint Robert burning rate
e (subscript) =exit equation, r = bP"
= internal energy n = gas volume in moles produced from unit
t:i..E = heat of formation = H1
weight of propellant = ~
/ (subscript) =partial value contributed by fuel
F = specific force or impetus = moles per unit weight of gas at isobaric
F =thrust adiabatic flame temperature
g = acceleration of gravity = moles per unit weight of gas at isochoric
g (subscript) = gaseous state adiabatic flame temperature
G = mass velocity of the gases in the port o (subscript or superscript) = calculated thermo-
Ghp = gas horsepower dynamic value
H = moisture content o (subscript) = initial condition
H1 = heat of formation = t:, ox (subscript) = partial value contributed by oxi-
Hu = heat of explosion = Q dizer
~ = enthalpy change p (subscript) = constant pressure conditions
i (subscript) = partial value contributed by ingre- p = pressure
dient I = chamber pressure
xi
LIST OF SYMBOLS (Continued}

Q = heat of explosion ::: H e;1o - - (overline) = average


r = linear burning rate = a constant
R = Rankine (temperature) = covolume
R . gas constant = R"
::: specific M = nozzle divergence half-angle
f1 = a constant
R0 = universal gas constant
f3 = volumetric cDefficient of thermal expan-
RF = relative force sion
RH = relative humidity
RQ = relative quickness y = ratio of specific heats = ~P u
s (subscript) ::: solid scare . . A.
S = area of burning surface t = nozzle-expansion area ratio = A;
S ::::: tensile stress = viscosity of solution
Sb :::: tensile stress at break :::: viscosity of solvent
S1 = final area of surface after burning
S, = initial area of surface == relative viscosity
snl = maximum stress
= nozzle divergence loss factor
=time
= propellant mass ratio, ratio of propellant
tb = burning time
mass of any stage to gross mass of that
t (subscript) ::: throat condition
stage
T = absolute temperature
T~ = initial temperature rrp == temperature coefficient of pressure at
T4 = pyrolysis temperature constant pressure-rate ratio = (0~:) P
T0 ::::: reference temperature

T0 = isobaric adiabatic flame temperature temperature coefficient of pressure at


T, = temperature at throat
Tu = isochoric adiabatic flame temperature constant Kvalue = (olnP)
oT ir
u = a constant p =density
v (subscript) = constant volume conditions
V =velocity = specific volume
V =volume p
V,, = volume of propellant aP = temperature coefficient of burning rate at
0
W :::: weight
. h . dW
constant pressure= ( ~;.') P
W = weig t burning rate = ~
aK = temperature coefficient of burning rate at
x = weight fraction 0
y == volume fraction constant K value = ( ~;:) K.
(superscript dot) = time derivative

xii
SOLID PROPELLANTS
PART ONE

CHAPTER 1

INTRODUCTION

1. Purpose. This Handbook is intended to pro- MIL-STD-444, Merriam-Webster's unabridged


vide a general description of solid propellants dictionary, or common usage.
used in small arms, artillery, rockets, and some
3. Plan. fn Chapter 2 is described how the
other devices. It is assumed that the reader has as
figures of merit-specific force for gun propel-
background the equivalent of an undergraduate
lants and specific impulse or characteristic velocity
degree in engineering or physical science, but" no
for rocket propellants-are derived from thermo-
previous experience in propellants or ballistics .
chemical data and empirically verified. Also in
2. Definitions. A solid propellant is a chemical Chapter 2 is discussed the mechanism of burning
or a mixture of chemicals which when ignited of propellants and the scheduling of gas evolution
burns in the substantial absence of atmospheric to meet the requirements of various engines in
oxygen at a controlled rate and evolves gas capable which prope\l:mls are used, such as guns, cata-
of performing work. In order to discuss certain pults, rockets, and gas generators. A few simple
phenomena, notably burning and detonation proc- numerical examples are given by way of illustra-
esses, it is necessary to define certain terms that tion, but detailed discussion of the ballistics of
are used with meanings differing significantly from such engines is omitted as being beyond the scope
those given in MIL-STD-444 . 1 The more im- of this work and available elsewhere. In Chapter 3
portant of these are: appears a discussion of certain physical properties
of propellants as related to system requirements.
A (solid) monopropellant is a single physical
fn Chapters 4-9 conventional propellants are dis-
phase comprising both oxidizing and fuel ele-
cussed, arranged according to their physical struc-
ments. Tills is analogous to common usage in
ture . Black powder is presented in Chapter 4.
the liquid propellant field describing a single--
Crystalline monopropellants appear in Chapter
phase liquid propellant.
5. Plastic monopropellants, commonly known as
A filler is a discrete material dispersed in
single-base and double-base propellants, appear in
substantial quantity in the continuous or binder
Chapter 6. These common tenns can be somewhat
phase of a composite propellant.
confusing, since the class contains propellants
Deflagration is a burning process in a solid
comprising, for example , cellulose acetate and
system, comprising both oxidant and fuel, in
nitroglycerin which are difficult to assign to either
which the reaction front advances at less than
ingle- or double-base . Composites comprising
sonic velocity and gaseous products if produced
monopropellant binder and m()noprnpe!lant filler,
move away from unreacted material. Whether
commonly known as triple-base, appear in Chap-
or not explosion occurs as a result of deftagra-
ter 7. Again the common term can be confusing,
tion depends on confinement.
as when a nitroguanidine propellant with a single-
None of these definitions is used for the first base (nitrocellulose) binder is to be described.
ti.me in this Handbook. Other definitions are intro- Manufacturing processes for the propellants of
duced in the text at appropriate places. Unless Chapters 6 and 7 are given in Chapter 8. Fuel
otherwise noted, definitions are in accord with binder composites are discussed in Chapter 9. A
Numbers refer to items Listed a.s References at the eod discussion of inert simulants, or dummies, for pro-
of each chapter. pellants is given in Chapter 10. Higher energy
systems are discussed in ORDP 20-176, Solid Pro- REFERENCES
pellants, Part Two (C), 1. MILSTD-444, Military Standard, Nomenclature and
Literature consulted in the preparation of this Definitions in the A.mm11ni1ion Area, Department of
Defense, 6 February 1959 .
Handbook includes publications early in 1960.
2. SPIA/M2, Propellant Manual, Solid Propellant In-
The reader is referred to SPIA/M2, 2 in which will formation Agency, Johns Hopkins University, CON-
be found data sheets for all of the propellants FIDENTIAL.
developed and used within the Department of De-
fense including those that will appear subsequent
to the publication of this Handbook.

2
CHAPTER 2

EVOLUTION OF GASES BY PROPELLANTS


4. General. The devices in which propeUants where R 0 is the universal gas constant. The term
are commonly used, be they devices, such as guns a is known as the covolume and may be thought
that comprise moving pistons, or vented vessels of as the space occupied by the gas when com-
acquiring momentum by discharge of gas, ,are de- pressed to the limit. It has the empirical value of
vices that convert heat energy into mechanical about I cc per gram for most propellants.' The
energy. They thus fall into the general classifica- significance of the covolume correction may be
tion of heat engines. The propellant gas is then shown by some simple numerical examples. Under
the working fluid that actuates heat engines. In standard conditions of temperature and pressure
solid propellant heat engines the working fluid is (273K, I atm), 1 gram of gas of molecular weight
generated in situ by burning the propellant within
22.4 occupies 1000 cc. A temperature of 2730K
the engine. The general problem in fitting a solid
and a pressure of 68 atm ( 1000 psi) are conditions
propellant to a heat engine is the generation of gas
typical of rocket ballistics. Under these circum-
of specified properties at a specified rate which is
a function of time. The specifications of gas prop- stances
erties and rate of generation are not usually inde- 2730 I
pendent of each other. Thus a given problem may V - a = 1000 X
273
X 68 = 147 CC

be solved by using gas with one set of properties


For I percent accuracy, V - a does not differ
at one rate schedule or, alternately, by using a dif-
significantly from V. It is customary, therefore, in
ferent set of gas properties on a correspondingly
rocket balJiscics to ignore the covolume correction
different rate schedule. The properties of the gas
are determined by the composition of the propel- and use the perfect gas equation
lant. The derivation of the gas properties from the
PV = WR 0 T (la)
composition is known as thermochemistry of pro- M
pellants. The rate of gas generation is determined
as the equation of state. On the other hand,
by the linear rate of burning and charge geom-
whereas we encounter similar temperatures in gun
etry. Of these, the linear burning rate as a func-
ballistics, the pressures are higher. Taking 3000
tion of pressure is a propellant property. System
atm (44000 psi) as typical, for 1 gram of gas
pressure and charge geometry are controlled at
least in part by the end-item specification. The 2730 l
overall problem of selecling a propellant formula-
V - a== 1000 X
273
X
3000
= 3.3 CC
tion and geometry to meet a given end-item per- Under these conditions, V - a differs significantly
formance specification is an exercise in interior from V, and the covolume correction must be
ballistics. Because the propellant developer owes made . For precise calculations, other equations of
the ballistician both thermochemical data and rate state of greater precision than Equation 1 are used .
versus pressure data, he should have a qualitative
These equations are more complex and contain
knowledge of interior ballistics in order to perform constants the physical significance of which is more
his function intelligently. difficult to understand . In such calculations the
5. Equation of state. The classical equation of departure from the perfect gas law is still called
state used by ballisticians is known as the Noble- the covolume correction . The covolume if evalu-
A bel equation. For unit mass of propeUant it is ated is no longer a constant bl!t is a variable with
usually written a value still in the neighborhood of Noble-Abel's a.

P(V- a)= RT 6. Ballistic parameters. Different systemsi-s of


interior ballistics have been developed by gun bal-
where R is the gas constant per unit mass o( pro-
listicians on the one hand and by rocket ballis-
pellan t, or more generally
ticians on the other. Both types of system depend
P(V - aW) - WRaT on the same primary thermochemical properties
- M (I)
of propellant gases, but use different parameters as

3
working tools . Thus, as a measure of the ability TABLE 1. REDUCED CHARACTERISTIC
of the combustion products of propellants to per- VELOCITY
form in their respective heat engines, gun ballis-
ticians use the parameter specific force (ofteo ~ I y+I

abbreviated to force), or impetus, F. Rocket bal-


Jisticians use for the same purpose characteristic y J=(~)2(~)~
velocity, c*, or specifi.c impulse, /P Auxiliary 1.1 s 1.566
power unit engineers sometimes use gas horse- L.20 1.542
power, Ghp . l.25 1.520
!.30 1.499
6-1. Specific force. Specific force, F, is a meas- L35 1.479
ure of the ability of the propellant gas to perform 1.40 1.461
work. Tt is defined by the equation
F = RoT.. (2 )
M characteristic velocity with changing y points out
and is ex.pressed in terms of foot-pounds per that the characteristic velocity is a stronger func-
pound.
tion of: than of y.
6-2. Characteristic velocity. Characteristic ve-
locity, c*, is not a significant physical quantity . 6-4. Specific impulse. Specific impulse, / 1 p , is
defined as the impulse (force x time) delivered
It is defined as P,~ iC, where P, is chamber pres- by burning a unit weight of propellant in a rocket
W
chamber. From rocket ballistic theory' 0 can be
sure, A 1 is nozzle throat area, and W is burning derived the equation
rate in pounds per second. Mathematical analysis 9

/~P= g~~:o'!_p1) [} -(~:)Y~I


shows that it can be computed* from the thermo-
dynamic properties of the gas as (4)
y+ l
(v +2 1)
~
.... _ ~ gR T ~
2 <-Y- il
Note that this parameter becomes a thermo-
C0 (3)
- yM dynamic function of the propellant only when the

6-3. Reduced characteristic velocity. Equation ratio ~ is specified. The current United States
3 may be rewritten c

convention is to consider P,, as one atmosphere

~p = (~)2 (y ~
L
lr(y-" y +1
(3a)
( 14. 7 psi) and Pc as 1000 psi unless otherwise
specified . Implied in this formula is the assump-
tion of zero half-angle of nozzle expansion. See
'\/--,;, c: also Paragraph 8-4.
lgR T 11
The quantity -'\) M
may be caJled the re- 6-5. Reduced specific impulse. Equation 4 may
be rewritten
duced characteristic velocity; it is dimensionless
and is a fWJction only of the specific heat ratio, y.
In Table 1 are shown the values of the reduced l~,, I
/RoT,,=,J-1.L_
[1-(Pa)J.l'...=-1
Y (4a)
characteristic velocity for different values of y.
'\j gM \J y - 1 Pc
The characteristic velocity is obtained by multiply-
l~p
ing the reduced characteristic velocity by,/g~TP .
The comparatively small change of the reduced
The quantity~ is known as the reduced
specific impulse; it is dimensionless, and depends
Compuled tbermodyoamic values a.re denoted by sub-
script or superscripL o, ro difiereoliate from values de-
only on the pressure ratio, :a.
c
and the specific
pending on direct measurements. See aJso Paragraph 8-3. heat ratio, y. A plot of the reduced specific im-
4
2.8
w
V> 2.7
_J
:::>
CL 2.6
~
2.5
0
u... 2.4
0
w 23
CL
en
2.2
0
w
0 2.1
:::i
Cl
w 2 .0 11 =1.1:5
fl::
11 =1.20
1.9 ~ =12:5
a :o 1,JO
1.8
'= J.35
'= 1.40
0.01 002 003 0.04. 0.05 0.06 0.07 0.08 0.09 0 .10

po/,
Pe
Figure J. Reduced Specific Impulse Versus Area Ratio and Gamma

pulse as a function of pressure ratio for various Here again is a parameter that does not become
y's is shown in Figure 1. The use of this chart in a thermodynamic function of the propellant unless
calculating specific impulse is illustrated :n the
numerical example, Paragraph 7-7.
the ratio ~: is specified. There appears to be no
.
United States convention 'h respect to Pi.
wit P2 G as
6-6. Volume specific impulse. The product of
specific impulse and density, expressed in units horsepower is therefore not purely a propellant
of pound-seconds per cubic inch, is known as the property.
volume specific impulse. If a proposed rocket 7, Tbermocbemistry. Thermochemical data re-
motor has a fixed propellant envelope, it will gen- quired for the determination of the above param-
erate impulse roughly in proportion to its volume eters are the burning temperatures at constant
specific impulse. Thus a propellant with lower spe- volume and at constant pressure, Tv and Tp, re-
cific impulse but higher density may sometimes
outperform one with higher specific impulse and spectively, specific gas volume, ~ and, ratio of
lower density. If the proposed rocket motor re- specific heats, y. The burning temperatures and
quires a given total impulse but has no envelope composition of the product gas are also impor-
requirement, the volume of the propellant, and tant from the standpoint of compatibiJicy with the
hence the size and weight of the (inert) cham- surroundings. In propellants the surroundings in-
ber, will be lower the higher the volume specific clude the inert parts of the heat engine which must
impulse. remain intact th.rough the cycle or even have a
service life of many cycles.
6-7. Gas horsepower. Gas horsepower is de-
fined as 7-1. Specific gas volume. Specific gas volume,

Ghp = W
550
x ___J__ RoT[ I -
1 M
(P2)x
P
~ t] (5)
~ is the number of weight moles of gas pro-
y - 1 duced in the burning of a unit weight of propel-
!ant. Jn all cases where only gaseous products where t.1 is the heat of formation of product J
result, M is the average molecular weight of the per mole.
product gas. The gas volume is determined from The quantities y, are derived from Equations
the conservation equations for the elements 6a-6c and various gas equilibrium equations, of
which the most important is the water gas equi-
IC= [C0 2 ) + [CO] (6a) librium
IH = 2[H 2 J + 2[H 2 0] +[HO] (6b)
IN= 2[N 2 ] (6c) (COUH20J _ K T (13)
[C02J[H2l - 0
!O = (HO] (6d)
IO= [CO] + 2[C0 2 ] + !H 2 0 (6e)
[C0 2 ] + [CO] + [H 2 l + [H20J + In actual systems there may be found small
[Nz] + [HO] = ~ (7) quantities of constituents other than those dis-
cussed above, such as CH 1 , NH 3 , NO, OH, H,
~= !C + Y2rN + Y.2!.H + lh!.0 (8) 0, and N, as well as products of other atomic
species if present in the propellant. For each such
In these equations, !C, e.g., is the total number constituent there is available an equilibrium con-
of weight atoms of carbon in a unit weight of pro- stant K,(T) similar to K 0 (T) (Equation 13) and
pellant and (C0 2 ) is the number of weight moles an estimate of its molar heat capacity.
of C0 2 in the gas from the unit weight of pro- The constants KiCJ) and the various C,,'s and
pellant. If X; is the weight fraction of ingredient I t:i.E's have been quite precisely evaluated as func-
in the propellant composition and C. the number tions of temperature, T .11
of weight atoms of carbon in unit weight of/, then
7-3. Flame temperature nt constant pressure.
(9)
The calculation of T,, is similar to that of T ,,,
!.H, !N, and !Cl are derived in the same way . except that instead of Equation 10 we must use
the foUowing
7-2. Flame temperature al constant volume.
The fl.arne temperature at constant volume is de-
(14)
termined by solving the equation

(10)
where C,, i. is the heat capacity at constant pres-
sure of gas constituent /.
Since burning is now at constant pressure, en-
where Yi is the mole (volume) fraction of a prod- thalpy instead of heat of formation must be used.
uct gas constituent J, e.g., C0 2 , in the gases
formed from the propellant and C,, 1 is the molar
heat capacity of the same gas constituent. The
heat of explosion or calorific value of the propel-
lant, Q, usually expressed in calories per gram, is
the difference at reference temperature, T 0 , be-
rween the he.at of formation of the products and
the heat of formation of the propellant. 7-4. Ratio of specific bents. The value of y for
a propellant is the weighted average of the y's of
-Q = 6produclo - li.Epropellol (11) the gas constituents
Assuming no heat effect of mixing
( 17)
6.Eoropellant = !(x~l) (12a)
where t:i.E; is the heat of formation of ingredient I
The values of y used are not the ratios of heat
per gram .
capacities at room temperature, but the ratios at
operating temperatures of the beat engines con-
cerned.

6
7-5. Exact calculation of flame temperatnre and
The gas volume, ~', is calculated by Equation 8 ,
product composition. The calculation of the flame
temperature and product gas composition is done and the force, F, by Equation 2.
by trial, starting usually with an assumed tempera- If T, is above 3000K, a better approximation
ture . This is an iterative process anti is profitably of T, . is given by the relationship
done with a machine calculator, particularly when .
gas equilibria other than the water gas equilibrium T,. = 3000 + 6046{- CC+ 0.01185) +
must be considered. Programs"H have been
worked out for such calculations, assuming essen- [(C,. + 0.01185) 2 + 1} (19)
tially only adiabatic conditions and chemical and 3.308(10- 4 )( - 500C,.)]2
thennodynamic equilibria, to give results of accu-
racy limited only by the thennodynamic data of In order to calculate characteristic velocity
the individual species considered. These programs from Equation 3 or specific impulse from Equa-
also are used for calculated specific impulse on the tion 4 (see also Reference l 7) we need the flame
basis of either frozen composition flow or equilib- temperature at constant pressure, T P and the ratio
rium flow through the nozzle . A JANAF Thermo- of specific heats, y, at the working temperature.
chemical Panel exists for the coordination of The value of y is given by the relationsh.ip' 8
thermochemical data and calculating pr"ocedures.
The exact calculation, even with a sophisticated y == 1 + 1.987 (20)
machine caJculator, is time consuming. Conse- C,.M
quently nearly every propellant development facil- from which TP is calculated by the equation
ity has for internal use a short-cul calculation
yielding approximate results useful for screening - T,.
and program guidance. Many of the data reported Tp- (21)
y
in the literature, including some SPIA/ M2 data
sheets, are the results of such approximate calcu- Additive constants for a number of propellant
lations and should be confirmed by exact calcula- ingredients are given in Table 2. Constants for
tions before important decisions are based on them. other organic ingredients can be estimated from
Two approximate calculations that have been the relationships 19
used by more than one faciJity are described in
Paragraphs 7-6 and 7-8.
(8)
7-6. Hirschfelder-Sherman calculation." 1t is
possible 16 to calculate Q from additive constants C,. I. = 1.620C, + 3.265Hi + S. 1930; + 3.384N(
Q, which are defined as the contributions of ingre- (22)
dients I to the heats of explosion of propellants
containing them . The Hirschfelder-Sherman calcu- Q, = (-AE); - 67421[2C1 + lhH( - 0,] (23)
lation takes as the reference temperature 2500K.
The beat of explosion, Q, of the propellant differs
E, = (-~); - !32771C -
from the heat required to bring the combustion
40026H, + 518190, - 6724N;
products rr - ~00K by an amount , which can
also be ted from addinve constants ,
where (-6), is the heat of combustion of ingre-
which are , Jperties of the ; ,1gredients / . Finally,
dient /.
the heat capacity of the pr.Jduct gas at 2500K is
Within the range 2000 to 4000K for T" this
estimated from additive constants c ... which are method gives results within a few percent of the
properties of the ingredients /. These heat capaci-
exact method. The method should not be used
ties are assumed constant for the interval from
for propellants with T" over 4000K as it does
2000K to 3000K. The burning temperature at
not allow for dissociation to free radicals, such as
constant volume, Tu, is then given by the equation
H, OH, and CI. lt should also not be used for
propellants yielding a substantial amount of con-
Tv == 2500 + C, ( 18) densed exhaust_

7
TABLE 2. THERMOCHEMICAL CONSTANTS FOR
HIRSCHFELDER-SHERt\'IAN CALCULATION' 1

Q, c,1 Et (b}
Acetone -1938 O.SJ04 -2842.S 0.10331
Ammonium dichromaie 1290 0.2700 610 0.0200
Ammonium nitrate 1450 0.4424 405.l 0.03748
Ammonium perchlorate 1603 0.3167 800.22 0.2128
Ammooium picratc 539 0.3213 -117 0.04470
Asphalt -2302 0.2179 -2305 0.09450
Bd-MVP copolymer (903 buudicne, 103 2-methy!-5-vinylpyridioe
copolymer) -2741 0.4132 -3183 0.1 !544
Butyl c:arbitol adipatc -1836 0.4923 -2629 0.09899
Butyl carbitol formal -1802 0.5229 -2652 0.10403
carbon black -3330 0.1349 -3187.5 0.08326
Cellulose acetate -1263 0.3953 -1971 0.06929
Diallyl maleatc -1358 0.3872 -1951 0.08155
Oi-n-butyl phthalate -2071 0.4258 -2656 0.09701
Dibutyl sebacate -2395 0.5108 -3159 0.1113
Di-(2-ethylhexyl) azelate -2612 0.5272 -2272 0.11876
Diethyl phthalatc -1760 0.3866 -2348.7 0.08550
Diglycol dinitratc 1073 0.3857 232.4 0.04589
Dinitropheooll:yethanol -15 0.3369 -633.4 0.05698
Dioctyl phtbalate -2372 0.4650 -3020 0.11026
Dipheoylamine -2684 0.3471 -3010 0.10637
Dipbenylguanidine -2270 0.3476 -2626 0.0994!
Ether -2007 0.5910 -2958 0.12143
Ethyl alcohol -1716 0.6083 -2785 0.10854
Ethyl ceotralite -2412 0.3905 -2766 0.10434
Grapb.ite -3370 0.1349 -3234 0.08326
GR-I rubber -3257 0.5719 -4006 0.14235
HMX, Cyclotetramethylenetetranitrarninc 1321 0.3414 575 0.0405
~d st.earatc -2000 0.3976 -2440 0.09180
M&V -1827 0.3976 -2440 0.09180
N-Methyl-p-oitroaniliDe -1095 0.35808 -1625 0.07887
Metriol trinitrate 1189 0.3052 377 0.04313
Mineral jelly -3302 0.5811 -475 0.1426
Nitrocellulose, 12.23 N 900 0.3478 137.7 0.04127
Nitrocellulose, 12.63 N 956 0.3454 198.9 0.04040
Nitrocellulose, 13.15% N 1033 0.3421 283.I 0.03920

8
TABLE 2. THERMOCHEMICAL CONSTANTS FOR
HIRSCHFELDER-SHERMAN CALCULATIO Nu (Continued)

Q, C.1 Ei. (i),


2-Nitrodiphenylarn(ne -1813 0.3226 -2201 0.08411
Nitroglycerin 1785 0.3438 95!.9 0.03082
N itroguat1idine 713 0.3710 - 68.6 0.04808
PETN, Pcntaerythritol tetran.itratc 1S31 0.3424 727 0.034.'!
Petrin 1202 0.3703 374 0.04109
Polyester -2184 0.3552 -2620 0.09123
Polyisobutene -3228 0.5798 -3981 0.14259
Poly (methyl acrylate) -1404 0.4231 -2111 0.08140
Polystyrene -2983 0.3739 -3309 0.11523
Polyurethat1e -3296 0.4073 -3773 0.10796
Poly(viuyl chloride) -1614 0.2080 -18.Sl 0.05600
Potassium nitrate 1434 0.2158 24.9 0.00989
Potassiwn perchlorate 1667 0.2000 800 0.00722
Potassium sulfate 300 0.1250 -800 0.00514
RDX. Cyclotrimethylenetrinitra.mine 1360 0.3416 615 0.0405
Sucrose octa=t.ate -1121 0.3941 -1825 0,06!}22
Triacetin -1284 0.4191 -1973 0.07333
Trietby!ene glycol dinitTate 750 0.40430 -89.24 0.05412
Trinitrotoluene 491 0.3037 -1!0 0.04843

7-7. Example calcnlation of F, I~ by the c:, lsochoric flame temperature:


Ri.m:hfelder-Sherman method. Consider a propel-
lant of composition: T by Equation 18: 2500
0 + ;~~531 = 4060"K

Nitrocellulose, 12.6% N 0.50 Since this is higher than 3000K, we must calcu-
Nitroglycerin 0.49 late by Equation 19
Ethyl centralite 0.01
Tv :::: 3000 + 6046{- (0 .3451 + 0 .01185) +
From the composition and Table 2, we have [(0.3451 + 0.01185)2 + 3.308 x 10- 4 x

Ingredient
Weight
fractioo x,Q, x,C. x,E, r.;M,
(53 8 .3 - 500 x 0.3451 )ft}
::::: 3855K or 6940R
Nitrocellulc:>se 0.50 47& 0.1727 99.5 0.02020
Force:
Nitroglycerin 0.49 &1S 0.16&5 466.4 0.01510
Ethyl centralite 0.01 -24 0.0039 -27.6 0.00104 F= R;Jv = 1543 x 6940 x 0.03634
Sununal..ions 1.00 1329 0.3451 S38 .3 0.03634 = 389,000 ft-lb/lb

9
Specific heat ratio: 8-1. Measurement of heat of explosion. The
_ I ...1... 1.987 x 0.03634 heat of explosion of a propellant, Q, also known
y- ' 0.3451 1.2092 as the calorific value, is measured by burning in
a bomb calorimeter under an inert atmosphere.
Isobaric flame temperature:
Two types of calorimeters have been in common
TP = ~-~~~ = 3 l 88K or 5738R use. In the Boas calorimeter the loading density,
or weight of propellant per unit volume, is fairly
Characteristic velocity, c!: From Table 1, the high, leading to pressures of some thousands of
reduced characteristic velocity corresponding to pounds. This calorimeter need not be prepressur-
y = 1.209 is 1.540. The characteristic velocity, ized. In a coal calorimeter, the loading density is
c:,is then low and an initial inert gas pressure of some 200
to 300 psi is required. Both types of calorimeter
ct = 1.540 v
32.2 x 1543 x 5738 x 0.03634
give essentially the same values of Q.
= 4950 ft/sec For thermochemical purposes, the observed heat
Specific impulse,//>,,: From Figure 1, the reduced must be corrected for the heat of condensation of
specific impulse corresponding to y = 1.209 and water and for shifting gas equilibrium during the
~: = 0.015 is 2.445. The specific impulse, 1.;, is
cooling of the calorimeter and its contents. This
correction amounts to about 10 percent and may
then be so approximated. 22 Uncorrected calorimetric
2 . 445
I 0
_ ~1543 X 5738 X 0.03604 values, denoted "water liquid," are of considerable
P - 32.2 utility as a quality assurance measure in volume
= 245 lb-sec/lb production of propellants to verify that successive
lots of propellant manufactured to the same for-
7-8. ABL short calculation for specific im-
mula actually duplicate each other within specified
pulse.21 In order to shorten tbe time and com-
limits. The calorimeter test can be run with much
plexity of the exact calculation for specific impulse
less effon and more precision than a complete
of propellants with condensible exhaust, the ABL
chemicaJ analysis. The procedure for the calorim-
method makes a number of simplifying assump-
eter test is given in a Navy Department Bureau
tions. Chief among them are:
of Ordnance report. 23 Calorific values encountered
(a) No product dissociation is considered. in propellants seldom exceed 1500 cal/g and are
(b) A priority system applies to the forma- accordingly much less than for ordinary fuels. The
tion of the products. Thus, oxygen first oxidizes obvious reason for this is that ordinary fuels draw
all light metal, then converts C to CO, then on atmospheric oxygen for their combustion re-
H 2 to H 2 0, and any oxygen still not used up actions, whereas propellants must carry their oxi-
converts CO to C0 2 . dants within themselves in order to function in
(c) Certain latent heats are completely re- the absence of air.
covered during nozzle expansion.
The calculation can be performed with a desk 8-2. Measurement of specific force. Combining
calculator, but is usually done with a larger calcu- Equations I and 2 we get
lator if available.
Results of this calculation may differ from exact p
F =- (V- uW) (25)
calculation results by as much as 3 percent. w
The results do not represent either frozen fl.ow
or equilibrium flow, but agree fairly well with A direct experimental measure of F should then
exact equilibrium fl.ow calculations. be obtained from the pressure developed under
The assumption of no dissociation leads to arti- adiabatic conditions by burning a weight, W, of
ficial values for TP. propellant in a closed chamber of volume, V. Be-
cause truly adiabatic conditions can only be ap-
8. Measurement of ballistic parameters. The proached, a related concept, that of relative force,
empirical determination of the ballistic parameters is used. If equal weights of two propellants with
is discussed in the next few paragraphs. the same burning time are fired consecutively in

IO
the same closed vessel at the same initial tempera- Unless the operating and discharge pressures
ture, W and (V - o:W) are constant. Then are 1000 psi and 14.7 psi, respectively, the meas-
ured I.,. must be corrected to these values. Cor-
F2 ~ F, (;~) rections must be applied also for the divergence
half-angle of the nozzle , since the amount of
F 1 , the force of the standard propellant, is arbi- impulse delivered decreases as nozzle angle in-
trarily assigned the value 100 percent, and the creases.27 The usual convention for half-angle is
relative force, RF, of the propellant under exami- 15 . Part of the difference between I ;P and /, 0
nation becomes is therefore due to the divergence loss. The 15
convention is unfortunately not always observed.
RF=~~ x 100% (26) Some measured I.,p data reported in the literature
have been corrected to zero half-angle. In using
Relative force is used in quality control of gun l , 0 data, one must identify which half-angle cor-
propellants to assure that successive lots of the rection has been used .
same formulation duplicate each other . In develop-
ing a new propellant to replace an existing one, 8-5. Example calculation of 1,9 rom measured
a measurement of relative force is useful as an l,JJ (del) at nonstandard conditions. The following
indication that the relationship between calculated data were taken from an actual rocket firing :
and delivered force is or is not similar to the rela-
tionship for the known standard propellant . The Expansion ratio, re ::::: ~ ',' = 2.779
procedure and description of apparatus for the de- Mean chamber pressure, Pc = 218 psia
termination of relative force may be found in an Nozzle divergence half-angle, a ::::: 20
Army Service Forces Directive. 2 ' Specific heat ratio, y = 1.17
8-3. Measurement o[ characteristic velocity. l,P (del) = 201.3 lb-sec/lb
Delivered or actual characteristic velocity, c*, is The correction of ' ~ (de!) to standard condi-
defined as tions involves the parameter thrust coefficient, CF,
from interior ballistics. The thrust coefficient, de-
c* =- gA,f P dt (27)
w fined as
lt is determined experimentally by static firing of a (29)
weight, W, of propellant in a vented vessel of
known throat area, A 1 , measuring cbe chamber measures the contribution of the nozzle to the
pressure as a function of time, and integrating. rocket thrust. Since c* is independent of discharge
The J ANAF Solid Propellanc Rocket Static Test
Panel has published 21 a survey of existing static conditions, for any given rocket firing i;.. is a
test facilities and is continuing to coordinate test constant independent of nozzle and external con-
procedures. Comparison of c"" wich c: gives a ditions.
measure of the operating efficiency of the vented The thrust coefficient has its maximum value
vessel. In similar heat engines with similar pro- when expansion in the nozzle is to zero pressure
(vacuum) and discharge is also to zero pressure .
pellants,*Co
c*
should remain nearly constant. The For any other exit pressure the vacuum thrust
difference between ct and c* is due largely to
heat losses to the motor walls .
coefficient must be corrected by a term t(;:). If
the ambient pressure differs from the exit pres-
8-4. Measurement o{ specific impulse. Deliv-
ered or actual specific impulse, /, 9 , is defined as sure another correct.ion involving f ( ~:) must be
applied .
1,11 =~ f F dt (28)
Values o( CF and f ( ~:) are obtained from
Th.is parameter is determined also by static firing Thrust Coefficient and Expansion Ratio Tab/es 11
a vented vessel,. but measuring thrust. ,q of which the tabul2.ted C,. is for vacuum discharge

11
and zero divergence angle. The divergence angle primary pyrolytic products are given off already
correction 21 is made by the equation premixed and in proportions ~uch that the final re-
A = 0.5 + 0.5 cos a action of the products among themselves will bring
the gas to flame temperature and thus duplicate the
so that the overall correction becomes hot atmosphere in temperature and compo>ition.
actual C,, == Although the temperature rise and compc,s; .)fl
A[CF (table) - f ( ~:) J+ ( ~: )- (~:) changes are continuous from the unchanged pro-
pellant to the products at flame temperature, it is
For the example at hand, using the table values: convenient for analysis to break the process down
into several phases as represented by Figure 2.
Firing conditions Standard conditions Region A represents the unheated interior portion
Cr 1.54358 1.75284

e (~:) 0.21405 0.13856 ABC DEF' G

A 0 .9699 0 .983
Inserting numerical values, and noting that for
standard conditions P, == P0 A COLD PROPELLANT
9. KEAT(O PROPELLANT
C,. (firing)* == 0.9699( 1.54358 - 0.21405) + C.
0
PYROLYSIS ZON[ tfOAM ZONE\
PRIMARY GASEOUS PVflOLYTtC PROOucrs

0.21405 - 2.779 x ~~-; E. GAS ~EAT ING ZONE (f'I Z Z ZON )


>. GAS REACTION ZONE <F"LAME ZONE)
= 1.316 G BURNEO GAS

Figure 2. Burning of Solid Monopropellanl


Cr (std) = 0.983(1 .75824 - 0.13856)
== l.587
The corrected value of l,P at standard condition of the solid. lo region B a thin layer of the solid
is_, therefore, is being heated to pyrolysis temperature, T 1 In
1.587 region C pyrolysis is taking place and gaseous
201 .3 X l})6" = 242.8 lb-sec/lb products are being formed. The pyrolytic reactions
9. Burning of propellants. Heat will be trans- may or may not involve the formation of liquid
ferred by radiation , conduction, and / or convec- intermediates (foam zone). A layer of primary
tion to the surface of a cold solid propellant gaseous pyrolytic products at temperature T< is
suspended in a hot atmosphere . 1f the solid is region D. Jn region E (fizz zone) these gases are
essentially a nonconductor-of heat, the heated sur- heated to ignition temperature. In this process
face will pyrolize, giving rise to gaseous products they may undergo low temperature reactions of
and exposing new surface to the hot atmosphere. an exothermic character and produce some heat.
The gas in immediate contact with the burning sur- The bulk of the heat is generated in the flame zone,
face29 will be the uncontaminated pyrolytic prod- region F, to yield finally burned gas at tempera-
ucts of the surface, at the temperature of pyrolysis. ture Tin region G.
Moving out from the surface the gases are raised At operating pressures in the neighborhood of
to the temperature of the hot atmosphere and several hundred pounds per square inch and
undergo reactions among themselves and with the higher, the thickness of the regions B through F
atmosphere so that the hot atmosphere continues is small, perhaps of the order of 1O- z inches in
to exist in a state of equilibrium among the sev- total. By operating at greatly reduced pressures
eral chemical species present. If the solid is a one can broaden these regions. The foam zone,
monopropellant and the hot atmosphere comprises fizz zone, and flame zone have been observed in
its combustion products at flame temperature, the experiments of this type. 3
The linear rate of burning of the monopropel-
Since lhis value is a theoretical value derived from
Jant depends on the rate at which the surface
approximate measured parameters, it does not necessarily
agr~ with a value of CY calculated by Equation 29 from receives heat from the surrounding combustion
measured/,, and c . products. Ali exposed surfaces that can "see" the

12
hot combustion products should receive heat at
the same rate and therefore burn at the same rate.
The burning surface should recede by parallel
layers. This conclusion, known as Piobert's Law3'
and first announced for black powder, has been
verified for monopropellants under both rocket
and gun conditions by examination and measure-
ment of partially burned grains. lt appears also to
hold for composite propellants, although the ex-
planation cannot be as simple .
The rate of regression of a burning propellant
surface , measured normal to the surface, is known
as the linear burning rate, r. It is usually expressed
in terms of inches per second. When r is multiplied
by the area of the burning surface, S, and by the
density we have, finally, the weight-or mass-
burninR rare, expressed as pounds per second
LOG PRESSURE
W == rSp (30) Figure 3 . Role-Pressure Relationship of Propellonls

Several factors are recognized as affecting the lor Wnich r = bP"

burning rate . Among these are pressure at which


burning is taking place, initial temperature of the pressures. In this region will be found propellants
propellant, gas velocity over the burning surface, giving the normal straight line log rate versus log
and composition of the propellant. pressure relationship, but also many propellants
9-1. Effect of pressure. Increasing the pressure deviating widely from it. Two types of curves are
at which burning takes place should increase the worthy of special mention.
rate of heat trans(cr from the flame to the pro- PropeUants showing a region of markedly re-
pellant by increasing the density of the gas phase duced n, as shown in Figure 4. are known as
and thereby decreasing the thickness of regions
D and E through which the heat must be trans-
ferred . The influence of pressure has been studied
in both closed bombs and vented vessels over
a period of years, and empirical equations in

~
various forms developed by different schools of
ballisticians.
de Saint Robert equation 32 r = bPn (31 a) I
Muraour equation 12 r =: a + bP (3 lb) /
t{OT
,A.1110\ENT I
"f_/
!._/
v
~ '/
/ COLO
~ = ~ + b(} )'1:i (3 lc)
/ , I

Summerfield equationl 1 I
,,
I
/
I

If the Jog P - log r relation for a propeUant <!>


0
..J
//;/
1s plotied we get a family of curves resembling
Figure 3 from propellants behaving according to
Equation 3 la, from which the values of b and n
can be evaluated. The constant n is the slope of
ihe Jog rate versus log pressure line. At gun pres-
sures, 10,000 to 50,000 psi, nearly all propeUants
LOG PRESSU~E
follow Equation 31 a, with n = approximately
0.9. 31 At rocket pressures, below '.WOO psi, n for Figure 4. Role-Pres;ure Relationship of Pfaleou
the same propellant is generally lower than at gun Propellants

13
"plateau" propellantsH This behavior is shown by
certain nitrocellulose system propellants contain-
ing small amounts of lead compounds and by
some fuel binder ammonium perchlorate compos-
ites. The effect of the lead compounds is to in-
crease the burning rate in the plateau region and
at lower pressures, as shown by the fact that with-
out the lead the propellant would show a normal
curve coinciding with the high pressure branch of w
the plateau propellant's curve and continuing nor-
.,
....
a:
mally into the lower pressure region (dotted line,
Figure 4) . The mechanism of plateau formation Cl
0
has not been fully elucidated . From Equation 31 a ....J

the pressure in a vented vessel is of the form 36

P::::: canst x ( A,bS)~ (32)

from which it is apparent that a low value of n LOG PRESSURE


is desirable in rocket propellants to decrease the
sensitivity of the operating pressure to small Figure 5. Role-Pressure Re/o/ion5hip of Mesa
changes in b (a function of propellant ambient Propellonl5
temperarure); S, the burning area: and A,, the
throat area. In practical terms, a low value of n reacrion becomes appreciable, one would expect
permits design of lighter weight rocket motor the temperature-rate relationship to assume the
chambers by decreasing the requirement for high form
safety factors 10 take care of deviations of b, S, b'P"
or A, from design values. r = (T' - T,) (33)
As a low value of n is desirable, a negative value
is even more desirable. Propellants are known where b' is a constant and T , is any initial tem-
which show negative values of n over short pres- perature . By measuring the linear burning rates
sure ranges, as shown in Figure 5. 1 : They are at the same pressure for the same propellant at
known, from the shape of the curves, as "mesa" two initial temperatures one could calculate T'.
propellants. In the region of negative slope, should Another frequently used relationship is
the pressure increase as a result of sudden expo- r = b"P"e"(T, - T~J (34)
sure of additional burning surface or by partial
constriction of the throat the rare would drop where b" and u are constants and T 0 is a refer-
immediately to restore the balance . The close ap- ence initial temperature. A linear relationship has
proach of the isotherms also contributes to a low also been noted. is The existence of regions of nega-
temperature coefficient of performance for vented tive temperature coefficient described above is not
vessels designed to ope rate in this region . Cross- consistent with eirher of these relationships, so
ing of isotherms indicates a region of negative the effect of propellant temperature on linear burn-
temperature coefficient. ing rate remains largely an empirical relationship.
In the SPIA/ M2 data sheets four temperature
9-2. Effect of temperature. As can be seen from coefficients may be found. Of these the tempera-
the isotherms of Figures 3, 4, and 5, the initial ture coefficient of burning rate at con slant pressure,
temperature of the propellant has a significant
effect on the linear bu ming rate. If aJl of the heat ap ::::: (olnr)
OT r' . . d
1s estimate f rom t h e rate-pressure

transferred to 1he propellant surface from the com- curves (Figures 3, 4 or 5) using the intersections
bus rion products were used to raise that surface of the curves for the dtfferent temperatures with
to a temperature T', at which vaporization or a vertical line at the constant pressure of interest.

14
Since for a real rocket motor the working pressure is the "port area" or the exit area of the tube
is not the same at different grain temperatures, and A, is the nozzle throat area, so Equation 35
this parameter does not have real significance. becomes
The temperature coefficient of burning rate at roo-
= + K1 ~ 1 ) (35a)
= ( ~;:) ir is determined em
r bP"(l
stant K value, <Tl( JI

pirically by static-firing rocket motors at different which is in a more convenient form for use by
grain. temperatures and dividing the known web rocket designers. The constant K 1 is caUed the
dimensions by the burning times to get the rates. "erosivity constant" and is a measure of the sus-
Since neither the burning surface nor the nozzle ceptibility of a propellant to erosion . Its value is
throat area changes appreciably with ambient of the order of 0.5 to I .0. Equation 35 will be
temperature,. the assumption of constant K value recognized as a linear approximation, applicable
between rocket motors of the same design at dif- over the range of gas velocities for which the con-
ferent temperatures is good. The temperature co- stant K 1 has been developed. A theoretical U'eat-
ment of erosion 40 has been based on the transition
efficient of pressure at constant !!... value, 71' p = from laminar flow to turbulent ftow of the rom-
r -.
bustion products within the perforation.
( olnP)
'OT ~ is determined from the rate-pressure An erosive burning law
curves, using the intersections of the curves for
the different temperatures with 45 lines which (36)
p
are lin es of constant- . In real rocket motors the
r has been devetoped 0 from consideration of heat
asswnpt:ton o constant -p w1"th c hangmg
. f . tempera- transfer to the propellant walls from the hot gas
' passing down the perforation. In this equation, a
and f3 are constants characteristic to the propel-
ture is better than the assumption of constant pres-
sure, but this parameter still has only qualitative lants burned, G is the mass velocity of the gases
value. The more significant temperature coefficient in the port, and L is the distance downstream from
0 the stagnation point.
of pressure at constant K value, "K =( ~'!}') K, is
again determined empirically by static fuing at dif- 9-4. Effect of composition. As the driving force
ferent temp_e ratures. All four of these parameters for the burning of propeUant is the temperature of
are expressed in units of percent per degree, usually the combustion products, all theories agree that
Fahrenheit. Low values of these coefficients are hot propellants should have a higher linear burn-
desirable. ing rate than cool ones. This is found quite gen-
erally true at gun pressures and also at rocket
9-3. Effect of gas velocity. Erosive burning. pressures where the rate-pressure relationship is
When burning occurs inside tubes of propellant "normal." This is a matter of no more than aca-
such as the perforations of gun propellant and the demic interest to the users of gun propellants who
interior surfaces of rocket propellant, it is found do not have the problem of reconciling grain
that the linear buming rate at and near the exit geometry to charge envelope requirements. In
of the tube exceeds the normal rate. The shape of rocket design on the other hand, where, in gen-
the "eroded" region suggests a velocity effect, and eral, single grains are used, it is necessary to be
indeed the erosion law may be written able to control burning temperatures and rates
independently in order to meet simultaneously per-
(35) formance and envelope requirements. To this end
rocket compositions quite commonly contain addi-
where V is the local gas velocity in the tube and tives known as burning rate catalysts which gen-
C is the velocity of sound in the combustion prod- erally increase or decrease the normal burning
ucts. In the case of a single internal-burning rocket rate of the propellant. The choice of catalysts and
grain in a rocket 39 motor, V As> = CA , where AP their proportions in the composition are deter-

15
mined by experiment. Temperature coefficients A e c D E

and erosivily constants are also properties of the


I
compositions. I
I
9-5. Burning rate of composite propellants. A /
I
/
composite propellant has been defined as a solid I
propellant system comprising two or more solid I......
phases inlimately mixed. In all important cases, >
with the possible exception of black powder, one
<......
of these phases is continuous and forms the matrix
B IN 0 E R [:<::::'.::>;::::::j FILLER~
or binder in which the other phase or phases is
dispersed. When a composite propellant burns, the Figure 6. Burning of Composite Propellanl-
burning surface comprises a web of binder filled Filler Rate Faster Than Binder
with exposed surfaces of filler material. Each ex-
posed material burns at its own linear rate at any c
A a 0 E G
given pressure and starting temperature and has
its own pressure index and temperature coefficient. I
A perfect match between the burning rates of I
I
binder and filler would be a coincidence, and easily ' '\
disturbed by a change in burning pressure. In gen- I
eral the fiUer surface will recede faster or slower I
than the binder, giving rise to an irregular and -~
time-dependent boundary between regions C and
D. Figure 6 shows the case of filler burning more ~II
rapidly than binder. Area I shows a filler particle /
not yet exposed. Area II shows a filler particle par-
tially burned, while at Area III is a pocket left B I N DE R ~~~;:;;:;:jj FILLER~
by a filler particle completely cooswned. The net Figure 7. Burning of Composite Propellanl-
effect of the faster-burning filler is to increase the Filler Rote Slower Than Binder
instantaneous burning surface of the binder. We
can no longer measure the burning area, only its coefficient and pressure index should also tend to
projection on a plane parallel to the original burn- follow the corresponding agures for the faster-
ing surface. By increasing the actual burning area, burning phase.
we attain a greater apparent linear rate, referred In a two-phase filler- binder composite various
to 1be projected area. In spite of the lower apparent combinations of monopropellants, fuels, and oxi-
burning rate of the binder, the burning rate of the dizers are possible. If both binder and fi.ller are
composite propellant approaches t.he linear rate of monopropellants, region D is all combustible mix-
the fast-burning filler. ture, although of a mixture of compositions. If the
The case of filler burning more slowly than binder is a monopropellant and the filler is either
binder is shown in Figure 7 . In Area I we have oxidant or fuel, region D is a continuum of com-
again a filler particle not yet uncovered, in Area 11 bustible mixture containing pockets of fuel gas or
a filler particle burning at a slower rate than the oxidizer gas, and a diffusion process as well as
surrounding binder, and in Area I[[ an incom- heating must occur in region E before the com-
pletely burned fi.Jler particle completing its com- bustion reactions can be completed . If the binder
bustion in the gas phase outside the piece of is fuel or oxidant and the filler is monopropellant,
propellant. In this instance the linear burning rate region D becomes a continuum of fuel gas or oxi-
of the composile should approximate that of pure dizer gas containing pockets of combustible mix-
binder. ture. If the binder is fuel and the filler oxidant
As the linear burning rate of the composite tends or vice versa, region D contains no combustible
to follow the burning rate of the faster-burning mixture.
phase, it is to be expected that the temperature A diffusion step is required to mix the fuel-rich

16
gas with oxidizer-rich gas before the reactions to detonation. This question has been and is being
produce the flame temperature can be completed. investigated intensively .
With larger filler particle size the distance either It is presumed that burning can give rise to
gas must move to accomplish diffusion is longer shock and that the shock thus produced can occa-
and, therefore, the distance between region D and sion detonation in the propellant. That continuous
region F should be greater than with smaller filler monopropellants can be detonated by shock has
particle size . This may explain qualitatively the been well documented_H. 47 The necessary condi-
observed slower burning rates of fuel binder com- tions are that the shock intensity be sufficiently
posites with large filler particle size . great and that the propellant be present in cross
The requirement of a diffusion step before a section greater than its critical diameter. That
combustible continuum is achieved is no essential burning of a properly consolidated rocket grain
handicap in a burning regime. [t is interesting to can give rise to shock has not been demonstrated.
note, however, that propellants with this require- A theoretical study 0 indicates that only when the
ment propagate detonation in the solid less readily pressure rises exponentially in a few microseconds
than do monopropellants. to several thousand atmospheres can coalescence
The preceding discussion of the burning rela- of pressure waves give rise to shock as a result of
tionships applies to steady state burning and burning. In an improperly consolidated propel-
assumes no pores, cracks, or fissures with com- lant, on the other hand, with regions of inter-
ponents perpendicular to the burning surface. Two connected porosity it is comparatively easy to
important problems are recognized in connection attain a condition of shock which will result in
with burning . detonation . Unfortunately much of the literature
9-6. Problem of unstable burning. For as long
which purports to study the transition from def-
as modern rockets have been under investigation lagration to detonation actually reports studies of
in the United States and undoubtedly earlier else- the transition from shock to detonation. 4 ~
where, some rockets have exhibited a tendency to
10. Propellant grain. A single piece of propel-
develop irregular pressure peaks at some time
lant is known as a grain. The exposed portion of
during their burning cycles. In severe cases this
the grain surface at any time during burning is the
has led to rupture of the motor chamber. With
burning surface. Any portion of the surface which
pressure-time instrumentation of sufficiently low
is covered by adhered nonburning material is in-
time constants these pressure irregularities have
hibited. The shortest distance, normal to a burn-
been shown to exhibit frequencies identified with
ing surface, that the grain burns until it loses its
axial, radial, and/ or tangential vibration modes
structural integrity is the burning distance. The
of the burning cavity . In separate instances the
thickness of the propellant wall so consumed is
phenomenon has been overcome by "resonance
the web. If a grain burns on only one side, as
rods" 12 placed inside the grain perforation, radial
is the case with case-bonded or otherwise inhibited
holes~ through the web, slotsq or bafftes 0 41
grains, the web is equal to the burning distance.
within the grain, and most recently by adding
If two parallel surfaces bum toward each other,
small qaantities of finely-divided al urninum 0 to
as in uninhibited single- or multiple-perforated
the composition. In each case a "quick-fix" has
grains, the web is twice the burning distance. The
been accomplished but no real explanation has been
relationship between web and burning distance is
given for the phenomenon . Considerable light has
thus not single valued. The dimensions of the grain
been shed very recently on this question by the
taken collectively are known as the granulation
appreciation that the propellant grain does not
when referred to multiple-grain or bulk charges, or
behave as a rigid body but has acoustic properties
as configuration when referred to a single grain.
similar to those of the gas in the burning cavity."
A grain that maintains its burning surface con-
9-7. Transition from deflagration to detonation. stant, or approximately constant, during burning
With the advent of very large, high performance has neutral geometry. Simple neutral geometries
rocket engines the question has been raised whether include sheets, squares, or disks with webs small
and under what circumstances a rocket motor can compared with surface dimensions or with edges
proceed spontaneously from a burning regime to inhibited, long tubes, or tubes with ends inhibited.

17
A grain whose burning surface increases during
the burning has progressive geometry . Examples
of progressive geometry are tubes with outer sur-
face inhibited and burning only on the perforation
surface, also grains with multiple perforations. A
grain whose burning surface decreases as burning
progresses has degressive geometry . Such geom-

- .."~\
etries include spheres, cubes, also cylinders and
cords of any cross section. The burn ing surface is
plotted against fraction of web burned for several
geometries in Figures 8-14. The portions of the
grain remaining at burn-through, shown shaded in
IL__ __ .. l
_,

Figure l 0. Star-Perforated Groin


- -~

10
,.
8
~
I
% c
z
;;
...
~
0::

.......,
w

0::
:>

..."'0
%

,_...,S!
.
~ I 0
I Q:A( llOlt Ol tlt!ih.CE b\l'l'JtifO

Figure J). SlolledTuhe Groin


0
0 1. 0

v
FRACTION OF wi:e BURN(O ~ 0

A LONG TUBE, NO-llolf81Tl:I) TUBE. SHEET,


END-SURNER /
B SHORT TUB(, WES 0.1 L(NGTH, STRIP
W(8 0 I WIOTw
/
C. OISJ<, WES 0.0!1 DIA~ETER
y
v
.., 2.0
Figure 8. Neutrol Geometry WU
LI ..
4 ...
u. 0:
<r. :::>
:> .. ../
"'
,. ..
"'-' v
i ~
~~
~ 0 1.0
I/

f0
"'lg I

fU(l;D1 1)1 :1tlUU' rJl.lfl


,.
00

FRACTION

A. INTERNAL
o; DISTANCE BURNED

BURNING ruec:. PERrORATtON '13 01 .. M


10

Figure 9. Rod ond She// Groin Fjgure J2. Progressive Geometry

18
11-1. Gun. The pressure-time relationship in a
gun is shown in Figure 15 . The propellant on
ignition starts to burn essentially in a closed cham-
ber. When the pressure has built up to a sufficient
level , known as shot-start pressure, the frictional
and other forces tending to hold the projectile in
place are overcome and the projectile starts to
move. As the projectile moves the volume of the
burning chamber increases, requiring generation of
more gas to maintain the pressure level. During
the early portion of the projectile travel the quasi-
constant volume of the burning chamber pennits
continued pressure build-up . By the time the pro-
jectile has traveled only a few calibers (distance
equal to the diameter of the gun tube), the rate of
o to
fi4C1l0. or Ol~lUtr 8U~D
addition of volume has caught up with the rate
of generation of gas, and the pressure has attained
Figure 13. Mu/tiple-Pedoraled Cylinder its maximum value. The remaining portion of the
propellant is consumed at decreasing pressure,
Figures 10 and 13 are known as slivers. after which the gases expand adiabatically until the
The terms neutrality, progressivity, and degres- projectile leaves the muzzle. The entire cycle is
sivity are also applied to the weight burning rate, accomplished in a matter of milliseconds.
. .
The gun cycle can be fairly precisely analyzed,
W. Since W is proportional to both linear rate
and burning surface, factors a.ff ecting the rate can but the analysis is complicated and requires ma-
affect the progressivity just as well as can geo- chine calculation . It is obvious that the mass rate
metric factors. Jn this sense a dual-composition of burning is very high and that the propellant
grain in which the first composition exposed burns mus< have either a very high linear burning rate or
more slowly than the ~cond can be progressive in a very large burning surface (Equation 30). Be-
spite of a degressive geometry. Such grains are cause propellants do not have very high linear
used for small anns charges. The slow-burning
()I.Iler composition is created by coating or apply- C>
~
ing a plasticizer to the outside of the grain and ~ 1.0
causing it to penetrate only part way through the "':I
web, leaving the interior of the web unchanged . '"er
Dtial-composition grains may also be used in '".,
rockets to create a boost-sustain situation . In this ..."'
"'IJ>::>
case the fast-burning composition is first exposed
and the slow-burning one later. Erosive burning is ..J

sometimes used to speed up the early burning of a


"';.;z
C<
normally progressive geometry and attain essen- 0

tially neutral burning. Finally, pressure changes ...


0
that affect the rate contribute to progressivity. 1n ::z
0
this sense all closed bomb burning is at least ;:
...
initially progressive, regardless of geometry, and
burning of a progressive or degressive geometry in
c
.."'
a vented vessel is more progressive or degressive
than is indicated by the geometry .
Fl'IACTIOH OF WES &UANEO
11. Scheduling of mass rate. Let us now con- A CORO
sider some of tbe operating cycles for engines in e SPHERE , CU9E
which propellants are used. Figure 14. Degressive Geomelry

19
PRESSURE - TRAVEL RELATIONSHIP IN PRESSURE - TIME RELATIONSHIP IN
GUN GUN

.
"'
~ 1--1-~+-~~+-~~+-'1..-~+-~~.....-~--1
"'
0:
;:>
~ t--~---,~-+----t~~--t~~----'11r-~-+~~~

"' ..,
"'a."'
0:
a.

TRAVCl Tl .. [

Figure 15 . Gun Cycle

burning rates, even at gun pressures, we are left the gun. For quality control purposes, firing in the
with the requirement of o very large surface . The closed bomb (Figures 16 and 17) can yield a rela-
geometric problem of accommodating a charge of tive quickness, RQ, along with the relative force
very large surface in the gun chamber or cartridge RF (see Paragraph 8-2). In this determination
case is very much easier to solve by breaking up
the charge into a nwnber of grains than by keep-
the bomb is instrumented to record directly r::;
ing it in one piece, and we find gun propellant versus pressure. The test propellant is fired in
charges are indeed multiple-grain charges. In comparison with the standard propellant, and RQ
Europe where charges are hand-loaded, gun pro- is determineda as the ratio of ~~ for the test
pellant charges are often made up of long strips
dP
or cords approaching the full length of the car- propellant to Tr for the standard at one or more
tridge case. In the United States where charges are
pressure levels .
machine-loaded, the shorter single- and multiple-
perforatcd cylinder form is preferred. Geometric 112. Catapult. The function of the catapult is
progressivity is not vital; guns have been quite to accelerate a load attached to a piston to a final
successfu"y .fired using degressive cord charges. velocity without exceeding a maximum accelera-
There are, however, marginal advantages to pro- tion . The ideal cat.apult should operate at constant
gressive or neutral burning geometries which tend pressure to afford constant acceleration . The ideal
to shift the position of the peak pressure to a later travel-time curve for the catapult is shown in
time and, therefore, to a larger burrung volume Figure 18. The same curve may be used to show
than when a cord-form charge is used . the volume of the burning cavity and the required
The practice in the United States in designing progressivity of the charge. It may be observed
a propellant charge for a new gun or in designing a not only that an extremely high progressivity is
new propellant charge for an existing gun is to required , but that the required progressivity is not
select a propellant composition on the basis of its linear. For personnel catapults there is an added
force , F, and flame temperature, T 0 , and estab- requirement that the rate of acceleration, a,
(jerk)
lish the optimum granulation empirically. Having not exceed a specified value. This sets an upper
established a given lot of propellant as the stand- limit on the slope of the rising portion of the
ard, additional lots that arc manufactured must pressure-time curve, Figure 18. Catapult grains
match the standard by actual comparison firing in may be designed in the form of multiple-perforated

20
ASBESTOS ANO GREASE MIXTURE\
I

\ GAUGE

L HOUSING
2_ GAIJGE HCA.JSING
3 GA!!GE BACKING
SCREW
4 . LOCK NUT
S GASKET RING
6. GASKET (ANNEALED COPPER)
7 CONE SPRING
6. FIRING HEAD NUT
9 FlRING HEAD : MUSHROOM NUT (_i>
10. FIRING HEAO MUSHROOM
11 WASHER (COPPER) 26. WASKER (ASBESTOS)
12- PISTON 27. WASHER (FIBER)
13. GAS CHECK 28. SEAT WASHER (COPPER)
14. LINER 29. VALVE SEAT
15 COUPLING AMINCO NO 406-95 30. SEAT SACKING NUT
16. TUSING- 114" 0 0. SUPER PRESSURE-AMINCO NO. 406-110 31. AUTOCLAVE 2-WAY ANGLE VliJ....VE WITH
17. WASHER (RED GASKET RUBBER) REMOVABLE SEAT
18 WASHER !NEOPRENE)
19. WASHER (BAKELITE)
2Q WASHER (BAKELITE)
2 l. FIRING PIN
22- GROUND PIN
23. FIRING PIN NUT (INTERIOR)
24_ FIRING PIN NUT (EXTERIOR)
2~ GASKET (NEOPRENE) - INTERNAL VALV~ -

figure 16. Closed Bomb AHembly


S"O "' l"'G. OtllC 11.HC\~ "'r >i>IJlil [ 11111 t trn
.u '0UA 11> 11: ( Si UM l !.. U10
roi:rcr d f>/4 .. , o l~ VO\ ... ~

' '

' "" .

. ~o

~ ' 00

~
0

<o

0.0~

0 . .::.,. O. '!.O D 1 ~ i. ()0

figure 17. Clot.ed Bomb Recotd

21
At this point in the design a propellant must
w
be selected. For this example, 010 propeliant (see
a:: SPIA/M2) which has the following characteristics
::::>
(fl
is chosen:
(fl
w ,,
a:: 1.11> = 212 lb-sec/lb at 1000 psia and optimum
a..
I e,xpansion

I \ C.o = 0 .00741
y = 1.25
T\ME OR TRAVEL r = 0.27 at 1000 psia and 70F
p = 0.0557 lb/ina
A chamber pressure is now chosen in the re-

I gion of plateau burning of the propellant, so that


changes in the burning surface of the propellant

I will cause only minimum variations in pressure


and thrust. The pressure selected is 1000 psia.
Because of heat loss to the rocket motor and
)
other inefficiencies, a delivered specific impulse

I with optimum -expansion of 95 percent of the


theoretical specific impulse is assumed. The weight
/ of propellant required is
I 40,000
~....-
.-V w = 119 = 212(0 .95) = 198 .5 lb
a Th.e weight flow rate is
00
CJ - - - -- - TIME . -
W -
w -
tb -
198.5 - 9 93 lb/
20 - . sec
0 FRACTION OF BURN DISTANCE

Figure I B. Cotopult Cycle At a chamber pressure of I 000 psia

cylinders inhibited externally, or rhomboid prisms


w 9.93 - 1 40 ' 'l
A 1 == CDPc = (0.00741)(1000) - . in
burning from the corner edges. A fuller treatment
of the ballistics of the catapult is given in reports or D, = 1.34 i.n
by the Atlantic Research Corporation .u
11-3. Rocket motor. The design requirements
for a rocket motor propellant charge usually
call for burning at a constant mass rate equal to I
the mass rate of discharge required to impart the
design thrust, and for the design duration which
may be from tens of milliseconds to tens of sec-
onds. The burning pressure should at least approxi-
mate a constant level. The pressure versus time
( \
\
record of the burning of a rocket grain usually
resembles Figure 19. I \

11-4. Calculation of a rocket propellant charge. I


A rocket motor is required to maintain an average
sea level thrust of 2000 lb for 20 sec at a design
operating temperature of 70F. The total impulse,
I, required is 20 x 2000 or 40000 lb-sec.
TlME

Figure 19. Rocket Mo/or Cycle


""
22
Continuing with 1his design, the surface area with-
The optimum expansion ratio of ~ obtained
out sloes and with the ends of the grain uninhibited,
I
from the Thrust Coefficient and Expansion Ratio is
Tablesu is found to be 8.4: 1.
Therefore
A,= 8.4(1.40) = J l.75 in2
S =2 ( * )(OD 2 - 10 2 ) + rr(lD)(L)

= 2(0.785)(12.442 - 1.64 2 ) + 3. 14(1.64)(29.8)


D~ = 3.87 in = 393 in 2
The average propellant surface during burning is
The surface of the slots is therefore

S av w 9.93 659 . ) s<lM> = 659 - 393 = 266 i.Jl 2


= rp = (0.27)(0 .0557) = in-
Using four slots at 90 , 5.40 in high , and 0.10 in
If a nearly neutral thr-ust is desired, then the sur-
wide, the: slot length becomes
face during burn ing should be as constant as pos-
sible, i.e. , Si = S1 =Sae The propeUant burning 266
distance is equal to L , 101 = 8( 5 .40) = 6.15 1n

rl 0 = (0.27)(20) = 5.4 in Disregarding the void volume of the slots for the
moment
At this point some type of grain design, such
as a star-type, slotted cylinder, cruciform, rod and S1 = 3.14(12..44)(29 .8 - 6. l5 - 5.4)
tube, etc., should be initially chosen . The design =714in 2
requirements can be met with a :>lotted cylinder .
An important parameter in grain design is the Within the accuracy of the calculations this design
ratio of the port area in an internal burning grain appears slightly progressive . The volume of the
to the nozzle throat area. For this illustration the slots is
port-to-throat ratio is set at the minimum of l .5: I
V,10 = 6.15(5.40)(0. 1)(4) = 13.3 in 3
to prevent erosive burning of the grain .
Therefore lhe port area and the actual propellant length is

A,,,., 1
n = 1.5A, = 1.5 ( 1.40) = 2 .10 in2 L = 29 .8 + (0. 785)( 121.~432 - 1.64 2) = 29 .9 in
The use of a minimum port area will result in the
smallest possi ble space envelope for the rocket In an actual problem the design should be
motor. With a port diameter of 1.64 in and a checked for undesirable variations of burning sur-
burning distance of 5.40 in, the outer diameter of face by plotting the calculated burning surface as
the propellant is 12.44 in . The volume of propel- a function of burning time . Final verification of
lant required is the design would be accomplished by fabrication
and static test of the grain.
v1> = w
p
= 0.0557
198.5 = 3560 .
in
3 While it is comparat[vely easy to design a rocket
grain to fit the performance requirements of a
The required grain length is approximately design. problem, it is often quite another thing to
fit the grain into the .required envelope. Where
3560 a gun charge designer can select a propellant com-
L = (0. 785 )(! 2.44 z - 1.64 2) = 29 .8 in position and determine the proper granulation, a
rocket charge designer is often forced by envelope
Jn more sophisticated design work the port-to-throar
rat io frequently is chosen as low as I: I, accepting erosive
requirements to start with a grain geometry and
burning. In the early stages of burning (until rhe por!-to- develop a propellant composition to give the re-
1hroa1 ratio equals l.5), .a portion of the propellant will quired burning rate. For this reason there are
bum al a higher rate than normal for the existing pres- nearly as many active rocket propellant composi-
sure, and the grain ge-0me1ry must compensate for this.
The design problem becomes thus more difficult , but by tions as there are rockets . The propellant geom-
no means impossible . etries and significant performance parameters of

23
most solid propellant rocket motors used by the REFERENCES
United States military services are summarized in l. J . Comer, Theory of !he Interior Ballistics of Guns.
the SPIA Jato Manual.~ 1 p. 101 , John Wiley & Sons, Inc., New York, New
York, 1950.
11-5. Gas generator. Gas generators are re- 2. Allegany Ballistics Laboratory, George Washington
University, Rocket Fundamentals, ABL-SR4, OSRD
quired to provide for a certain duration (a) a spe- 3992, 1944 (SPIA Abs1rac1 No. 0576B).
cific volumetric ftow rate, or (b) a specific mass 3. M . Barrere, A. Laumoue, B. F. DeVeubeke and J.
flow .rate, or (c) a specific gas horsepower. In addi- Vandenkerckbove , Rocker Propulsion, Elsevier Pub-
tion, a maximum gas temperature is usually speci- lishing Company. Inc., New York, New York, 1960.
4. J. Corner, toe. ci1.
fied, and the exhaust gases from the propellant
S. C. Cranz. lnnere 80/lis1ik (Lehrbuch der Bal/is1ik,
must be clean. Bd. 2), Julius Springer, Berlin, Germany, 1926.
6. F. R. W. Hunt, Edito~. Infernal Ballistics, Philosophi
11-6. Calculation of a gas generator propellant cal Ubrary, Inc., New York. New York, 195L
charge. Assume a gas generator must be designed 7, G. P. Sulton, Rocket Propulsion Elements. An Jntro-
to provide 20 gas horsepower for 30 seconds. du.clion to the Engineering of Rocke1s, 2nd edition,
John Wiley & Sons, Inc., New York. New York, 1956 .
The maximum aUowable flame temperature, Tv, is
8. R. N. Wimpress, Jr11ernal Ballistics of Solid-Fuel
1900K. OGK propellant (see SPJA/ M2), which Rockets. Milirary Rocke1s Using Dry-Processed
meets the temperature requirement, has the fol- Double-Bose Propellant as Fuel, McGraw-Hill Book
lowing characteristics: Company, Inc., New York, New York, 1950.
9. M. Barrere, et al., fo e. cit ., p, 98 .
y = I.25 l 0. Allegany Ballistics Laboralory, George Washirig1on
Tv = 1888K = 3398R 11.
Univer.>ity, Loe. cit.. p . 24 .
F. D. Rossini, D. D. Wagman, W. H. Evans, S. Levine
I
M = 0.04576 moles and I. Jaffe, Selected Values of Chemical Thermo -
dynamic Properties. Circular of the National Bureau
r = 0.28 in/sec at I 000 psia of Standards 500, U. S. Government Printl.ng Office,
Washington, D. C., 1952.
p = 0.055 lb/in 3 l 2. S. L. Levy and 0. A. Reynolds. Rocker Propellant
Performance Computations Program for the IBM
If the nozzle exit pressure is 50 psia, substituting 650 Compurer, Allled Chemical Corporation, Gen-
in Equation 5 eral Chemical Division, 16 May 1960, C-Ontract
DA-30-069-0RD-2638 ,
13. T. 0. Dobbins, Thermodynamics of Rocker Propul-
20 = 5~0 x ~:;~ x 1543 x 3388 x sion and Theoretical Evaluation of Some Pro101ype
Propellant Compositions, W ADC TR-59-7 57 (ProJ-

50
0.25]
)1.2::. ect J 148). Wright Air Development Cen1er , Dayton,
0.04576 [ I - ( lOOO
14.
Ohio, December 1959.
Joint Army-Navy-Air Force Ad Hoc Panel on Per-
formance Calculation Methods and Thermodynamic
W = 0 .0254 lb/sec Data, Bulletin of the Second Meeting, 27-29 April
1959, PCMT D2, Solid Propellant tnformatioo
Using a single-end burning grain design Agency. Applied Physics Labora1ory, The Johns
Hopkins Universily, Silver Spring, Ma ryland, CON-
FJDENTIAL
S -- w- ____JlQ~ - J 65 ' 2 l 5. J. 0 . Hirschfelder and J . Sherman, Simple Calcufo-
rp - (0.28)(0.055) - in tion of Thermochemical Properties for Use in Bal-
listics, NDRC A-IOI , OSRD 935 , October L942.
The propellant diameter is I .45 in. The propellant CONFIDENTIAL (SPJA Abstract No . OJ03A); ibid. ,
length is NDRC A-I 0 I (addenda), OSRD 935 (addenda)
(OSRD-1300, A-67M-A-70M), March 1943, CON-
L = rt 0 :::: (0 .28 X 30) = 8.4 in FIDENTIAL (SPIA Abstract No. 0303B).
16. P. de Pauw, "Die Verbrennungswarme des rauchlosen
1f a certain mass rate of flow is required, the Pulvers," Z. ges . Schiess- u . Sprengsrofjw .. 32, IO, 36.
60 (1937).
design proceeds as above . If a volumetric flow
l 7. A. 0 . Dekker, "Rapid Estimarion of Specific Impulse
rate is defined, this can be converted to a mass of Solid Propellants," Jet Propulsion, 26, 572 (1956).
flow rate by using a variation of the perfect gas law 18. Allegany Ballistics Laboratory, George Washington
University, foe . cit . p. 274.
PM !9. Allegany Ballistics Laboratory, George Washington
pg= RoT (3 7)
University, Joe. cit. , p. 27 5.

24
20. Allegany Ballistics Laboratory, Hercules Powder 35. W. H. Avery, R . E. Hunt and M . N . Donin, Burninp
Company, uapublished data. Rate Studies of Double-Base Powder, Allegany Bal
listics Laboratory, Geoq~e Wnshins<on University,
2 l. C . A . Orlick and A . M. Jacobs, The ABL Procedure ABL/P-1, OSRD 5827, January 1946, CONFLDEN-
for Colcu/Dtion of the I., of Propellants Which Yield TIAL (SP!A Abstract No. 0514); S. Zmachinski and
u Condensible Exhausl Product , Allegany Ballistics R. F. Preckel, Strand-Rate Ballistic Studie.< of P/4-
Laboratory, Hercules Powder Company. ABL / X-34, teau Type Propellant~. Hercules Powder Company,
March 1959, Conrract NOrd 16640, CONFION- ABL/ P-13, December 1948, Conrract NO rd 9709,
TIAL (SPIA Abstract No. 19064). CONFIDENTIAL.
22. J. Corner, /oc. cit., p. 128. 36. Allegany Ballistics Laboratory, George Wasbingron
23. Standard Methods and Procedures for the Determi- Universily, /oc. ci1 ., p. 45.
nation of Heat of Explosion of Rock(/ Propellant
37. J. H. Godsey and R. F. Preckel, Strand Rate Ballistic
Powders, Navy Department, Bureau of Ordnance. S1udies of Plateau Type Propellants. Part IV . Char-
NAVORD OD 9375 , 8 June 1953 (SPIA Abstract
acteristics of Various Ballistic Modifiers, Allegany
No. LUIS). Ballisrics Laboratory, Hercules Powder Company,
24. Army Service Forces . Proof Directive 12, 3rd revi- ABL/P 2 5, April 1955, Contract NOrd 10431, CON
sion. 12 February !946. FJDENTIAL (SPTA Abstract No. 15.209).
25. Joint Army-Navy-Air Force Solid Propellant Rocket 38 . J . Comer, Joe. cit., p. 73 .
Static Test Panel. Descrip1ion of Static Test Facilities
at Participuring Organization .<, CONFIDENTIAL. 39 . F . T . McClure, R. W. Hari and J. F. Bird, Solid
Solid Propellant Information Agency , Applied Physics Propellant Rocke! Moton as Acousric Oscillators,
L3.bor.a1ory, The Johns Hopkins University , Silver Applied Physics Laboratory, The Johns Hopkins Uni
versity, Report TG 335-3, 5 October 1959, Contr.act
Spring, Maryland.
NOrd 7386.
26. F. A . Warren, E. L. Anderson and P. M . Ku. Evalu-
ation of Solid Propellant Properlies. Pan 1-A Sarvey 40. J. Corner, 'The Effect of Turbulence on Heterogene-
of Current Met hods, Southwest Re~earch Insritute. ous Reaction Rates ." Trans. Faraday Soc. , 43, 635
Report RS 287, 31 January 1959, CONFIDENTIAL (1947). (Summarized in J. Corner, Theory of the !11-
(SPIA Absrracr No . J 919 l ). terior Bol/iJtics of Guns, p. 74, John Wiley & Sons,
Inc., New Yorlc New York, 1950.)
27. F . J . Malina , "Characteristics of rbe Rocker Motor
Unll Based on rhe Theory of Perfect Gases," 1 . frank- 4 I. Rohm & Haas Company. Redslone Arsenal Research
lin Inst. , 230, 433 ( 1940). Division, Quarterly Progress Repor/ on Interior Bal-
/is1ics. Repor t No. P-54-9, 15 April-15 July, 1954,
28. H . S. Seifert and J . Cr~m. Thrust Coefficient and Ex- Coniract W-01-021-0RD-334. CONFIDENTIAL
pansion Rorio Tables, Ramo Wooldridge Corpora- (SPIA Absrract No. 14391); G. Robillard and J . M .
tion Guided Missile Research Division. 29 February Lenoir, The Development of a New Erosive Burning
1956 (SPLA Abmact No . !7368). Law, Jet Propulsi<Jn Labornlory, California Institute
29. H. Murao1.>r, "Sur les lois de combustion des poudres of Technology, Bulletin of the Thirreenth Meeting of
collo'idales. 3 note," Bull. soc. chim . France, 41, the Joint Army Navy-Air Force Solid Propellant
145 l (l 927); ibid., "Sur les lois de combusrion des Groui.i, Vol. IT, p. 441 , CONFIDENTIAL, Solid Pro-
poudres collo'itlales. 4' nore ," Bull. soc. chim. Fronce, pellant Information Agency, Applied Physics Labora
47, 261 ( 1930) ; ibid., "Sur une rheorie de la com- tory, The Johns Hopkins Universiry. Silver Spring,
busrion. en vase clos, des poudres colloldales," Compt. Maryland.
rend .. 192, 227 ( 193 J ); H . Muraour and W. Schu- 42. A . L. Antonio, Development of Internal-Burning Solid
macher, ''La vitesse de combustion des poudres col- PropellantRockers, Aerojet-General Corporation,
lo'ldales sous la pression atmospherique," Mem . Aerojet Report L3032/35-2, 16 November 1950.
poudres, 27, 87 ( 1937). (Summarized in J. Corner, CONFIDENTIAL (SPIA Abstracr No. 10731).
/oc . ci1., pp. 43-5.)
43. R. P. Smith and D. F. Sprenger, Dewdopmeni of
30. B. L. Crawford, Jr., C. Huggett and J. J . McBrady,
Internal-Burning Solid-Propellant Rockets. Funda-
'The Mechanism of the Burning of Double-Base Pro-
mental Studies of Unstable Burning of Aeropln: Pro-
pellants," 1 . Phys. Chem., 54, 854 (1950).
pellants, Aerojet-General Corporation, Aerojer Report
3 l. Piobert, Troile d' Arti//erie, 1839 as cited io J . Taylor, 606 (Final), 4 June 1952, CONFIDENTIAL (SPIA
Solid Propel/en/ and Exothermic Compositions, p. 56, Abstract No 12J89).
Inrerscience Publishers, Inc., New York, New York,
44. G. E. Miles, lnves1iga1ion of Unstable Resonance
!959.
Burning, Allegany Ballistics Laboratory, Hercules
32. J. Taylor, Solid Propellent and Exothermic Composi- Powder Company. ABL/MPR 46 (p. 7 of Monthly
tioM , p. 56, Jntcrscience Publishers, Inc., New York, Progress Reporr 46), I August 1955, Contract NOrd
New York, 1959. 10431. CONFfDENT!AL (SPIA Abstract No . 15552).
33. M. Summerfield, Burning Mechanism of Ammonium 45. R. L. Lou and R. C . Kriger, Ef}ect of Chemical Addi-
P1:rchlora1e Propellants. Part II . Theory of Burning 1ives on ()n5tt~b(i: Burning, AerojelGenernl Corpora-
of a Composite Solid Propellanl, paper presented at tion, Aere jet Report L2 798-18, - 19 ( 16 Occober-1 S
American Roc.kel Society !3th Annual Meeting. December 1957), 10 January 1957. Conrract NOrd
17-21 November 1958, New York . New York. 16879, CONFIDENTIAL ISPIA Absiract No .
34. J. Celmer. Joe. ci1 ., p. 71 . 18.003).

25
46. V. Pbilipchuk, Double-Bose Cust Propellant, Assess- 50. L. E.. Smith, Jr., C. S. Iogram and T. Walsh, Bal-
ment of Fire and Explosion Howrd During Manufac- listic Test Methods-Closed Bomb Test Variables. A
tuu, Naval Proving Ground, Re.pon 834, 11 August Review of Proof Directive 12, 3rd Revision, Febn.1-
1951, CONFIDENTIAL (SPIA Abstract No. 11162). ary 12, 1946 , Suni!ower Ordnance Works , Hercules
Powder Company, 8 July 1959.
47. Rohm & Haas Compaoy, Redstone Arsenal Research
Division, Quorur/y Progress Report on Interior Bal- 5 J. M . L. Rice, J . Hull, B. Wales and A. C. Scurlock,
listics (April /5, 1956 10 July /5, 1956), Repon No. A Study of Propel/ont Chorge Requirements for the
P-56-14, JO August 1956, Contract W-01-02>-0RD C-10 Cotopult, Atlantic Research Corporation, No
334, CONFIDENTIAL (SPlA Abstract No. >6482); vember 1952, Contracl NOrd 10721, CONFJDEN
ibid., J. R. Hyndman, W. W. Brandon, H . M. Shuey, TIAL (SPJA Abstract No. lJ,037); M. L. Rice, T.
Def/ogra1ion-De1onotion Studies of Solid Propellants, Davis and A. C. Scurlock, A Comparison of Stet1m
Bulletin of the Twelfth Meeting of the Joint Army- and Powder Catapults, July 1954, Contract NOrd
Navy-Air Force Solid Propellant Group, Vol. JJ, p. 99, 10721, CONFIDENTIAL (SPJA Abstract No.
CONFJDENTlAL, Solid Propellant lnformation J 4,403).
Agency, Applied Physics Laboratory, The Johns Hop-
kins University, Silver Spring, Maryland. 52. Jato Monuo/. Volume I. Eorly Experimental Joto
48. A. Macek, "Transition from Deflagration to Dcton~
Units, Solid Propellant Information Agency,
SPIA/M I, CONFIDENTIAL; Rocket Motor Manual.
tion in Cast Explosives," 1. Chem. Phys .. .'.H, 162
(1959). Volume 11 (of Jato Manual). Units of Current lnter-
ert, SPIA/M 1, CONFIDENTIAL, Solid Propellant
49. S. J . Jacobs, '"Recent Advances in Condensed Media lnfonnation Agency, Applied Physics Laboratory, The
Detonations," ARS Journal, 30, J51 (1960). Johns Hopkins University, Silver Spring, Maryland.

26
CHAPTER 3

PHYSICAL PROPERTIES REQUIREMENTS

12. General. Just as propellants have different 14. Gravimetric densily. Gravimetric density i~
ballistic requirements depending on the uses to measured on bulk gun propellants as the weight
which they are put , the physical properties re- of propellant required to fill a specified con-
quirements of propellants will be different depend- tainer when charged at a specific rate from a
ing on use. hopper at a specified height. 3 (The density of pro-
pellant as loaded into cartridge cases can also be
13. Density. Since in a solid propellant heat determined.~)
engine the propellant is always contained within This datum is influenced not only by density
the engine, the propellant must have a density high and dimensions but by the smoothness of the sur-
enough that the charge can be so contained . Two face and the presence or absence of tailings from
factors enter into the determination that the charge the cutting operation. It is used as an indication
will fit into the chamber: the density of the pro- that the required charge weight can be contained
pellant itself, and the volumetric efficiency of the in the cartridge case.
charge geometry or the fraction of the propellant
envelope occupied by propellant. 15. Hygroscopicity. Most propellants contain
The density of a propellant is calculated from constituents that are hygroscopic and this property
the densities of its .ngredients, assuming no volume is passed along in some degree to the propellants.
change as a result of mixing. The mechanism of sorption and desorption of
hygroscopic moisture probably involves a rapid
_!_ _ ,.x; attainment of the equilibrium, dependent on rela-
p - -p, (38)
tive humidity, at the surface of the grain, followed
ln the case of a propellant undergoing chemical by slow diffusion within the grain. The effect of
reaction during the mixing operation, as is the case hygroscopic moisture is the same as if the formula
of many fuel binder composites, the ingredients contained the same fraction of water .
include the reaction products (e.g ., polymers) and Hygroscopicity of propellants for cannon is de-
not the reagents actually charged (monomer). In fined as the equilibrium moisture content at 90
the case of a propellant manufactured with in- percent relative humidity and 30C temperature.
clusion of a volatile solvent later substantially For small arms propellants hygroscopicity is de--
removed, that portion (residual solvent) of the fined as the difference between the equilibrium
solvent remaining in the finished propellant must moisture contents at 90 percent relative humidity,
be considered an ingredient . 30C temperature and at 20 percent relative hu-
Density can be measured with a mercury dis- midity, 30C temperature . The procedure for small
placement volumeterl or with a pycnometer 1 or, arms propellants~ involves successive exposure of
more roughly, from the weight and dimensions the same sample to controlled humidity atmos-
of the grain . Comparison of the measured density pheres, whereas for cannon propellants a single
with the calculated value gives a measure of poros- exposure and a chemical analysis for moisture are
ity, cracks, and fissures in the propellant. Micro- required .
scopic individual pores, as around crystals in Hygroscopicity of propellant charges loaded in
composite structures, have no apparent effect on engines has been controlled by hermetic sealing
the burning of the propellant, but cracks and fis- of the engine or its shipping and storage container,
sures constitute undesirable burning surface that or by loading a desiccant either into the engine or
cause excess pressure and interfere with the sched- the shipping container. Hygroscopicity of incli-
uled mass burning rate, and interconnected general vidual grains has been minimized by formulating
porosity can lead to detonation. ln monopropel- to a minimum con1ent of hygroscopic material and
lants measured density is usually very close to in the case of coated grains by building a layer of
calculated density. In composi Les a difference of material of low permeability into the surface of the
more than 2 percent indicates trouble. grain.

27
16. Coefficient of thermal expansion. At the ing. The rates of loading in actual rocket motors
level of about I 0- 1 per degree C, the thermal ex- vary from low rates during storage due to tem-
pansion coefficient is of little moment to mu! tiple- perature changes to very high rates during firing .
grain charges. For single-grain charges loaded into J ANAF mechanical properties test data are sig-
chambers at small clearances, care must be taken nificant to the extent that they compare propellants
to verify that the clearances between grain and under test conditions and imply that the same com-
wall do not disappear in the upper range of stor- parison will be valid under operating conditions.
age or firing temperatures because of the different
expansion coefficients of propellant and chamber 18-1. Ultimate tensile strength. Tensile strength
material. In this event the chamber wall would is important for rocket grains supported at the
exert stress on the grain causing it to deform or head end during acceleration. For other applica-
even fracture. If the grain is enclosed in a rigid tions it is of academic interest, or perhaps useful
inhibitor, the coefficients of the grain and inhibitor as a quality control measure to assure that succes-
should match as closely as possible for the same sive Jots of a given propellant resemble each other.
reason. If the grain is to be case-bonded to the Tensile strength ranges from about I 0,000 pounds
chamber, it is not ordinarily feasible to match per square inch for straight polymer monopropel-
the expansion coefficients and the grain must be lants to below 50 pounds per square inch for some
formulated to accept the stresses due to differen- case-bonded propellants.
tial expansion.
18-2. Elongation in tension. Case-bonded
17. Thermal conductivity. Propellants are in grains must deform to accommodate changes in
general very poor conductors of heat. This prop- dimensions of their containing cases with changes
erty is a useful one for ballistic des.ign, as it can in temperature . Although requirements vary from
be safely assumed that the unburned portion of a rocket motor to rocket motor, a minimum of 15
grain will remain at its initial temperature through- percent elongation at rupture at the lowest storage
out the combustion process. On the other hand, or operating temperature is a typical requirement
in a large grain the time required to bring the for a case-bonded propellant in a large rocket.
propellant to a uniform temperature following a Many such propellants have reported values of
change of environment may be several hours or 50 to 100 percent elongation at normal ambient
even days depending on temperature differential, temperature.
air circulation, and grain size. If the grain is fired
while it contains a temperature gradient, the rate 18-3. Modulus in tension. A low value of modu-
of gas production will refiect the temperature gra- lus is required of case-bonded grains in order to
dient. Thermal shock from too rapid change from avoid distortion of the case or rupture of the
very cold to very warm or vice versa may lead to adhesive bond when the motor is cooled . A typicaJ
cracking of the grain . The interior of grains stored value for modulus of a case-bonded propellant is
in munitions in hot climates fails by a wide margin 300 to 600 pounds per square inch per inch per
to attain the maximum diurnal temperatures. 1 inch, or dimensionally pounds per square inch.
Ultimate tensile strength, elongation, and modu-
18. Mechanical properties. The mechanical lus are all determined in the same test. 8 A test
properties of propellants must be such as to enable installation is shown in Figure 20 and a test record
them to withstand the mechanical loads imposed indicating the derivation of data in Figure 21.
during shipping, handling, and firing. These re-
quirements differ widely from one engine to an- 18-4. Stress relaxation. It is advantageous in a
other. Methods for measuring physical strength case-bonded propellant for the stresses produced
and deformation are reviewed by the JANAF by distortion to be relaxed as the grain becomes
Panel on Physical Properties of Solid Propellants accommodated to its new environment so that
and reported in the publications of that panel. residual stresses will not lead to cracking in areas
Numerical values below are as measured by stand- of stress concentration. The propeny of relaxation
ard JANAF tests.b Results in such tests are strong under tension may be measured by measuring the
functions of the rates of loading, propellants gen- tensile stress at fixed elongation as a function of
erally appearing stronger with higher rates of load- time. 1

28
CD PROPELLANT SAMPLE (})LOAD CELL
@SAMPLE GRIPS @STRESS-STRAIN RECORDER
Q) MOVABLE CROSSHEAD 0 RECORDER CONTROLS
@FIXED CROSSHEAD @ CROSSHEAD CO NTROLS

Figure 20. Tensile Tesl Setup

29
th l
C.t1 e l t f'l il"' 2,7 11\ fM "',.{,. llongatO,.. ((-.. 1cn ~OI" )
W1d 1h ..: 0)7~ I" (Joe.I'! l nCh o f CliC '1 ~ 0 2 1t1 j(it )
f h 1c'ine ts 0.1~0 or\ SllO t'I ( 11\) ;:: 6 9 r. ~ . 2 11\ ~ I Jaa 1n
0 _09 l7S ,,...
Cro n
R ,;1~
S~1 1 oru1
ot t.oJchr.1
Mu
- 0 JS t n / m/ ~f".t ~:~~.~~cS~~~o~ ~ 6s;~o1~ :c1f;J~~~~.
- l,.._..,_.,.._P+,F, -
1--

_, . I
.'l.o<J11,1lu~
1.J~ u~"" Ct.)11 - io% Stt.)l'I
l o.1d 4.f 10% S 1r.1m - 6 I()
L o~ .al ~ !Mn -0 6 JD
Lo.11d ,u t % S'''" .:: 4 4 o~
MOO:ulu\ ~ b .4 / IC-0 : 61-0 PS l-l-U+.l-l-l-1-1-l

A,tMtViuy Po1M 01 Rupt11,1re-


9~ % 01 M1i11mum

<J J H++,_
M~ ximum l oatJ - 16 JS lb

St''-n. in.

Figure 21. Tensile Test Record Showing Derivolion of Ultimate Slrength, Elongation, and Modulus
(Read curve from right lo /elf)

30
18-S. Creep. A lower limit on tensile modulus strength at the bond between the propellant and
of case-bonded propellants is set by the requ ire- the case. Per unit of propellant length, neglect-
ment that under its own weight the propellant not ing the perforation , the weight of the propellant
deform so as to decrease port areas or subsran- under acceleration and therefore the total shear
tially change shape and dimensions. Whether such
force is idZpa where d is the grain diameter in
deformation is elastic due to too low modulus or
inelastic due to cold flow it is known as creep. incties, p the propellant density in pounds per
Creep has been responsible also for departures cubic inch, and a is the acceleration in g's. The
from design ballistics of cartridge-loaded rocket total shear force is applied over an area of '!Td.
grains . The best criterion for assessing the tend- The required minimum shear strength 1 in pounds
ency to creep still appears to be experience . per square inch, is
18-6. Compressive strength. Cartridge-type ;rd Zpa _ dpa
rocket grains supported on traps or otherwise at 4,,-d 4
the nozzle end are subjected to compressive stresses Procedures for measuring shear have been re-
during firing . The magnitude of such stresses and, ported .' 1
therefore, the compress ive strength to withstand
them can be computed for any instance from the 18-10. Brittle temperature. For many plastics
designed acceleration of the rocket. Compressive the second-order transition temperature ' 1 sig-
strengths of propellants are usually of the same nals the onset of brittJeness . This appears to be
order of magnitude as ultimate tensile strength, the case with case-bonded propellants. lt has not
and for design purposes the tensile strength of the been established that the same significance of the
propellant is frequently used with suitable safety second-order transition temperature holds for car-
factors. Compressive strength can be readily meas- tridge-loaded propellants which perform well at
ured on equipment shown in Figure 20 . temperatures considerably below that of a second-
order rransition .
18-7. Deformation al rupture in compression. The second-order transition temperature may
The most severe stresses on a gun propellant occur
be measured 11 by noting a break in the curve of
during ignition when the grains impact on the
specific volume versus temperature or an abrupt
cartridge case or ch<imber wall and on the base decrease in mechanical properties such as impact
of the projectile as a result of having been accel-
strength at that temperature.
erated by the igniter gases. If the grains shatter in
such impact, the added burning surlace leads to
excess pressures in the gun . Redesign of the igniter REFERENCES
is the usual remedy, but the propellant is required
t. C . G. Jackson, "A Mercury Oisplacerncni Volumeler,"
not to be brittle. The test !>pecified for brittleness J. Sci. Instr ., 6, 26 1 0929).
is deformahon in compression at rupture. Unless 2. M lL-ST0-286, Propellant!; Sampling, lnspection and
otherwise specified the required minimum value is Testing, Method 510 ./ .J-Speci/ic Gravity (Pycnom-
30 percent to eter Method), 28 June 1956.
3. MILSTD-286, Propellcmts: Sampling. Inspection and
18-8. Modulus in compression. For cartridge- Tes1ing , Method 502./-Bu.lk Density, 28 June 1956.
loaded rocket grains the deformation due to com- 4 . MIL -STD-286, Propellan1s: Sampling, Inspection and
Testing. Method 507.1-Density of loading, 28 June
pression during acceleration must not be great 1956.
enough to cause significant departures from design 5. MIL-STD-286 , Propellants: Sampling , Jnspection and
geometry. This fixes a lower limit on the permis- Temng, Method 503 . / .2-Hygroscopicity, Small Arms
sible value of compressive modulus . The value of Propellants (Equilibrr'um Method), 28 June 1956 .
6. MlL-STD-286, Propellants: Sampling, Inspection ond
this limit has not been precisely evaluated as high Testing, Method 503.2.1-Hygroscopicity , Cannon
values of compressive modulus usually accompany Propel/ants I Equilibrium 1\fethod), 28 June 1956.
the required compressive strength. 7. J . N. Sherman and H. M . Burns, Temperatures Pro-
duced in Solid Propellant Rockets by Ex posure 10
18-9. Shear properties. Case-bonded grains are Climatic Extremes, Allegany Ballistics Laboratory,
stressed in shear during aa:eleration. The weight Hercules Powder Company , ABL / X-37, June 1959,
Contract NOrd 16640, CONFIDENTIAL (SPIA Ab-
of the propellant must be supported by the shear stract No. 19341).

31
8. Joint Army-Navy-Air Force Panel oo Physical Prop- May 1958, CONFIDENTIAL, Solid Propellant In
erties of Solid Propellants, Mel/uJdJ for Determining formation Ageocy, Applied Physics Laboratory, The
the Te11.Jile Propertie.<J of Solid Rocker Propellants. Johns Hopkins University, Silver Spring, Maryland.
Part I. Nitrocellulo1e Base Propi!l/ants, SP1A/PP8,
10. MIL-P-270A, Propellant, Artillery, 5 March 1959.
March 1956; Part ll . Composite, SPIA/PP8, Feb
niary 1957, Solid Propellant information Agency, 11. F . A. Warren, E. L. Anderson aod P. M. Ku, Evalua-
Applied Physics Laborawry, The Johns Hopk.ios Uni- tion of Solid Propel/ant Properties. Parr 1-A Survey
versity, Silver Spring, Maryland. of Current Methods, Southwest Researd1 Institute,
9. K. H. Sweeny and K. W. Bills, Jr., Apparatus for the Report RS287, 31 January 1959, CONFIDENTIAL
Measurement of Stress Relaxation Behavior, Aerojet- (SPIA Abstract No. 19191).
General C-Orporation, Bulletin of the Seventeenth 12. F . W. Billmeyer, Jr.. Textbook of Polymer Chemistry ,
Meeting of rhe Joint Army-Navy-Air Force Panel oo p. 40, lntcrscicnce Publishers, Inc., New York, New
PhysiC3l Properties of Propellants, SPIA/PP 11, p. 91, York, 1957 .

32
CHAPTER 4

BLACK POWDER

19. General. Black powder is our oldest pro- 22. Granulation. The standard granulations of
pellant. lt is older than any of the heat engines potassium nitrate and sodium nitrate powders are
(guns, rockets) in which propellants are used, and shown in Tables 4 and 5 , respectively.
has been used as a pyrotechnic and as a bursting
23. Thennochemistry. Lacking knowledge of
charge for centuries. It is an intimate mixture of
the nature of the volatile matter in the charcoal,
saltpeter, charcoal, and sulfur. There are two types
and considering that manufacturing tolerances per-
of black powder, one made with potassium nitrate
mit l percent variation in the fraction of each
and the other with sodium nitrate .
The potassium nitrate type is the older, and for
ordnance uses is still the more commonly used. TABLE 3. NOMINAL COMPOSITIONS OF
In ordnance circles black powder is the potas- BLACK POWDER AVAILABLE IN
sium nitrate type unless otherwise designated. The THE UNITED ST A TES
name black powder is a translation of the German
KN03 type' Na NOl type$
"Schwarzpulver," named after Berthold _Schwarz
who experimented with it in the fourteenth cen- KN0 3 , 3 14.0
tury.' In the Eng.Ji sh language the material was
known as "gunpowder" until the use of smokeless
NaN0 3 , % 72.0 =2
powder in guns made it necessary to differentiate Sulfur, % 10.4 12.0 ='- 2
between the black and the smokeless varieties of Charcoal, 3 15.6 16.0 =2
gun propellant. Gunpowder included Musket Pow- Ash, maximum, % 0.80 1.5
der and Cannon Powder, later Rifle Powder and Moisture, maximum,% 0.5-0 0.70
Sporting Gunpowder. When used for blasting, gun- Specific gravity 1.72-1.77 l.74-1.82
powder was called Blasting Powder. The present
United States terminology is "A" Blasting Powder. 2
ingredient, it is practically impossible to calculate
The sodium nitrate type of black powder was
the gas composition or volume of black powder.
developed in the United States in the middle of the
A rough approximation may be got by assum-
nineteenth centuryJ and is known comm ercially as
ing that the volatile matter is largely carbon, that
"B" Blasting Powder. When used for ordnance it
the potassium appears in the product as K 2 C0 3 , the
is called sodium nitrate black powder.
nitrogen as N 2 , the carbon as CO + C02 , and
20. Appearance. The appearance of black pow~ that the sulfur and such hydrogen as is in the vola-
der is shown in F igure 22. The grains are irregu- tile matter do not make an important contrib ution
larly shaped solids, resulting from the fracture to the gas volume. Under these assumptions the gas
of large r pieces on the rolls of the corning mill, of volume would be given by (CJ + 'h [NJ - 'h [K].
roughly uniform size as a result of screening. Black Since the (NJ and [K] are present in eq ual num-
powde r may alternatively be pelleted into grains bers, the gas volume of black powder is deter-
of uniform size and s hape. mined roughly by the fraction of charcoal in the
fo rmula. In the United States grade of potassium
21. Composition. The nominal composition of nitrate type of black powder, one gram contains
black powde r as available in the United States is 0.0 130 gram a toms of carbon which when burned
shown in T able 3. T he same composi tions are should give 0 .0130 moles or 290 cc (STP) of gas .
used for both milita ry and commercial grades. An experimental value of the gas volume from
Selection of the charcoal has an important bearing three samples of British black powder recently
on the quality and performance of black powder. examined in the Imperial Chemical Ind ustries
The charcoal is not pure carbon, but contains 13 laboratories has been reported at 280 cc (STP). 6
to 20 percent volatile matter and 2 to 5 percent The same author reports a heat of explosion, Q,
moisture. of 720 cal/g and a calculated flame temperature,

33
Figure 22. Block Powder, Grade FFFFG, 8 X Mogriif'icolion

34
TABLE 4. GRANULATIONS OF POTASSIUM NITRATE BLACK POWDERS

Retained Through
Sieve size (maximum percent) Sieve size (maximum oercent)

Military grade
A-I 4 3.0 8 5.0
A-2 4 3.0 12 5.0
Cannon 6 3.0 J2 5.0
A-3 12 3.0 16 5.0
A-3a 12 3.0 20 S.O
Muskec 14 3.0 25 5.0
FFG 16 3.0 30 5.0
A-4 16 3.0 40 5.0
Shell 16 ).0 50 5.0
FFFG 20 3.0 50 5.0
A-5, Fuzc 40 3.0 100 5.0
FFFFG 45 3.0 140 5.0
A-6 100 5.0 140 15.0
A-7 100 3.0 140 50.0
Meal !00 5,0 200 50.0

Sp hero-hexagonal: I 28 =" 2 grains per pound, 0.6-inch grain diameter

Commercial grade l
Sporting
Whaliog 32/64. 3 4 J2
Life Saving Service 6 3 12 12
Cannon 6 3 12
Saluting 10 3 lo 12
Fg 12 3 16 12
FFg 16 3 30 12
FFFg 20 3 50 12
FFFFg 4() ) 100 12

":\"Blasting
FA 20/64 3 5 12
'.:'.FA 4 3 12 J2
JFA 10 ) 16 12
4FA !2 3 20 12
5FA 20 3 50 12
6FA 30 3 50 12
7FA 40 3 !00 12
Meal D 40 3
Meal F 100 3
Meal XF J 4() 3

Diameter of circular per for at ions in plate.

35
TABLE 5. GRANULATIONS ()F SODIUM NITRATE BLACK POWDERS

Retained Through
Sieve siie (maximum percent) Sieve size ( maximum percent )

Military Grade ~

JANC 9/16 inch 0 3/8 inch 0


JAN B 4 3 J6 5
JAN A 12 3 40

Commercial Grade ~
"B" Blasting
CCC 40/64 7.5 32/64 7.5
cc 36/64 7.5 24/64 7.5
c 27/64 7.5 18/64 7.5
F 20/64 7.5 5 7.5
FF 4 7.5 8 7.S
FFF 6 7.5 16 7.5
FFFF 12 7,5 40 7,5
Meal BB 16 7.5
Meal BD 40 7.5
Diam~tcr of circular pcrforatiolls in plate.

T of 2800C. Products identified in the com-


0 , nized in the familiar slogan "Keep your powder
bustion products include mainly K 2 C0 3 , K 2 SO~, dry." This hygroscopicity is primarily due to the
K2S 2 , C0 2 , N 2 , some H 2 , H 2 S, CH NH 3 , H 2 0, saltpeter. It may be explained oo the basis of
KCNS, and some unreacted KN0 3 , C, and S.' moisture pickup at any time that the atmospheric
As the fraction of charcoal increases and the frac- humidity exceeds the parlial pressure of water
tion of saltpeter decreases, the gas volume should over a saturated solution of the saltpeter.
increase and T . should decrease. The force, F, Humidity cycling results in a slow deterioration
calculated from the Imperial Chemical Industries due to crystal growth of the nitrates. Submergence
data, is 110,000 ft-lb/lb, of black powder under water causes the saltpeter
The initial condensed phase reaction in the to leach out.
burning of black powder has been identified as 25. Shelf life. At elevated temperatures, physi-
the reaction of molten sulfur with occluded hydro- cal changes in the sulfur can occur. The hygro-
gen~ or oxy hydrocarbons in the charcoal, 8 or with
scopic effects are also deleterious to shelf life.
the potassium nitrate. 1 A sulfu.rless grade of black Apart from these influences, black powder is very
powder is manufactured in Great Britain. This has stable thermally and under optimum conditions
a considerably higher ignition temperature than black powder can be stored for many years with-
normal black powder because molten saltpeter is out serious deterioration.
required to initiate its combustion. 10
The concept of linear burning rate as presented 26. Manufacturing process. Both types of black
in Paragraph 9 has little significance when applied powder are manufactured by the process shown
to the irregular shapes of black powder . The term schematically in the ftowsheet, Figure 23 . The
linear burning rate, when speaking of black pow- charcoal and sulfur are ground together in the pul-
der, is applied to the rate of propagation along a verizer, which ls essentially a ball mill using short
column of the granular material, i.e ., a fuse. steel cylinders for balls . The "composition dust"
is discharged from the pulverizer through a "reel"
24. Hygroscopicity. The hygroscopic nature of or screen which rejects the coarse material. The
black powder has long been known and is recog- saltpeter is added to the composition dust and

36
OVERSIZE 8 OUST
SALTPE TC R GRINO & SCREEN

MEAKOOWN
WATER WHEEL ,_.ILL PRESS
AOLLS

CHARCOAL PlJLVEIHZER FINES


SULFUR (REELJ

REL CORNING MILL CUTTING ROLLS

GLAZE 8LENO SCFIEEN

Figure 23. Black Powder Monufoclurin9 Process

rework in the wheel miU, shown in Figure 24, volumes of smoke and to a corrosive barrel residue
along with a small quantity of water. The indi- requiring thorough cleaning of the gun daily or
vidual wheels of the whee! mill may weigh 10 tons after each use. When propellants known as smoke-
and stand 7 feet high. The functions of the wheel less powders with higher force and substantially
mill include in addition to grinding and mixing without solid products became available, black
the achievement of a. state of "incorporation." powder became obsolete for gun use. The change
Although incorporation is little understood, it is was not made overnight because a gun designed
believed to be a state of very dose contact among for black powder was not ideal for use with smoke-
ingredients, perhaps without intervening films of less powder and vice versa. There are still a few
air on particles, and accomplished by very con- antique sporting pieces in the hands of hobbyists
siderable mechanical effort in the form of shearing who fire them, but the use of black powder as the
pressure. 2 When the wheel mill cycle is complete, propelling charge for guns no longer is significant.
the wheel cake is shoveled out and transported During World War II a need arose for a ft.ash
to the press house where it is first broken down suppressant for use with certain guns, particularly
by passing through rolls, then pressed into cakes the J55-mm gun . lt was known that pot.a.ssium
using a horizontal press shown in Figure 25. salts are effective in suppression of flash. As black
The press cakes are broken lnto pieces of about powder is roughly three-quarters potassium nitrate
~-inch size on the cutting rolls shown in the back- and a propellant in its own right, the use at night
ground of Figure 25. The size is reduced further of an auxiliary charge ot black powder was under-
on the corning rolls. The product from the corning taken with considerable success . This use of black
mill is screened on a reel, the dust being sent back powder is not expected co outlive the present in-
to the press. The product size and shape do not ventories ot smokeless powder, however, si1Jce new
change essentially after the corning operation. The propellants containing largely nitroguanidine have
remaining operations are glazing and screening to been developed which have at the same level of
separate the various grades produced. The glazing force lower burning temperature than those of the
operation is carried out at elevated temperature World War ll smokeless powders. These nitro-
in order, simultaneously, to evaporate water down guanidinc: propellants exhibit much less tendency
to the specified level. If fuse powder is being made, to ft.ash, and the incorporation of small fractions
two or more grades of different burning rate are of potassium salts in them generally inhibits flash
produced by varying the ratio of sulfur to char- completely.
coal in the .formula and these are blended to meet Black powder was also the original rocket pro-
burning rate specifications. pellant. 1n the decades before World War II, ex-
cept for Goddard's experiments, rocketry In the
27. Uses. With a force, F, of ] I 0,000 ft-lb/lb, United States was confined 10 fireworks and small
black powder was an effective gun propellant. The signal rockets of modest range and velociry and
presence of solid react.ion products led to large small payloads. For such rockets, black powder

37
CotJ1''nY of F: 1 dtAPonl d~ ;\/emo11r~ & Co . lrr c_

Figure 24. Block Powe/er Wheel Mill

38
Com es y of E . l . d.ul'ont <U fll omo u rs d< Co. , lnc

Figure 25. Block Powder Press

39
has been quile satisfactory. The smoke and sparks TABLE 6. CONSUMPTION OF BLACK
of the exhaust were desirable and there was no BLASTING POWDER (ALL TYPES)
disadvantage connected with residue in the spent IN THE UNITED ST ATES 1t
motor chamber. When military rockets were de- Pounds
veloped during World War 11, first abroad and Year (thousands)
later in the United States, it was recognized that
1915 197,722
the low calorific value of black powder took it out !920 254,880
of competition with the more energetic propel- !925 156,964
lants that were available. Manufacturing processes 1930 99,813
moreover were not available to form black powder 1935 68,888
1940 59,754
into the grain geometries required for these higher
1945 36,948
performance rockets, and it is doubtful that the 1950 20,655
physical properties of black powder would be com- 1955 6,624
patible with the thermal and acceleration forces of 1956 5,598
such rockets. 1957 3,684
1958 2,492
As a bursting charge, black powder has been
supplanted largely by more potent high explosives
whereas the slower burning black powder main-
except for some practice bombs and projectiles
tained pressure longer and gave more "heaving" of
where the smoke puff helps locate the impact
the burden. Coal miners like black powder be-
point. cause it breaks the coal into higher priced lump
In primers for gun charges and igniters for coal and produces less fines than even the low
rocket charges the easy ignitibility of black pow- rate permissible high explosives. Unfortunately the
der has made it a preferred ingredient. The high reaction time of black powder lasts longer than
content of potassium nitrate has also been recog- the initial fracture of the coal, resulting in occa-
nized as favorable for such use, because potassium sional ignition of methane (fire damp) and dust in
salts are good emitters of radiation and radiation the atmosphere of gassy mines and even of the
may be an important means of transfer of heat coal itself. Use of black powder for blasting in coal
from the primer or the igniter to the surface of the mines engaged in interstate commerce is now for-
main propellant charge. bidden by federal law.
As the first civil as well as military explosive, The largest current use of black powder is for
and for a long time the only available explo- safety fuse. This is a column of black powder en-
sive, black powder has been extensively used for closed in a fabric tube. The rate of burning is
blasting. For this use the sodium nitrate black carefully standardized so that the shooter can pre-
powder has been preferred ever since its introduc- dict the length of time between lighting his fuse
tion, in spite of somewhat greater hygroscopicity and the shot. Black powder has also been used
and slower burning rate, because of its lower price. as the timing element in some military fuzes. It
Black powder does not detonate, even when ini- has the disadvantage of producing a considerable
tiated with a blasting cap. The observed propaga- volume of gas which either must be vented or it
tion rates of l 00 to 600 m/sec11 11 when confined increases the pressure on the powder train and
in steel pipes and initiated with a detonator are hence its burning rate . Jt has the further disadvan-
accounted for by shattering of the black powder tage that it is difficult to ignite at reduced pres.-
by the initiator and burning at the attained pres- sures and impossible to ignite at pressures below
sure. Black blasting powder was first supplanted 100 mm. For use at high altitudes it is necessary
by commercial high explosives for blasting in rock to assure that any device relying on the burning of
because the detonation of the high explosives was black powder be pressurized.
very much more effective than the burning of black The decline of the black powder industry in the
powder. For blasting in earth, black powder with- United States is shown in Table 6.
stood the competition of high explosives for a Recognizing the obsolescence of black powder,
longer time because the shock of detonation of the military forces have sponsored research on
high explosives was rapidly d issipated in earth substitutes fo r black powder in all applications.

40
REFERENCES

L A. P. VanGelder and H. Schlatter, History of the Ex- 8. 1. D. Blackwood and F . P. Bowden, "The Initiation,
plosives Industry in America. p. I 0, Columbia Uni- Burning and Thermal Decomposition of Gunpowder,"
versity Press. New York, New York, 1927. Proc. Roy. Soc. (London), Al13, 285 (1952).
2. C . W. Broo'l:s (. I. duPont de Nemours & Co., Inc.),
private communication. 9. C. Campbell and G . Weingarten. "A Thermoanalyti-
3. L. du?ont (to E. I . duPont de Nemours & Co., Inc.), cal Study of the Ignition and Combustion Reactions
U.S. Patent 17,)21 (!857). of Black Powder," Trans. Faraday Soc., SS, 2221
4. JAN-P-223A, National Milirnry Establishment Speci-
(1959).
fication Powder, Black (12 January 1949) with SCN
I 0. J . Taylor, foe . cit., p. 21.
No. I (23 March 1959).
5. J AN-P-362, Joint Army-Navy Specification. Powder, I I. Hercules Powder Company, unpublished data .
Black. Sodium -Nitrate (28 June 1946) with Amend-
ment-I (23 December 1946). 12. U . S. Bureau of the Census. Statistical Abstract of
6. J. Taylor, Solid Propellent and Exothermic Compo- the United States: 1940. 62nd edition, p. 860, Wash-
sitions, p. 19, Interscience Publishers. Inc., New York, ington, D. C., 1940; ibid .. Statistical Abstract of rhe
New York. 1959. United States: 1959, 80th edition, p. 815 , Washing-
7. H. Debus, "Chernische Theorie des Schiesspulvers," ton, D . C., 1959; U. S. Bureau of Mines, Mineral
Ann., :Z 12, 257 ( 1882); 113, 15 ( 1882). (Summarized Market Report No. MMS 2973 , Washington, D . C .,
in J. Taylor, loc. cit., p. 20) . 1959.

41
CHAPTE!l 5

CRYSTALLINE MONOPROPELLANTS

28. General. The shape of black powder grains these materials have been extensively investigated
suggests crystalline material. A crystalline chemi- in connection with their use as high eJ(plosives. In
caJ with better thermodynamic properties than general, they exhibit long shelf life and are very
black powder should have advantages over black stable at temperatures up to nearly their melting
powder not only in ballistics but also in uniformity points.
of composition and ease of manufacture. Such 1n common with black powder grains, single
chemicals exist. They have not been exploited as crystals of monopropellants are nor subject to
propellants because they became available at a being shaped to accurately controlled dimensions
later daie than nitrocellulose and smokeless pow- and large sizes . Again like black powder, however,
der, and the background knowledge that would they can sometimes be pelleted under sufficiently
have led them to be appreciated is of still more high pressure to moderately well consolidated
recent origin. large grains of controlled dimensions .
The list of possible monopropellants includes The densities, melting points, and ballistic pa-
many chemicals used as military high explosives, rameten, of several possible crystalline monopro-
as the thermochernistry of propellants is essentially pellants are tabulated in Table 7.
the same as that for high explosives. The difference 29. Nitroguanidine. Nitroguanidine may, as an
between combustion and detonation of a crystal- approximation, be considered to react according
line monopropellant is merely a difference in re- to the equation
action rate . 1 Except for primary explosives, which CH.i0 2 N 4 ==CO+ H 2 + H20 + 2N2 (39)
can detonate from burning and are therefore ex-
cluded by definition from possible monopropel- The gas volume, ~, of nitroguanidine is quite
lants, these chemicals will burn quietly when high, and the fraction of nitrogen in the gas is un-
ignited . They will detonate only under the influ- usually high for propellant gas. The burning tem-
ence of a mechanical shock of severity far greater perature of nitroguanidine is some 150K lower
than can be found in a gun or rocket chamber. than that of a smokeless powder of the same force
The thermal stability as well as the sensitivity of level (see Ml in SPJA / M2), indicating that nitro-

TABLE 7. PHYSICAL AND BALLISTIC PARAMETERS


OF CRYSTALLINE MONOPROPELLANTS

Density Melling Q, l/M Tv T, Force 1..


(g/cc) point ("C) (cal/g) (moles/ lb) ("K) ("K) (ft-lb/lb) (lb-se;:/lb)
--- ~
--- - ---- ---- - - -- ----
Ni1roguanid1ne 721 0.048! 2268 303,000
Nitroguanidinet l.715 246 2405 1819 321,000 199
RDX,
cyclotrimcthylene-
trinitramine J.82 202 1360 0.0405 4020 3250 452,000 255
HMX,
cyclotetramethylene-
tclr'lnirramine 1.92 276 1321 0.0405 3940 3180 430,000 253
PETN,
pentacrythritol
tctranit rate I 77 140 1531 0.0348 4220 35!0 40,900 250
Ammonium nitratet 1.72 170 354 0.0437 1622 1245 197,000 159
Ammonium pcrchloratct ! .95 Decomposes )35 0.0362 1849 1408 186,000 15)
Hirschfelder-Sher man calculation (see Paragraph 7-6).
~Exact calcula1ion (see Paragraph 7-5).

42
guanidine should cause less gun barrel erosion 30. RDX. RDX (cyclotrimethylenetrinitramine,
than a comparable service gun propellant. The cyclonite, hexogen) may be considered to react
higher content of nitrogen in the gas should result 3ccording to Equation 43
in Jess tendency to Rash than a service gun propel-
(CH2N20 2)J :::: 3CO + 3H20 + 3N 2 (43)
lant at the same flame temperature and an even
more pronounced advantage at the same level of The force and specific impulse, from Table 7, are
force. quite attractive , although the flame temperatures
The usual crystal form of mtroguanidine is are higher than desirable for gun applications.
needles, resulting in quite low gravimetric density ROX has been fired in sporting and small arms
and small web. No successful work has been re- successfully 1 with ballistics comparing favorably
ported on growing crystals of size and shape that with those of smokeless powder. As expected, the
would permit using nitroguanidine as a gun pro- quickness was found to depend on the crystal size,
pellant. The linear burning rate has apparently finer crystals beirig quicker than coarser. The high
not been measured. burning temperatures may be tempered by formu-
Although nitroguanidine has not found use as lating to a composite with a binder of lower burn-
a monopropellant, the disadvantages of its crystal ing temperature.
form have been overcome at the cost o[ some RDX is manufactured by the Woolwich proc-
compromise of ballistic parameters by formulating ess5 by the nitration of hexamethylenetetramine
nitroguanidine as filler with plastic monopropellant
(CH2)aN 1 + HN0 3
binders into composite propellants. Development
::::: (CH:2N202h +gaseous products (44)
of such composites has also permitted a continu-
ous spectrum of force and flame temperatures in or by the Bachmann process~ by reacting ammo-
the triple-base system described in Chapter 7. nium nitrate and nitric acid with hexamethylene-
Nitroguanidine is synthesized by the fusion of tetramine under dehydrating conditions
calcium cyanamide or dicyandiamide with ammo-
nium nitrate under high pressure and temperature (CH2)11N~ + 4HNO:i + 2NH 4 N0 3 -6H 20
:::: 2(CH2N202h (45)
to yield guanidine nitrate, followed by dehydration
with mixed sulfuric and nitric acids 2
31. HMX. HMX (cyclotetramethylenetetrani-
CaNCN + NH 1 N0 3 + 2H 2 0 tramine) is homologous with RDX and may be
::::: Ca(OH)2 + NH: C(NH 2)NH 2 HNO~ (40a) assumed to react
NH : C(NH 2 )NHCN + 2NR1 NO:i
= 2NH: C(NH 2)NH2 HN0 3 (40b)
(CH2N20z).1 = 4CO + 4H 2 0 + 4N 2 (46)

NH : C(NH 2 )NH2 HNO:i - H 2 0 The ballistic parameters are similar to those of


== NH: C(NH 2 )NHN0 2 (40c) RDX . It is somewhat more dense than RDX and
has a somewhat higher melting point (Table 7).
Other syntheses are known. The thiocyanate
Like RDX, HMX can be compounded into
process 1 depends on the series o[ reactions
composites such as PPL 949 (see SPIA/M2).
2NH 4 CNS HMX 6 appears as a by-producl to the extent
.::: NH: C(NH 2 )NH 3 CNS +.H 2 S (4la) of about 10% in Bachmann-process RDX. No
NH: C(NH2)NH:iCNS + NR1 N0 3 attempt is ordinarily made to separate it from the
=NH: C(NH 2)NH 2 HN0 3 + NH~CNS (4lb) RDX, because for most uses it is the full equiva-
3 lent of RDX. By changing the conditions of opera-
The Roberts process proceeds through ethyl
pseudourea and guanidine sulfate tion of lhe Bachmann process, the fraction of
HMX can be increased substantially to where iso-
CO(NH 2)z + (C 2H,JhS0-1. lation of the HMX is practical.
:::: NH : C(NH2)0C 2 H 5 + C2H 5 HS0 4 (42a)
H2S04 + NH: C(NH2)0C 2 H 5 + NH 3 32. PETN. PETN (pentaerythritol letranitrate,
=NH: C(NH2)z H2S0 4 + C 2H 5 0H (42b) penthrite) may be assumed to react
NH: C(NH2h H2S0.1 + HN0 3 - H 2 0 C(CH2N0 3 ) 4
::::: NH :. C(NH2)NHN0 2 + H 2 S0 4 (42c) = 2CO + 3C02 + 2N 2 + 4H 2 0 (47)

43
With higher burning temperature and lower gas 34. Ammonium perchlorate. Ammonium per-
volume, the force and specific impulse of PETN chlorate may be assumed to react
are comparable to those of RDX and HMX
(Table 7). Since PETN has lower density and
lower melting point than RDX and HMX, these
latter materials should be preferred to PETN As a monopropellant, ammonium perchlorate is
either as monopropellants or as filler for composite even more oxidizing than ammonium nitrate. Like
propellants. ammonium nitrate, ammonium perchlorate is hy-
PETN is manufactured' by the nitration of groscopic. The presence of hydrogen chloride in
pentaerythri tol the products of combustion makes ammonium per-
C(CH 2 0H)~ + 4HN0 3 chlorate unattractive for use in engines used repeti-
== C(CH 2 N0~) 4 + 4H 2 0 (48) tively, such as guns. For these reasons ammonium
perchlorate has not been used as a monopropellant
33. Ammonium nitrate. Ammonium nitrate charge. It is widely used as an oxidizing filler
may be assumed to react in composite propellants for rockets, as discussed
(49) funher in Chapter 9, and in ORDP 20-176.
Ammonium perchlorate is prepared by electro-
As a monopropellant, ammonium nitrate produces lytic oxidation of sodium chloride,
a working gas containing free oxygen. For this
reason, although its force and specific impulse are NaCl+ 4H 2 0::::: NaC101 + 4H 2 (51 a)
somewhat modest, when compounded into com-
posites with any incompletely oxidized binders followed by metathesis with an ammonium salt
ammonium nitrate behaves in part as an oxi- (51 b)
dant. Such composites are discussed further in
Chapter 9.
Ammonium nitrate is hygroscopic at relative REFERENCES
humidities above 40 percent. Any propellant I. L. Wohler and F. J . Roth. "Ueber die Brisani: von
charges comprising anunonium nitrate must be Explosivstoffen," Z . ges. Schiess- u. Sprengsioff w., 29,
protected from humidity. Ammonium nitrate also 9 ( 1934).
undergoes a series of phase changes at different 2. G. B. L. Sniilh, V. J. Sabetu and 0. F. S1einbacb, Jr.,
"Quantitative Study of the Prepararions of Guanidine
temperatures including one at 32.2 C, 8 all of Nitrate and Nitroguanidine," Ind. Eng . Chem ., 2l,
which are accompanied by changes in density. 1124(\931).
This is destructive to the integrity of single crys- 3. The Syntliesi.r and Fineness of Nitroguanid1ne, Naval
tals. When compounded into a composite with Powder Factory, lndian Head, Reports QR 9. IO.
hydrophobic or nonhygroscopic binder, aU of the 15 June 1950, CONFIDENTIAL (SPlA Abstract
No. 10680); Synthesis of Nilroguar11dine. ibid .. Re-
ammonium nitrate crystals within the binder are port QR 12, 15 July l951, CONflDENTIAL (SPlA
protected from moisture pickup. The phase changes Abstract No . t 146 l).
can also be contained, as the crystal size of the 4. Hercules Powder Company, unpublished data.
ammonium nitrate is preferably very small and 5. W. M. Rinkeobach. Explosives (High), in Encyclo-
the stresses produced by the volume change of the pedia of Chemical Technology , Vol. 6. p. 40, lnter-
sci~nce Publishers, Inc., New York, New York., 1951.
individuaJ particles can be absorbed by the binder.
When formed into large grains by compression 6. W. E. Bachmann, U.S. Patent 2,798,870 ( 1957).
molding, hygroscopic effects are likewise confined 7. E. Berlow, R.H. Barth and J. E. Snow, The Penta-
erythritols, p. 54, Reinhold Publishing C<Jrporation.
to the material near the surface. Phase changes in New York, New York, 1958.
such propellants cause them to swell somewhat 8. lntemarional Cririca/ Tables of Numerical DaJa.
on aging, but do not appear to interfere with their Physics, Chemistry and Technology , Vol. 4, p. 7.
normal burning processes. Such grains have been McGraw-Hill Book Company, Inc., New York, New
York, l926.
studied 9 but have not found service use.
Ammonium nitrate is an article of commerce, 9. F. R . Groves, Jr. and L. Greiner, Ammonium NilraJe
Solid-Propellanr lnves1iga1ion. Ei1;periment Incorpo-
being widely used as a fertilizer ingredient and as rated, Technical Publication 148, 8 April 1957, Con-
a constituent of commercial high explosives. tract NOrd 16890, CONFIDENTIAL

44
CHAPTER 6

PLASTIC MONOPROPELLANTS
JS. General. Plastic monopropellants, com- of pure polymer. To the right of PH, they are
monly known as smokeless powders,* have been "hotter,'' have higher calorific value (higher force
in use for about 75 years_ The first such propellant or specific impulse). The line BC represents com-
was made by Vieille in France in 1884. 2 Vieille's positions of the minimum practical Young's modu-
product was essentially nitrocellulose, changed lus for propellant use. Below BC the propellant
from its originally fibrous form to a dense plastic cannot be relied on to maintain its geomelry, even
by colloiding with ether and alcohol, forming into when supported by being bonded to the chamber
grains, and subsequently removing most of the walL The line AB defines the lowest calorific value
solvent. A few years later Alfred Nobel introduced that an end-i tern designer can p_rofitably use. All
a different variety of smokeless powder in which useful nitrocellulose monopropellants are, there-
nitroglycerin is used as a colloiding plasticizer for fore, formulated within the polygon PABC.
the nitrocellulose. 3 Propellants containing nitro- Since gun erosion limits the allowable flame
glycerin are known as double-base because they temperature of a propellant, gun propellant for~
contain two explosive ingredients in contrast to mulas tend to fall to the left of the line PH,
single-base propellants which contain nitrocellu- although for some applications they may be well
lose as the only expl~ive ingredient. Addition of to the right. High performance rocket propellants
fuel-type or "deterrent" plasticizers to the formu- are found to the righLof the line PH. Case-bond-
lation gives the necessary flexibility for calorific able propellants fall in the neighborhood of the
value and nitrocellulose content to be varied inde- line BC. Propellants to generate gas at moderate
pendentJy, an important consideration when both temperatures for aircraft starter engines and simi-
ballistic qualities and physical properties may be lar applications are found in the neighborhood of
specified. Ballistic qualities are largely determined the line AB. There exists con sider able overlap
by the calorific value, and physical properties by between the formulation areas for different types
the polymer content. A smokdess powder, looked of end use. In addition to the three basic ingre-
at in this light, is a single-phase or monopropeUant dients a stabilizer is universally used to increase
comprising three ingredients: a polymer, usually the storage life of the propellant, and additives
nitrocellulose; an oxidant plasticizer, usually nitro- may be incorporated to reduce flash, to improve
glycerin; and a fuel plasticizer, for example, ignitability, to reduce metal fouling in gun barrels,
di-n-butyl phthalate. The terms single-base and to reduce the pressure exponent, n, to provide
double-base have lost their significance, single- opacity, and for various other reasons.
base being just a special case in which the oxidant
36-1. Polymer. Nitrocellulose is the usual poly-
plasticizer content happens to be zero.
mer in plastic monopropellants, but other polymers
36. Formulation. The relationships within the can be, and have been, used.
family of nitrocellulose rnonopropellants are shown
qualitatively in the triangular diagram of Figure
26. For ballistic purposes the scale of Figure 26
should be considered about linear in weight frac-
tions. For physical properties it is about linear in
volume fractions. In this figure the line PH rep-
resents all possible compositions with the same
calorific value as pure polymer, P. Lines parallel
to PH are lines of constant calorific value. Com-
positions to the left of PH are "cooler," have lower C0h'3fAN'
CALOJl:I, IC VALUE
calorific value (lower flame temperature) than that
Although the term "smokeless powder" is still current t PUlt.. Pc..A$flCILE R) tOXIOAN' P.lAS:fl(.IZ(f+ I
abroad and in United States commercial circles, the De-
partment of Defense has discontinued Lbe usage.1 Figure 26. Nilroce//ulose Monopropellont Syslem

45
36-Ll. Nitrocellulose. Nitrocellulose is the fore force, specific impulse, or characteristic
product of partial nitration of cellulose, which is a velocity of the propellant is higher the higher the
natural polymer of empirical formula (C 6 HJ(10 5 )n nitrogen content.
and structural formula
36-l.1.2. Solubility. Nitrocellulose at 12.2 per-
cent or 12.6 percent nitrogen is completely soluble,
r-------0 i.e., miscible in all proportions, in a mixture of 2
H
0 parts by volume er.her and I part alcohol, used in
H the reqwred solubility determination! At 13.4 per-
cent nitrogen only a small fraction of the nitro-
H OH cellulose enters the solvent phase. No attempt is
made to measure the solvent content of the nitro-
n cellulose phase . Neither the high solvent fraction
Of the three -OH groups, those at the 2 and 3 nor the proportion of ether and alcohol used in
positions are secondary , while that in the 6 posi- tbis determination is representative of the system
tion is primary. All of the -OH groups can be involved in the manufacture of propellants, where
nitrated, and when cellulose is completely nitrated the nitrocellulose imbibes all of the solvent and no
the resulting nitrocellulose has a nitrogen content separate solvent phase is present . Nevertheless, as
of 14.15 percent. Nitrocellulose as used in com- shown in Figure 27, under the microscope indi-
merce, and as used in propellants is less than vidual fibers can be seen to have maintained their
completely nitrated. Nitrocelluloses are character- identity in unplasticized propellant made from
ized by nitrogen content and viscosity as inde- military blend with ether-alcohol solvent. lntr<>-
pendent variables. Hygroscopicity and solubility in duction of plasticizer into the fonnula usually
various solvents depend primarily on the nitrogen obliterates this phenomenon completely. The rea-
content . Significant commercial grades of nitro- son for this is that imbibition of solvent plus plasti-
cellulose are those used for lacquers at 12 percent cizer so softens the nitrocellulose fibers that the
nitrogen, for dynamite at i 2 percent nitrogen, and fibrous structure is destroyed by the mechanical
for plastics at 11 percent nitrogen . The grades of forces acting during mixing and subsequent opera-
significance to propellants in the United States are tions. Solubility of nitrocellulose in nitroglycerin
gun cotton or high grade at 13 .4 percent nitrogen, follows generally the solubility in ether-alcohol.
pyrocellulose at 12 .6 percent nitrogen, and one as Solvents when used to fabricate double-base pro-
yet not officially named at 12.2 percent nitrogen . pellants usually contain acetone, in which all of
Foreign propellants frequently contain nitroceJlu- the military grades of nitrocellulose are soluble.
lose of lower substitution than 12 percent nitrogen . Determination of el.her-alcohol solubility has little
Guncotton is not used as the only nitrocellulose in real significance either to the manufacture or per-
American propellants, but is commonly blended formance of a propellant. It does serve to indicate
with pyrocellulose to yield a "military blend" at that a given lot of nitrocellulose resembles the
about 13 . lS percent nitrogen or a blend at 13.25 particular nitroceUulose used when the propellant
percent nitrogen . All fibrous nitrocelluloses look was originally standardized .
alike, and indeed look much like the original cellu-
lose . While there could be merit in separately for- 36-1.1.3. Hygroscopicity. The moisture content
mulating two nitrocelluloses into a propellant, the of nitrocellulose in equilibrium with a saturated
elimination of possible confusion between differ- atmosphere at 25C has been expressed 1 by the
ent grades of nitrocellulose and the opportunity equation
of adjusting the ratio of the nitrocelluloses while H = 405.8 - 28.7N (52)
in the fibrous state to an exact blended nitrogen 31.11-N
content argue strongly for blending.
where N is the percent nitrogen in the nitrocellu-
36-1.1.1. Nitrogen content. As indicated in lose. From this equation have been calculated the
Table 2, the contribution of the nitrocellulose to values shown in Table 8 for the nitroceUuloses
the calorific value, flame temperature, and there- used in propellants.

46
CDuTl)I C>/ E . I . iWPon / de Netnours & CC>m pdny . I nc.

Figure 27. Cross Section of Groin of /MR Smoke/eH Powder /or Small Arms,
Phologrophed in Ultraviolet light, J J 2 X Magnifico lion

47
TABLE 8. HYGROSCOPICITY OF nitrate), poly(petrin acrylate), poly(trinitroethyl
NJTROCELLULOSE acrylate), and even fuel-type polymers such as
Ni1rogen i:'\ cellulose acetate or poly( methyl methacrylate) . In
Nitrocellulose Water these cases the negative or deficient contribution
(percent) (percent) on the part of the polymer to the force of the
13.40 !.19 propellant is overcome by the use of oxidant plasti-
13. !5 1.57 cizers such as nitroglycerin and other ni Irate esters.
12.60. 2.38 Cool polymers if used must be physically com-
12.20 2.93
patible with the hot plasticizers. This accounts for
e nature of this relationship may be explained the fact that the cool polymers cited above are all
the basis that it is the unnitrated -OH groups esters.
the nitrocellulose that sorb moisture. Cellulose acetates, like nitrocellulose, are de-
rived from cellulose, are not completely esterified,
36-1.1.4. Viscosity. Viscosity in very dilute so- and are characterized by degree of esterification
ion is a quantitative measure of the average (expressed as percent combined acetic acid) and
lecular weight of a polymer, as shown by the by viscosity. Also like nitrocellulose , a cellulose
1ation acetate in a propellant has its highest degree of
11mc-+ 0 J.(..!L
C "?o
_ I J-_200
DP (53) polymerization at the time of introduction into the
mixer.
ere ,, is the measured viscosity of the solution, Synthetic polymers may be polymerized in ad-
is the viscosity of the solvent, C is the concen- vance of introduction, in which case charac-
tion of the nitrocellulose in the solution, and terization is possible. Alternatively, they can be
'is the degree of polymerization. The value 200 polymerized in situ after mixing.
:mpirical and varies slightly wilh the degree of
lStitution and with the solvent used . The figure 36-2. Stabilizer. In common with other organic
)Wn here is used for acetone solution. The left chemicals, nitrocellulose tends to deteriorate with
mber of Equation 53 is known as the intrin- age by a process known as thermal decomposition.
Jn the case of nitrocellulose, thermal decomposi-
viscosity. The ratio !l. is called the relative tion starts with the splitting off of N0 2 from the
'lo
cosity. nitrate groups. 7 This N0 2 reacts immediately with
At higher concentration secondary effects, not organic material in the propellant (including nitro-
npletely identified, influence the viscosity. For cellulose) and is evolved as NO. The. secondary
lmple, two nitrocelluloses of different origin, reaction of the N0 2 with the nitrocellulose accel-
1wing the same intrinsic viscosity, may have erates the thermal decomposition. Hence thermal
lely differing measured viscosities in more con- decomposition should be minimized by adding to
ttrated solution. For propellant use viscosity is the formula a chemical that will react with the
asured' by timing the fall of a Yi 6 -inch steel N0 2 to give a stable product' and thus prevent
I through a l 0 percent solution of nitrocellulose secondary reaction of N0 2 with nitrocellulose.
acetone. Typical values of nitrocellulose vis- The other product resulting from the loss of the
;ity for propellants are -6 to 25 seconds, but N0 2 is a bound free radical which also tends to
rocel\uloses of higher and lower viscosities are react further to more stable products . An additive
netimes used . The conditions of the viscosity to remove the free radical character of the residue
umination are not representative of any con- should also result in stabilizing the propellant.
ions present during propellant manufacture. Nitroglycerin behaves in a manner similar to that
e determination has as its principal significance of nitrocellulose and can be stabilized in the same
assurance that the mtrocellu lose examined re- way . The stabilizers in current use in the United
nbles that used in the standardized propellant. States are diphenylamine, 2-nitrodiphenylamine,
and ethyl centralite. These are all weak bases,
36-1.2. Other polymers. The polymer io the but they function by being nitrated rather than
1pellant need not be nitrocellulose. Other ener- by formation of salts. Other stabilizers that have
i<: polymers may be used such as poly(vinyl been proposed include N-ethylaniline, carbazole,

48
,B-nerolin, and N-methyl-p-nitroaniline. Mineral Nitroglycerin was the original oxidant-type plas-
jelly, an unsaturated aliphatic, functions as the ticizer and it is still the most used of this type
stabilizer in some British propellants. plasticizer in the United States. lt is usually pre-
pared on the propellant plant site, by the nitration
36-2.1. Diphenylamine. Diphenylamine, of glycerin with a mixture of nitric and sulfuric
(C 6 H 5 hNH, is prepared by subjecting aniline to acids.
high temperature in an autoclave . Nitrate esters other than nitroglycerin have aJso
(54)
been used. In many cases these plasticizers are
cooler than the nitrocellulose; nevertheless, propel-
I ts history in the aging of propellants has been lants in which they are contained are still known
traced .8 The first reaction product is diphenyl- as double-base. Diethylene glycol dinitrate, DGN,
nitrosoarnine, (C 6 H:;)iNNO, followed by ring N0 2(0C 2HJ 20NO:.b and triethylene glycol di-
nitration. Diphenylamine is sufficiently basic to nitrate, TGN, N0 2 (0C!H 4 )aON0 2 , are the most
attack nitroglycerin, so that its main use is in important of these nitrates. The ether bonds in
single-base propellants. these esters are considered advantageous in im-
proving low temperature physical properties of
36-2.2. 2-Nitrodipbenylamine. 2-Nitrodiphenyl- the propellant. DGN has been used more abroad
amine is less basic than d.iphenylamine and is inert than in the United States . Other nitrate& for which
toward nitroglycerin while still being a good sta- feasibility is established are
bilizer. It is preferred to diphenylamine as a stabi- metriol trinitrate
lizer for double-base propellants. It is made by CH 3 C(CH20N02)a
reacting l-chloro-2-nitrobenzene with aniline .
1,2,3-butanetriol trinitrate
CH 2 ON0 2 CHON0 2 CHON02 CH 3
1,2,4-butanetriol trinitrate
(55)
CH 2 ON0 2 CHON0 2CH 2CH 2 ON0 2
petrin
36-2.3. Ethyl centralite. Ethyl centralite, cen- CH 20HC(CH 2 0N0 2)s
tralite-1, or centralite for short, is sym-diethyldi- diethanolnitramine dinitrate (DINA)
phenylurea, CO[N(C 2 H 6 )(C 6 H~)lz . It is made by N02N(C2H40N02)2
reacting phosgene with N-ethyl- or N ,N-diethyl-
aniline. Its reaction history is considerably more 36-4. Fuel-type plasticizers. As is the case with
complicated than that of diphenylamine, ending the oxidant-type plasticizers, fuel-type plasticizers
up with nitrated anilines .' The methyl analog, must be physically compatibl2 with the nitrocellu-
centralite-2 or sym-dimethyldipheny\urea, is also lose and should have sufficiently low vapor pre&-
known and is used somewhat abroad . The cen- sure to remain in the propellant during its life.
traJites are considered to be somewhat less effec- In contrast to the oxidant-type plasticizers, fuel-
tive as stabilizers than 2-nitrodiphenylamine, but type plasticizers contribute no oxidant or only a
they are also quite good plasticizers. When found little oxidant to the e-0mposition and thus tend to
in propellants they are frequently used at higher reduce the force and flame temperature of the
fractions than the diphenylamines to take advan- propellant. It is difficult to draw a sharp line be-
tage of their plasticizing properties. tween chemicals which are oxidant-type plasti-
cizers and those which are fuel-type plasticizers;
36-3. Oxidant-type plasticizers. The required this distinction is not really very important and
properties of an oxidant-type plasticizer are that one is perhaps better off to consider both as plas-
it contribute oxidizing as well as fuel elements to ticizers. Fuel-type plasticizers are frequently the
the composition, that it be physically compatible same plasticizers that are found in eommercial
with the polymer, and that its vapor pressure over plastics and protective coatings. They are used
the composition be low enough that the composi- because they are available in quantity at reason-
tion will not change substantially over the life of able prices. They may be esters such as diethyl, di-
the propellant. methyl, di-n-butyl, or di-(2-ethylhexyl)phthalate;

49
triacetin; the adipates and sebacates; nitre com- burning rnte in double-base rocket propellants.
pounds such as dinitrotoluene; substituted ureas Carbon black and other pigments have been used
such as the centralites; or even mineral jelly as in some propellants to provide opacity and thus
used in the British cordite. 1f the propellant is prevent malfunction due to ignition below the sur-
made by a process involving a volatile solvent, the face at the site of minor imperfections. Metal wire
residual solvent behaves as a fuel-type plasticizer either in chopped form or strung continuously
and differs from the rest of the fuel-type plasti- parallel to the axis of end-burning grains increases
cizers only in that it has a higher vapor pressure the effective burning rate of grains in which they
than is desirable. Gradual loss of residual solvent are incorporated by increasing the burning surface.
on aging of propellants will change the ballistic Other additives of claimed virtue are found in
characteristics. Choice among the fuel-type plasti- some propellants.
cizers is usually made on the basis of availability Solid products in the propellant gas resulting
and cost plus the contribution to the physical from the incorporation of additives contribute to
properties of the propellant. smoke, which is objectionable for reasons similar
to those for flash. The amount of additive used
36-5. Additives. The combustion products of for a given purpose, e.g., flash suppression, must
plastic monopropellants contain gases such as CO be considered in the light of the contribution to
and H 2 which are combustible in air. If the tem- smoke. As discussed in the next section, carbon
perature at time of discharge to the atmosphere is may also appear in smoke.
high enough, ignition of these exhaust products
in air may take place. This phenomenon is known 37. Ballistic characteristics. The calorific values,
as (/,ash, or more specifically secondary flash. Flash flame temperatures, and gas volumes of plastic
is undesirable in gunnery because it discloses the monopropellants may be estimated from the data
position of the piece and tends to interfere with of Table 2 (page 7), from which can be derived
the vision of the gunners, particularly during night the force, characteristic velocity, and specific im-
firing. ln rockets flash can likewise afford data on pulse as outlined in Paragraph 8. Calorific values
the position of the launcher. Flash is also respon- range downward from a maximum of about 1300
sible, at least in pa.rt, for the attenuation of radar calories per gram to quite low or even negative
signals to and from rocket missiles, interfering values. It is surprising perhaps that a propellant
with guidance and telemetry. To avoid or diminish with a negative calorific value will bum to pro-
flash, additives are frequently included in propel- duce a useful working fluid. That it does so is due
lant compositions to suppress this ignition. These to the fact that thermodynamic equilibrium is not
additives may take the form of potassium salts attained at low flame temperattUe and endothermic
which function as negative catalysts for the re- species appear in the gaseous products.
actions of CO and hydrogen with atmospheric Flame temperatures, T "' at constant volume
oxygen. Of the potassium salts available in the may be somewhat over 7000R for sporting or
United Stales, potassium sulfate is the most fre- pistol propellants and may be below 2000R for
quently used, though potassium nitrate has been gas generator propellants.
used in some propellants. Potassium cryolite has The composition of the gaseous products may
been used abroad in propellants mixed in water be determined as outlined in Paragraph 7. In gen-
slurry since it is insoluble in water. eral, only minor quantities of solid products will
Potassium nitrate and barium nitrate have been be found from the combustion of plastic mono-
used in some propellants to make the propellant propellants. The solid products a.re derived from
more readily ignitible . Metallic tin and metallic the additives except that some cool-burning gas
lead are examples of additives in gun propellants generator propellants tend to be smoky. The smoke
to reduce metal fouling. They function by lower- is carbon derived from the propellant composi-
ing the melting point of copper which is deposited tion. Choice of fuel-type plasticizers has a con-
in the barrel by the projectile during travel through siderable effect on smoke. It is claimed that long
the bore. carbon chains and particularly benzene rings in
Certain lead and copper salts have been found the fuel-type plasticizers are more prone to smoke
effective in lowering the pressure coefficient of than are short aliphatic chains. 10

50
12,500 125
c
0 HYGROSCOPICITY
c COllPRESSIYE STREIGTH
T TEISILE STIEIGTH
COllPRESSIYE DEFORllATIOI
x TEISILE DEFORllATIOM

10,000 100

I- c
(/)
z
a.. w
<..>
-I : er
1.5 I- 7 ,500 ~ 75
C)
z z
w 0
er I-
I- <(
I- (/)
::i;!
z c
w w 0::
<..> I- 0
er <( IL.
w
w ::i;!
a.. I-
0
>--1.0 3 5,000 50
c
I-
<..>
a::0
<..>
(/)
0
er
C)
>-
I
o.5 2,500 25

~ "c
C>
o- To
.., Tz..,.,; 0 N
0
)( z"' ~iO :lE i "'
:lE :lE
0 0 0
0.50 0.75 1.00 1.25 1.50 1.75
POLYMER CONCENTRATION, Q/cc

Figure 28. Physical Properties Versus Polymer Concentration

38. Physical properties. Plastic monopropellants ultimate strength, deformation at rupture, and
are thermoplastic, translucent unless pigmented, hygroscopicity typical of these propellants.
and resemble generally the inert thermoplastics of
commerce. Many of the physical properties are 38-1. Ultimate strength. Unplasticized nitro-
determined by the polymer content, probably best cellulose has an ultimate tensile or compressive
expressed in terms of concentration (weight frac- strength near 10,000 psi. As plasticizers of any de-
tion multiplied by specific gravity) of polymer in scription are added the strength decreases rapidly
the propellant. Figure 28 presents data on the to values in the order of 2000 psi at a nitrocellu-

51
lose concentration of 0.9 g/cc and continues to 38-7. Coefficient or thermal expansion. Avail-
decrease to 500 psi at 0 .7 g/cc. ab\e data indicate a thermal expansion coefficient
for propellants comprising largely nitrocellulose
382.. Deformation al rupture. Unplasticized of about 10-~ in/in/"'C. This is considerably
nitrocellulose is bard and somewhat brittle, rup- greater than the expansion coefficient of chamber
turing in either tension or compression at less than materials usually used . Cellulose acetate plastic
I 0 percent deformation. Plasticizers improve this has about the same expansion coefficient as nitro-
property, to about 50 percent at a concentration cellulose propellant, aod this explains the use of
of 0.9 g/cc and to 100 percent at 0.7 glee. cellulose acetate as peripheral inhibitor for many
large grains. ff the propellant is to be case-bonded,
38.J. Cold flow. In common with other thermo-
the existence of a consider able differential in the
plastics, plastic monopropellants have a tendency
expansion coefficients requires that the propellant
toward cold flow that becomes more pronounced
be deformable, have low modulus and large defor-
as the polymer concentration is decreased. This
mation (e.g., BUU, SPIA/M2).
tendency can be counteracted by cross-linking the
polymer. Bifunctional OH~reactive chemicals such 38-8. Plasticity. Below a nitrocellulose concen-
as dusocyanates and anhydrides have beeo used tration of about 0.9 g/ cc, propellants can be
successfully.11 formed under pressure at temperatures considered
safe for manufacturing operations. If the polymer
38-4. Hygroscopicity. Tue hygroscopicity of concentration is much higher than this limit, vola-
unp.lasticized nitrocellulose propellant is roughly tite solvent must be used in the manufacturing
the same as that of the nitrocellulose from which process. When volatile solvents are so used, they
it is made. Upon add.it.ion of plasticizers the hygr~ arc customarily added in sufficient amount to per-
Sc:opicity of propellants drops off a little more mit mixing and granulating at ambient tempera-
rapidly than can be accounted for by simple dilu- ture. This requires adding enough solvent to lower
tion of the nitrocellulose, indicating that as a rule the polymer concentration to about 0 .6 g/ cc.
plasticizers tend to interfere somewhat with the
sorption of water by the unnitrated OH groups of 39. Thermal properties. The thermal decom~
the nitrocellulose. position of nitrocellulose propellants has been
introduced in Paragraph 36-2 under the subject of
385. Density. The assumption seems to be gen- stabilizer. Thermal stability of plastic monopropel-
erally good that no volume changes occur during Jants is measured by the 134.5C heat testu for
the mixing of nitrocellulose propellants. Theo- single-base propellants, by the 120C heat test14
retical densities are computed according to the for double-base propellants, and by the Taliani
formula testH for the larger grains used in rockets and
gas generators. lo addition a surveillance test 11 at
(38)
150F (65.5C) is used to indi~ate the useful life
where x, is the weight fraction and p 1 the density of propellants. These tests are all run at elevated
of ingredient / . Measured densities of propellants temperatures in order to get an end point, and are
are quite close to the computed values. subject to the objection that the temperature c~
efficients of the decomposition reactions are not
38-6. Vapor pressUl'e. Nitrocellulose itself is precisely known . In the I 34.5C heat test a life of
nonvolatile. Plasticizers in general do have meas- 45 minutes is required. The 65 .5C surveillance
urable but low vapor pressures. Propellants in life ranges from about l year for a propellant con-
which these plasticizers are used should and taining 40 percent nitroglycerin to about 3 years
actually do .have vapor pressures which are the for a plasticized single-base propellant. A sample
sum of the partial vapor pressures of the plasti- of 40 percent nitroglycerin sporting propellant
cizers and volatiles, including hygroscopic mois- stored under water since 1899 is still stable and
ture and residual solvents. The vapor pressure reproduces its original ballistics. 17
of nitroglycerin over, propellants bas been exten- The development of supersonic aircraft carry
sively investigated, 11 1, without, however, substan- ing munitions and propellant-actuated devices has
tial agreement as to its value. focused attention on the life of plastic .monoprc:r

52
1250

"'
......
0

"
1000 0
4000
~ z
0 0
(/)
.._.> 0
_J
a..
w >(
Q: w
~
.._. LL.
cl 0
a: 3000 750
w ~
cl
a.. w
::E :I:
w
f.-
w N Gl
~ Q) ::E
cl ,
__J )(
U)~ 0 tl'l N (I) "1
LL.
l! ~::E ::E ::E ::E ::E I-
2000 500
225 250 275 300 325 350 375 400

FORCE, F, It-lb/lb it 1ol

Figure 29. Relotioris/iips Among T"' F, ond Q /or Gun Propellants

peUants at elevated temperatures. The test for this, flame temperature can be predicted reasonably
known as the autoignition test, 13 is comparatively from the calorific value. The accuracy of such
new, and not many data are available. Values of prediction approaches that of the Hirschfelder-
280F for J hour and 250F for 8 hours are Sherman calculation (Paragraph 7-6). If more pre-
typical or propellants containing 40 percent nitro- cision is needed, the exact calculation (Paragraph
glycerin. 7-5) should be performed. Experimental calorim-
etry becomes unreliable at values of Q somewhat
40. Uses. Plastic monopropellants have been
below 800 cal/g, due to failure to attain chemical
used in all types of engines, including guns, rocket
equilibrium at the low resulting temperature in
motors, and gas generators.
the calorimetric bomb.
40-1. Gun propellants. With the exception of There is a difference in physical properties be-
antiques, and some signalling guns as well as mov- tween single- and double-base propellants at the
ing picture and television weapons where the same force level, double-base being softer because
smoke puff is at least as important as any other of lower polymer content. In the United States
effect, all guns use propellants ba~ed on nitrocellu- nitrocellulose concentrations of gun propellants
lose. Figure 29 shows the relationships among have been held to a minimum of about 1.3 g/cc
flame tern peratu re, T v. force, F, and heat of ex- except for thin-webbed ignition or lrench mortar
plosion, Q, of selected gun propellants from propellants . This has necessarily led to residual
SPIA/M2 data sheets. From these data it is ap- solvent, particularly in propellants of large web.
parent that there is no systematic ballistic differ- That this high polymer content is not really re-
ence between single- and double-base propellants quired for functioning in guns is witnessed by the
at the same force level, and indeed the force and fact that gun propellants with polymer concentra-

53
240

.Cl
...... 230
-,g x
-
I
+--

_.
220
w
ti>
_J
::J
c... x
~ 210
0
LL.
0 x
w
Q..
(/}
200
c
w
x
a::
::;:,
ti>
<'[ \90
w
~ x.. .
..
0

...
..."'
,_~
~
),,.
0
-!!!
0

z'
!!
:.
<n'cu
~ )(
.....,z ..

180
O>-
"'

1500 mo 2000 2250 2500 2750 3000 3250


FLAME TEMPERATURE, T, I
OK

figure 30. Specific Impulse ol Double-Bose Rocket Propellants o.s o function of TP

tion below 0.8 glee have long been used in guns firing rate machine guns has now shown that the
abroad. British Cordite S.U. and S.C., is an ex- flame temperature, 2835K, of IMR is too high.
ample of such a propellant. ResiduaJ solvent can Cooler propellants such as Ml8, Tv == 2577"K,
be dried out of large web propellants with polymer are now preferred. A recent study 2 ~ has shown
concentration as high as 1.1 g/cc, 19 and propel- that other propellants of the same T v as M 18 will
lants with polymer concentration below 0.9 glee yield comparable barrel life.
can be manufactured without volatile solvent.
40-1.3. Propellants for mortars. High force has
40-1.1. Propellants for cannon. Barrel life and been the design goal of mortar propellants. Barrel
secondary flash are factors in the selection of erosion appears to be unimportant and flash can
propellants for cannon. Probably the most widely be tolerated. Flash can be eliminated by using a
used cannon propellant in the United States mili- cooler propellant, but at the cost of increased
tary services is M6. Hotter propellants are used charge weight.' 1
when higher muzzle energy is required than is
40-2. Rock.et and gas generator propellants.
delivered by M6. Cooler propellants are used for
Propellants for rockets and gas generators have
guns in which M6 exhibits muzzle flash or un-
usually considerably greater web than gun propel~
acceptable barrel erosion.
!ants have. For this reason the polymer concentra-
40-1.2. Propellants for small arms. For many tion must be kept low in order to pennit removal
years IMR propellaht was the standard propel- of volatile solvent or manufacture without volatile
lant for small arms. Limited barrel life in high solvent. In 'Figure 30 are shown the measured spe-

54
0.8

-u
0.7 '----
I ll

CD )(
fl)

'c
"J.
0.6 ~ --

LL
0
0,..._

0.5
"'0.
0
0 I )(
0
r- 0.4 ~
<l 'I. ~

w
......
<[ 0.3
a:: x
<.!) xx
z
z I
~ 0.2 't
CD
u
l x
(JI
-
t--
Cf)
. ~ U) !'--'!It:
0 IO U)
-~ a:>
zQ_
0.1
:::::i
(/) ' - ft)
Xr rO
(.!)
0
I
:z '
)( ....,
I'--
~

180 200 220 240

0
CALCULATED SPECIFIC IMPULSE, I 1
P

figure 31. Burning Rotes of Double-Bose Rocket ond Gos Generalor PropelJCJnlt

55
ci!ic impulses of a number of double-base rocket OTO is used in the Honest John rocket and in
propellants as a function of flame temperature, the booster (first stage) motors for the Nike Ajax
Tp, taken from selected SPIA/M2 data sheets. and Hercules, Terrier, and Talas missiles.
The significance of the line shown is merely that
OGK is used in the Terrier sustainer motor.
the points above the line are all high because they
were either measured at higher than standard pres- T 16 is used in a 1ine charge projector.
sure or calculated, while those below the line were
measured at lower than standard pressure or with 40-2.2. Propellants for gas generators. As con-
insufficient expansion and should be corrected trasted with rocket motors, gas generators usually
upward. These data, representing for the most part require smaller mass flow of propellant gas for
propellants in service use, were reported before longer times, therefore lower burning rates. The
the adoption of the standard practice of correcting difference is qualitative, and for specialized appli-
measured specific impulses to the standard condi- cations a rocket motor may be best fitted with a
tions described in Paragraph 8-4. gas generator-type propellant and vice versa. Other
Burning rates of double-base rocket and gas requirements for gas generator use may be cool
generator propellants at 1000 psi, 70F as a func- flame temperature or high performance, depend-
tion of calculated specific impulse are shown in ing on the application. Typical of double-base gas
Figure 31. generator propellant com positions is X -13, used
in the Sidewinder gas generator.
40-2.1. Propellants for rockets. Design specifi-
cations for rockets have usually required propel- REFERENCES
lant burning rates between 0.25 and 0.5 inches per
l. M!L-STD-444, Military Standard, Nomenclature and
second in suitable geometries. For short range Definitions in the A mmimilion Area (6 February
applications, short burning times and high accel- 1959).
erations may be more important than high burn- 2. T. L. Davis, The Chemistry of Powder and E;cp/o-
out velocity, and propellants with higher burning sives, Vol. 11, p. 292, Job.n Wiley & Sons, Inc., New
York, 1943.
rate than 0.5 are used. With heavy payloads,
specific impulse is frequently sacrificed to take ad- 3. A. Nobel, British Patents 1471/1888, 9361/1889.
(See also T. L. Davis, loc. cit., pp. 2934.)
vantage of lower flame temperature and the asso-
4. JAN-N-244, Nitrocellulose (for Use in Explosives)
ciated ability to use cheaper materials in the inert (31 July 1945) with Amendment-I (27 December
parts. Plastic monopropellants in service use in- 1945).
clude: 5. E. C. Worden, Technology of Cellulose Es1ers, Vol. l.
Part 3. Nitrocellulose-Theory and Practice, p. 1750,
M7 is used in the shoulder-fired rockets com- D. Van Nostrand Company, New York, New York,
monly known as bazookas. High burning rate is 1921.
attained by using potassium perchlorate as a con- 6. H. Staudinger, Die hochmolekularen organischen
Verbindungen, p. 56, Julius Springer, Berlin. Ger-
stituent in order to satisfy the requirement that many, 1932. (Summarized in M. L Huggins, Physical
burning be complete before the rocket leaves the Proper1ies of Cellulose and /rs Derivatives in Solu-
launching tube. tion. Section E. Theory of the Viicosity of Dilute
Solu1ion of Long-Chain Compounds, in E. Ott, er al.
(editors). Cellulose and Cellulose Derivatives, 2nd
JPN was widely used during World War II, edition, Part !II, p. l l 94, lntersciencc Publishers. Inc ..
notably in the 5.0-inch HVAR. New York, New York, 1955.)
7. J. Barsha, Derivatives of Cellulose. Section 8. ln-
X-8 is a. more recent high-rate propellant less organic Esters. in E. Ou, el al. (editors), Cellulose
sensitive than JPN to ballistics changes with chang- and Cellulose DerivaJives, 2nd edition, Part 11, p. 742,
ing temperature and pressure. Interscience Publishers, lnc., New York, New York,
1954.
M 16 is used -in a booster for 1a unchi ng small 8. L Pauling, Quanlitative Studies of the S1abiliza1ion
target drone aircraft. of Smokeless Powders. Chemical Changes of Sw-
bi/izers in Double-Base Powders During S1orage at
Elevated Temperatures, California lnscitute of Tech-
N-5 is used in the 2.75-inch FFAR "Mighty nology, ClT-FR-3, l July 1946, Contract NOrd 9652.
Mouse." CONF!DENTlAL (SP!A Abstract No. 3388).

56
9. California lnsCi!Ute of Technology, Stabilization of 16. F. A . Zihlman, el al .. A Critical Evaluation of Known
Smokeless Powder by Ethyl Centralite. I. Tronsfor- Methods of Stobiliry Testing . Naval Powde r Factory,
matio11 Products of Ethyl Centralite in Double Base Ind ian Head, Technical Report 25, 3 March 1950,
Powder, OSRD 5967, October 1945 (SPlA Abstract CONFIDENTIAL (SPIA Abstract 10299). F. A . War
No. 0276; see also Nos. 2398-2412). ren, E. L. Anderson and P. M. Ku, Evaluation of
So/id Propel/an/ Properties. Port I-A Survey of Cur-
10. E. Whitworth and C. H. Rigby (lo Imperial Chemical
ren/ Methods , Southwes t Research Institute, Report
Industries Limited), Canadian Patent 541,559 (! 957).
RS 287, 31 January 1959, CONF JOENTIAL (SP IA
11. J. H. Godsey, Cast Propellants with Cross-Linked Absrract No. 19191 ).
Nj1ro,e//u/ose, Allegany Ballistics Laboratory, Her- 17. Hercules Powder Company, unpublished data.
cules Powder C-Ornpany, ABL/MPR 44 (p. 6 of J 8. M IL-0-26389 (USAF), Data Presentation Require-
Monthly Progress Report 4-4), 1 June 1955, Contract ments for Determining Safe Handling, Storage and
NOrd J 0431, CONFIDENTlAL; Propertjes of Cross Shipping Procedures: A eronauticol RockeI Mowrs
Linked PropeJ/onrs. ABL/MPR 48 (p . 6 of Monthly and C ompon en ts ( 14 Novern ber 19 58); MI L.C-2 5641
Progress Report 48), I October 1955 . Conrract NOrd (USAF), Car1ridge , Ca.r Generating, Solid Propellant,
10431, CONFIDENTIAL (SPIA Abstract No. 15565).
Aircraft and Missile, Secondary Power Systems. Gen-
12. W. deC. Crater, "The Vapor Pressures or Glycerol eral Specification For (28 January 1958).
Trin itrate and Certain Glycol Dinitrales," /11d. Eng. 19. A . W. Baum, EIJect of Varialions on Total Volatile
Chem., 21, 674 (1929). Content of 7-8 lnci1 Stick Powder, Radford Ordnance
13 . F . M. Ernsberger, J. G . Wyllie and L. Olsen, Physi- Works, Hercllles Powder Company, RD I , 19 June
cal Instability of Double-Base Propellan1s. Par/ 1. 1944 (SPIA Abstrac t No. 0726) ~ The Modified M-2
Vapor Pressure of BallisJiJe, Naval Ordnance Tesl Formula1io11 , RD 12 , 12 February 1945 (SPIA Ab-
Station. NOTS 240, NAVORD 1184. 29 September s1ract No. 1149).
1949 (SPIA Abstract No. 10386). 20. Research and Development of on Improved Small
Arms Propel/an/ . Non -Erosive E;rtruded Double Bose
14. MIL-STD-286, Propellants: Sampling , lnspec1io11 Propellant fo r Calihu .50, Hercules Powder Cam-
and Testing, Method 404.1.1-Heat TesJs (/ 20 and pany, Kenvil, New Jersey, Final Report of ) 1 De-
/34.5"C.) (28 June 1956).
cember 1956, Contract DA-36-0340RD- I 393RD
15 . MIL-STD-286, Propellants: Sampling , Inspection and (SPJA Abstract No. 17,002).
Testing, Method 406.I (T) To/iani Test (28 June 2 l. A. M. Ball (lo Hercules Powder Company), U. S.
1956). Paten! 2.577,298 (1951 ).

57
CHAPTER 7

COMPOSITES COMPRISING CRY ST ALLINE MONOPROP ELLAN TS


IN PLASTIC MONOPROPELLANT BINDERS

41. General. As was shown in Chapter 5, crys- binder phase, although such propellants have not
taJline monopropellants have limited feasibility as proven unstable.
propellants, the limitations being due to the diffi- The binder will have to withstand a different
culty in getting crystaJs of the size and shape re- set of mechanical forces during drying and tem-
quired for many applications, and to the fact that perature cycling from those encountered in a plas-
pure chemicals do not yield a continuous spectrum tic monopropellant, due to the presence of the
of thermochemical properties. The force or char- crystalline material. The binders are usually well
acteristic velocity of a given crystaJline monopro- plasticized, containing roughly equal weights of
pellant, while within the range of desirable values nitrocellulose and oxidant plasticizer. If stabilizers
for propellants, is seldom optimum for a specific other than ethyl centraJite are used they will be
use. These deficiencies are overcome by accepting- found in the binder phase. Potassium salts, such as
an available particle size distribution or grist of the sulfate or cryolite, may be added to inhibit
the crystalline monoprope\lant, and dispersing it in flash.
a plastic monopropellant. Such composites partake
largely of the properties of the crystalline com- 43. Ballistic characteristics. Due to the low
ponent. The function of the plastic is to act as molecular weight of the combustion products of
a necessary diluent to permit attaining the de- nitroguanidine, nitroguanidine propellants at the
sired geometry with acceptable physical proper- same level of force wiU have lower flame tempera-
ties, and as a modifier to vary the thermochemical tures Tv than single-phase propellants. At the same
properties. level of flame temperature, nitroguanidine system
The field of gun propellants is the only field in propellants will have greater force than single-
which two-monopropellant-phasc composites have phase propellants. Advantage has been taken ot
been widely adopted. Only those composites using this situation in the development of two separate
nitroguanidine have been standardized by the series of propellants, for reduction of secondary
United States military forces, although ROX com- muzzle fl.ash and for increase of force.
posites1 have been demonstrated feasible for gun
and rocket propellants and ammonium nitrate
43-1. Nonflashing nitroguanidine propellants.
compositesi have been studied as rocket or gas
Secondary muzzle fl.ash is due to the combustion
generator propellants.
in air of the gases issuing from the muzzle of the
Containing three explosive in6redients; e.g.,
gun after projectile exit. These gases always con-
nitrocellulose, nitroglycerin and ni troguanidi ne,
tain combustibles such as H 2 and CO. Among the
these propellants are commonly known as "triple-
factors controlling Lheir ignition are temperatUre
base."
and composition at the muzzle, lower tempera-
tures and lower contents of combustibles decreas-
42. Fonnulntions. As with any composite, each ing the tendency to produce muzzle flash. The
phase must be separately formulated, as well as presence of small amounts of potassium salts also
the total composition. The important consideration tends to diminish flash by a negative catalytic
of the crystalline phase is grist, or particle size effect on the reactions of H 2 and CO with atmos-
and size distribulion. In general the finest pos- pheric oxygen.
sible grist is preferred. In the case of nitroguani- Nonflashing nitroguanidine propellants were ex-
dine propellants formulated with ethyl centralite, ' perimented with in this country in the 1920's, but
the centralite forms a crystalline compound with the present standard compositions are based on the
ni troguanidine,1 which indicates that the centralite British Cordite N, disclosed to us during World
will not be in the binder phase. This might be less War II. The American Ml5Al has about the
advantageous than to have the stabilizer in the same combustion temperature as the monopropel-

58
TABLE 9. NONFLASHING PROPELLANTS
Ml5Al T34 Cordlle N M6

Density, ,a 1.66 1.65 l.64 I 60

Force, F, ft-lb/lb 332.000 3 35,000 319 ,000 3 l 7,000

Flame temperature . T., K 2546 2608 2441 2570

Gas molecular weight. M 21.3 21,7 21.2 22 .6

!ant M6 and correspondingly greater force. The function of combustion 1empera1ure and increases
red 1ction in flash compared with M6 is therefore rapidly above some temperature level . An eco-
due largely to the reduction of the combustible nomic balance between muzzle velocity and gun
fraction of the product gas . The corresponding wear for weapons of 3-inch or larger bore indi-
German nitroguanidine propellant 1 is considerably cates that the cost in barrel life is too high to pay
cooler, employing diethylene glycol dinitrate in- for added muzzle velocity if the gun chamber gas
stead of nitroglycerin as the plasticizer. Since temperature is higher than about 3000K . For
M 15A I h 2.~ greater force than M6, a somewhat rapid-fire weapons the economic chamber gas tem-
cooler propellant could still be used effectively in perature is considerably lower than 3000 K .
guns chambered for M6 propellant. Three non- As shown in Table 10, propellants containing
flashing nitroguanidine propellants are shown in nitroguanidine are considerably better than pro-
comparison with M6 in Table 9. peUants without nitroguanidine in the attainment
Two avenues are open for formulating cooler of force within a permitted maximum gas tempera-
nitroguanidine propellants. One is to increase the ture. The propellants M 17 and T36 contain nitro-
fraction of nitroguanidine in the propellant at guanidine; MI 0 and M2 do not contain it.
the cost of a decreased binder fraction . This may High force nitroguanidine propellants were ap-
be limited by a corresponding adverse effect on parently originally developed in the United States.'
physical properties . The other course is to de- Further development of this type propellant de-
crease the calorific value of the binder phase by pends on the ability to increase the fraction of
substituting a cooler plasticizer for that presently nitroguanidine in the propellant, presently limited
used. Such a cooler plasticizer may be diethylene by physical properties.
glycol dinitrate as in the German formulation or
a cooler mixture of nitroglycerin and fuel-type 44. Physical properties. The physical proper-
plasticizer. ties of these composites differ considerably from
those of the plastic monopropellants. They are
43-2. High force nifroguanidine propellants. opaque, chalky white in color unless glazed, and
For certain field uses it is desired to give a pro- exhibit generally lower physical strength. As may
jectile the highest possible muzzle velocity . To a be seen by comparison with the fuel binder com-
first approximation the muzzle velocity should be posites, Chapter 9, the decrease in physical prop-
proportional to the force of the propellant. The erties is not necessarily due to the volume percent
limitation on attainment of muzzle velocity by of filler . It is more probably due to the shape of
increasing propellant force is that gun erosion is a the nitroguanidine crystals, which are needles.

TABLE 10. HIGH FORCE PROPELLANTS


Ml7 T36 MIO M2
Density, p 1.67 1.66 L67 1.65
Force, F, ft-lb / It 364.000 364,500 339,000 360,000
Flame temperarure, T,., K 3017 3040 3000 3319
Gas molecular weight, M 23 . J 23.2 24.6 25.6

59
figure 32 . Cross Secliori ol Triple-Bose Gun Propelloril Grain, Crossed Nicols, 32 X Magnification

60
With an optimum crystal shape, a volume frac- cutting, in order not to deform the cross section at
tion of 70 percent or a weight fraction of a little the cut. Removal of solvent from the composites
more than 70 percent should be feasible without is much more rapid, due possibly to diffusion of
serious degradation of physical properties or manu- solvent with.in the grain along the crystal-plastic
facturability. As the nitroguanidine-filled propel- interfaces. This does not mean that drying times
lants are customarily manufactured by solvent should be reduced . In order co make a good
extrusion, nonparallel orientation of needles may quality grain it is necessary to use lower drying
be expected to cause bridging and to interfere with temperatures and times comparable to those for
normal shrinkage during drying . The resulting conventional smokeless powders in order to avoid
residual . stresses in the binder phase may explain steep solvent gradients and resulting distortion and
the physical property deficiencies of these propel- cracking.
lants. Nitroguan idine has been prepared 1 with a A photomicrograph of a cross section of a nitro-
more favorable crystal habit which improved the guanidine propellant grain' is shown in Figure 32 .
manufacturability of existing formulations . lt is
interesting to note that in the early American
llEFERENCES
srudies, experimental propellants containing up to
80 percent nitroguanidine were fired in artillery l. 0 . J. Z.auder, Developmenr of Improved Propellani~ .
pieces at Aberdeen Proving Ground .' P1caliony Arsenal, Technical Reporc No. ! 923, 5 June
1953, Ord. Proj. TA!-3601, CONFIDENTIAL (SPtA
Abstract No. 13 ,287).
45. Thermal properties. The crystalline mono-
2. Redstone Arseoal, Quarterly Report (Solid Propellant
propellants are generally more stable than plastic and Igniter Development). Rept. No . 3M 7N24 (Oct.
monopropellants, becoming unstable only neat Dec. 1957), I January 1958, CONFJDENTlAL (SPJ A
their melting points. The aging of composites con- Abstract No. 18 ,085).
taining them is therefore due mainly to the binder, 3. J. N . Pring (by mesne assignmenls w Imperial Chem
ical Industries, Ltd .), U.S. Patent 2,557,463 (1951).
which is a plastic monopropellant. Stability tests
4. R. A. Cooley, 1. Waser aod K. Mislow, German
dependent on measuring the evolution of oxides Powder Development Be/ween 1918 and 1942 ( A
of nitrogen from a fixed weight of propellant in- Translation of the German Book Die Gnchii1z/a ung
dicate better stability for these composites than by U. Gallwi12), California Institute of Technology,
15 September 1945, NAVORD 43-45 (SPI A Abstract
for ordinary nitrocellulose mooopropelJants . Trus No. 3597).
indicated increased stability may not be real. Aut0- 5. A. W. Baum, J . G . Fihcky and R Wirier. Production
ignition temperatures for various lengths of expo- of Ni1roguanidine Propellan1s in Severa/ Connon
Powda Gronulntions, Radford Ordnance Works
sure may be expected to be higher than for the Hercules Powder Company, Radfo rd RD 8, I l Jun~
binders alone, due to this same binder dilution, 1945 (SPlA Abstract No. 1093).
provided that the melting points of the crystaJline 6. V. Milanc, R. Evans, S. Skolnik and F. C. Thames,
rnonopropellants are not too closely approached Preparation of High -Bulk-Density N11roguanidine ,
Naval Powder Factory, fodian Head, Technical Re-
in the test. porl No. 66, NAVORD 3037, 14 De.:ernber 1953.
CONFIDENTIAL (SP!A Abstract No. 14009); J.
46. Manufacturing process. The manufacturing Cohen and R. A. Henry, A New Method for the
pr.:>eess used for the nitroguanidine propellants in Prepara1ion of Ni1roguonidine wilh . High Bulk De11 -
the United States has been uniformly solvent ex- si1y, Naval Ordnaoce Test Station, NOTS 182,
NAVORD 1062 , 31 December 1948, CONFfOEN-
trusion . The nitrocellulose concentration in the TIAL (SPTA Abs1ract No. 3640) .
binder phase is low enough to suggest that a sol- 7. W. F. Jac kson (E. I. du Po11L de Nemours & Com-
ventless procedure could be used . The amount of pany, Inc.), private communication.
solvent used is guite low aad the propellant during 8. C. W. Hock, Microscopical Examination of Propel-
lants ConJaining Nitroguanidi!U!, Hercules Powder
extrusion is very sofr so that it is sometimes neces- Company, RI 3112. 25 Augus1 1954, CONFIDEN-
sary to dry the extruded strand partially before TIAL (SPIA Abs!ract No . 15.01 ll.

61
CHAPTER 8

MANUFACTURING PROCESSES FOR SMOKELESS POWDER

47. Genera\. No one manufacturing process 48. Nitrocellulose. The process installed in the
will produce the whole spectrum of plastic mono- ordnance works, and a!so widely used commer-
propellanrs . As is the case with commercial inert cially, is the Du Pont mechanical dipping process. 1
thermoplastics, a wide variety of manufacturing Continuous processes have been instal!ed by one
processes has been developed 10 make different or more commercial producers but the details have
propellant grains. Nearly every fabricarion proc- not been published . It is believed that these proc-
ess used by the commercial plastics industry has esses are engineering adaptations of the mechani-
been used for propellants; in fact some processes cal dipping process . The ftowsheet of the Du Pont
used for propellants have nor yet been used by the process 1s shown in Figure 33.
plastics industry. For any given process 1he dif- Cellulose in the form of cotton linters is dried on
ference between use for prope!lanrs and use for a moving belt in a tunnel drier to a moisture con -
inerr plastics is that the consequences of a fire tent well below 1 percent. Alternatively, sheeted
during processing propellants are severe and ex- wood cellulose may be dried in the drier and rhen
traordinary precautions must be taken to prevent shredded. The dried cellulose and mixed nitrating
fires and to control them if they do occur. Aside acid are in1roduced concurrently into the nitrator
from details in 1he design of equipment, the most (Figure 34) where the cel!ulose is converted to
striking feature of propellant manufacturing proc- nitrocellulose. At the end of the nitration cycle,
esses has been the requirement to handle 1he ma- about 25 to 30 minutes, the nitrator is discharged
terial in process in batches of finite size, separated by gravity to the centrifugal wringer (figure 35)
from other operations by distances such that the where the spent acid is removed. Part of the spent
loss of a charge and its containing equipment will acid is sent back to the process for reuse after
not entail propagarion to neighboring operations. butting up with fresh acid. The remainder is re-
This requiremenr has, until recently, discouraged worked 10 remove from the system the water
the development of continuous processes, and is picked up from the nitration. The wrung nitro-
still a problem to people currently working on cellulose, wee with spent acid, is quickly drowned
continuous processes. and transferred to the boiling tubs (Figure 36).
Important processes used for nitrocellulose sys- There, for a period of several hoursi depending
tem propellants are solvent extnisiDn, solvent on the degree of ni1ra.11on of the n1trocellulose, it is
emulsion, rolling of sheets, solvencless extrusion, boiled in the weak acid resulting from the dilution
the cast double-base process, and slurry casting. of the spent acid no1 removed in the wringing
Since nitrocellulose is commonly manufactured operation. This boiling treatment serves to hydro-
also at the propellant facility , its manufaciure too lyze any sulfate ester formed during the nitration.
is described here. The nitrocellulose is nex1 pulped, e.g ., in one or

SHll(OO[R

CR1[A
OOllHG
BEATERS ~OACf<ERS
rues

4 Cl 0 MtX

ACID
~-------------ll'---lcQt<cfNTJIATOR WRING RS WAT[>l -
W( T HC

figure 33. Nitrocellvlose Manulocture

62
l/. S Army Phi>togroph Rodford A r~ena/

Figure 34. Cellulose N itrator

63
V . S. Army Ph.otof{TO.Pll Ra.d/nrd An~naJ

Figure 35. Nitrocellulose Wringers

64
U. S .4rmv PMlog'aph Radford ArBenal

Figure 36. Nitrocellulose Boiling Tubs

more Jordan engines similar to those used in the acid, becoming diluted by the residual moisture in
papermaking industry, and finally "poached" or the cellulose and also by the by-product water
boiled in a slightly alkaline solution to neutralize of the nitration reaction penettates on through the
and remove any residual acid. Thorough washing particle, leaving behind nitrocellulose of slightly
completes the purification cycle. In order to accu- decreasing degree of substitution . The first nitra-
mulate lots of sufficient size, or to produce a mixed tion reaction is quite rapid , but subsequent equi-
nitration grade such as military blend, poacher libration in acid of different composition is much
batches are blended in blending tubs. The finished slower and is not complete by the end of the
nitrocellulose is centrifugally wrung to a water nitration operation. for this reason, careful frac-
content of about 25 to 30 percent for transfer to tionation of nitrocellulose reveals a spectrum of
propellant operations. nitrogen contents in the nitrocellulose .
Cotton linters fibers which have thin cell walls
48-1. Nitrngeo content. The degree of nitration and enough twist to keep them essentially apart in
is controlled by the equilibrium between the nitro- the nitrator produce a nitrocellulose of a narrower
cellulose and t.he spent acid. 4 As the acid pene- substitution spectrum than wood cellulose shreds
trates the cellulose particle the surface is first where regions of compaction are found. The cellu-
nitrated to equilibrium with the fresh acid. The lose-acid ratio for wood cellulose is higher than

65
that [or cotton, result 1ng in <! greater change of volume production operation it is preferable to
add strength during the nitration operation. This m;iintain the nitration degree of the 1'.i'.rocellulose
adds 10 the width of the nit rat ion spectrum for the constant, by control of the niir:ttion opcratiN1 ;ind
wood nitrocellulose. Finally, while conon cellulose by blending, rather than to adjust the fornwl<1.
is almost pure po!ymeri2cd dextran, wood cellu- The viscosity and solubility have secondary effect~
lose usually con 1ains an admix tu re of other sugars in the manufacturing ope ratiom in that tlic; <iffcct
such as xylan And mannan These become nitrated the amount of solvent (and plasticizer) required
and their nitrJtes burn like nitrated dextrnn but to work the propellant. This is panicularly trUL'
they have secondary effects on the physical during !he solvent extrusion operation where the
strength of the polymer and its solution properties. applied pressure is constant and requires approx i-
For most purposes wood nitrocellulose is a com- mately constant plasticity of the green (solvent-
plete substitute for cot ton nitrocellulose. wet) propellant. The finished dimensions of the
Transpiration of moist air in the wringer can propellant are determined by the solvent content
cause a lowering of the nitrogen !eve! by denitra- and the die dimensions, so that if the plasticity is
tion. A slight hydrolysis occurs also in the boiling controlled by varying solvent content the dimen-
operation. Both o( these effects are minor in a sional control is forfeited, Similarly for solventless
well-conducted operation. extrusions the finished dimensions are con!roiled
by extrusion temperature and die si7.e, and if tem-
48-2. So!ubilif)' At 12.6 percent nitrogen or peratures are changed to control plast1ci ty dtring
12 .2 percent nitrogen ni trace l\ulose is miscible in extrusion, control of dimensions is less good. For
all proportions with ether-alcohol. Since the nitro- these reasons nitrocellulose specifications call for
gen content measured is the average across a spec- control of solubility and viscosity as well as con-
trum, a poorly nitrated cellulose with average tra! of degree of nitration.
nitrogen content in the soluble range may contain
fractions either more or less highly substituted 49. Solvent extrusion. Tn Figure 26 (page 45),
than are completely miscible. In such cases this the line SS divides the polygon PABC ir.to two
would be detected by a residue in the solubility regions. Below SS the physical properties of the
determina1ion. 3 G uncotton contains a small frac- system are such that the composition can be
tion that is soluble, either by reason of low sub- worked and formed at tenable temperatures.
stitution or low degree of polymeri2ation. Above the line SS they cannot be so worked. A
48-3. Viscosit.'. The l'iscos1ty of nitrocellulose composition X in the upper region can be made
is determined by the v1scosi ty (degree of polymeri- only by a process using a volatile solvent which
zation) of the original celh..: lose and by (he rec.Juc- is subsequently removed. A propellant made by
tion of the degree of pcl~'merizlltion incident !o a vola1ilc s0!vcn1 process always contains some
the ni trocdl ulo<;e 1n anu (acturi ng operation~. Most residual so\wnt, and residual solvent is one form
of this reduction occurs c.Juring the nitration step, of fuel pl'1s!icizcr. One should first establish a
where it is dependent on the nitration tempera- composition X' such th:i1 the addition of the re-
~idual solvent to X' will produce X. To the com-
ture. Higher nitraling temperatures result in lower
viscosity nitroce!!uloses. posi!ion X' 1s ad<.lcd enough volatile solvent to
enable the propellant to be procc~se<.I. This re~u!!s
48-4. Significance of nitrocellulose properties. in the compo~ition X" i:1 the mixer which is well
Of the three propertic5 discus5cd above only the below the !inc SS. Compo~ition X" is frequently
degree of nitrntion has ballistic significance, affect- so far !o 1he left of line PH thnl the mix will not
ing !he molecular weight <1nd temperature of the burn without air, and the h<mird situation is
combustion products. In order to manufacture a thereby somewhat dimini>.hcd. Solvent evapora!es
propellant of a specified force, F, (or specific im- dunng processing :ind the composition of the ma-
pulse) one must either have the proper nitration terial m process creeps back toward X. It must
of the nitrocellulose or compensate for the differ- not cross the line SS until after the last forming
ence between the prescribed niirocellulose and the operation has been completed. Final drying leaves
nitrocellulose at hand by adjusting the proportion the ma!erial at composi!ion X. No1e that X', X.
of oxidant plasticizer and fuel plastici~er. In a X''. and F arc collinear.

66
NC---
O(HY
ALCO~OL PRESS

SRtAX AIR ORY


BLOC~ EXTRUOE CUT
8LOC><S

r.------ --- -- ------------- -l


'
L - - - - - - - .. - - - - - -

H
I '
NG
CE lONE - !
t>fi(MIX
(SCHRAEOER l
M4CERl>T[
I

PREBLOCK H MACAllONI ~-j


'

'I( COVER
SOLVENT
Wi>TER ORY

50LVEl>f1 ------~

PL4511CIZ(I> - - - - ----'

AOQ111vE - -- - - - -- '

~----'~i
L ~ SCRELN
f" '-----'
H.__B_LE_NO
_
-
_,H __ t--
.
"A_C_K_.....
-
DISK
CORD
' I
'- - - -~ ~ -- " - - --- - - - -- SINGLE P(RrOAATEO
j. I I C"t LINDER
~-CO_A_T--~ll_J L_l
n GLAZE
j
MULTIPL(-PEAfORATEO
CYLINO(R
TO 1 - INCo< OD

Figure 37. So/vent EJ<lrusion Process

For nitrocelluloses used for propellants in the of the ingredients and solvents used in the par-
United States the position of the line SS corre- ticular propellant, and it is the function of the
sponds roughly to a nitrocellulose concentration mixer to mix them thoroughly into a single homo-
(weight fraction multiplied by propellant density) geneous plastic phase. The sigma blade mixer is
in the finished propellant of about 1.0 g/ cc. A capable of a good mixing job but it has certain
volatile solvent process must be used for all pro- disadvantages. The shafts of the sigma blades pass
pellants with a greater nitrocellulose concentration through the end walls of the mixer below the upper
than this. The solvent extrusion process is. some- surface of the material being mixed . The treat-
times used for propellants wirh lower nitrocellu- ment of the glands through which the shafts pass
lose concentration in order to reduce the calorific is different for different types of propellant being
value of the mix. Because the residual solvent con- processed. For double-base propellant it )s cus-
tent increases with polymer content and with the tomary to remove the packing, leaving a clearance
web, the solvent extrusion process can be used between the shaft and the wall aperture. A small
only on grains with fairly thin webs. It is widely amount of the mix leaks out through this clear-
tJ~-;d for propellants for guns, including small arms ance and must be collected and destroyed. lt is
: :i::l spornng pieces. recognized that a mixer without submerged glands
1r.e ftowsheet of the solvent extrusion process would be preferable.
:s ~iiown in Figure 37.
49-1.1. Premixing operations. The ingredients
!'he es~en tial operations of the solvent extru-
may be added singly or in combinations. If a
(;O process are mixing, forming, removal of sol-
combined add is made, a premixing operation is
vent, and finishing. To these operations have been
required. Thus nitrocellulose is premixed with
added a number of auxiliary operations designed
alcohol by displacing the water, present in the
to save operation time and improve the quality of
nitrocellulose as received, in a hydraulic press
the product. As indicated by the dotted lines, these
equipped to pass alcohol through the block under
auxiliary operations arc not invariably used .
pressure . The dehy press has two rams. The basket
49-1. Mixing. The heart of the mixing opera- is first filled with loose, water-wet nitrocellulose.
tion is the sigma blade mixer, shown in discharge The press is then closed and the nitrocellulose
position in Figure 38. To this mixer are added all compressed to a "block" to express a portion of

67
U. S . 1\rm_y Phc1o~ruph Radford Arsenal

Figure 38. Sigma Blade Mixer

the water. Alcohol is then pumped through the tives may be dissolved in the solvent before adding
block, displacing the remainder of the water. The to the sigma blade mixer.
dehydrated block is broken, sometimes in a " block The solvents used in the United States for
breaker" or picking roll, sometimes by hand dur solvent-extrusion process prope!lanrs are usually
ing the charging of the sigma blade mixer, some- 3 ether : 1 alcohol by weight for single-base pro-
times by the sigma blade itself during the mixing pellants and about 1 acetone : 1 alcohol for double-
operation. base. Other solvent systems, including esters, are
Addition of nitroglycerin or other oxidant plas- feasible .
ticizer to the dehydrated nitrocellulose is usually,
but not always, accomplished in the Schraeder 49-1.2. Post-sigma blade m1X1Jlg operations.
bow! shown in Figure 39 . The purpose of this is Post-sigma blade mixing operations are also some-
to a void the presence of a free nitroglycerin phase times employed to shorten the sigma blade mixer
in the sigma blade mixer at any time. Nitrocellu- cycle and 10 improve the quality of the mix. The
lose and nitroglycerin are sometimes mixed in macerator, shown in Figure 40, works the mix on
water slurry, followed by drying and re-wetting toothed rolls, subjects it to a vigorous tearing
with solvent before mixing in the sigma blade action, and reduces the bulk density of the finished
mixer. sigma blade charge, particularly if the fiber struc-
Fuel-type plasticizers and solvent-soluble addi- ture has not been completely destroyed at that

68
V S . Army P/uJtogrnph Rad.lord A,,.cna.I

Figure 39. Schroeder Mixer

69
U S_ Arm,v P"'11ograph Radford An~nal

Figure 40. Macera/or

70
U S Army Photograpil lfo.ct./ord A r uno1

Figure 41. Macaroni and Blocking Presse.

71
point. The macaroni or screening press works the from single-base powders, the final stages of sol.-
propellant by flow through screens and dies, sub- vent removal may be accomplished under water
jecting it to shear forces. It serves also to filter out in order to shorten the total elapsed time. The
incompletely colloided particles of nitrocellulose w:iter assists solvent diffusion by preventing pre-
remaining after mixing, as well as foreign bodies. mature formation of an impervious skin on the
propellant surface. A final air dry removes the
49-2. Forming. The cylindrical surfaces of the
water.
grain are formed by extrusion through a die, using
either horizontal or vertical hydraulic presses. The 49-4. Finishing. Propellants for small arms may
die dimensions must be such as to yield a green be coated with a deterrent plasticizer to retard
(solvent-wet) strand of such cross section that on gas evolution during early travel of the projectile.
subsequent drying the final dimensions will be as This operation is performed in a rotating "sweetie"
designed. The shrinkage of propellant is almost barrel, similar to equipment used for sugar-coating
entirely in the cross section a,od the vol~es of pills, whence the name. The equipment is showo
propellant and solvent are approximately addi- in Figure 43. The barrel is equipped with a warm-
tive, so the desired green dimensions are readily water jacket to heat the charge to. a temperature
calculated. where the coating agent will flow evenly onto the
The charge for the finishing press is prepared by grains and be driven into the outer layers. The
compacting in a blocking press which is a hydraulic grain shown in Figure 27 (page 47) has been SC'
press working against a closed end. A similar coated.
blocking operation known as preblockiog precedes Some propellants are "'glazed" or coated lightly
the macaroni operation ii used . In Figure 41 are with graphite to decrease the accumulation of
shown strands emerging from the macaroni press static electricity during handling and to increase
and entering the blocking press. the bulk density through better pa.ding. This oper-
Extruded strands are cut to length, usually while ation is also performed in a rot.a.ting barrel, which
still containing solvent. The equipment for this may be an unjacketed sweetie barrel or a larger
varies with the grain length. A cutting machine barrel on a horizontal axis .
used for gun propellant is shown in Figure 42. Propellant at this stage may contain tailings
The cutting knives are mounted on a rotating disk, from the cutting operation, clusters of grains from
and the strand is fed into the machine by feed the drying operations, and dusts of various ~
rolls synchronized with the cutting bead. scriptions from cutting, coating, and glaZing. These
are removed by screening. Screening is usually
49-3. Removal of solvent. The mechanism of accomplished dry just before blending. As an alter-
solvent removal involves diffusion of the solvent nate procedure sc~ning may be done wet with
to the surface of the grain and evaporation from water following the coating operation.
the grain . The rate of diffusion controls the drying
rate, the surface of the grain being normally dry . 49-S. Blending. As solvent-extruded propel-
_Plasticized compositions dry more rapidly than lants are almost invariably used in multiple-grain
unplasticized, and thin webs dry to lower residual charges, they are blended into lots cpntaining up to
solvent content than thick webs within tolerable 500,000 pounds. This blending may be done in a
operating cycles. tower, in which case .!he entire lot is taken to the
In the manufacture of single-base propellants top of the tower and allowed to cascade over hori-
the solvents are recovered for reuse. This is not zontal ha.files. Alternatively blending may be done
ordinarily done with double-base propellants be- in a barrel, in which case a number of pre.-blends
cause the recovered solvents would be contami- are made, a barrel charge at a time, and the final
nated with nitroglycerui. Capital and operating blend is accomplished by blending in the bJrrel of
costs to reel.aim them safely for reuse outweigh the aliquots from each preblend. For barrel blending,
value of the recovered solvents. The amount of the glazing operation may constitute prebleoding.
solvent used with these more highly plasticized 49-6. Propellants made by solvent e:drasioa.
propellants is considerably less than that used for Products of the solvent extrusion process include
single-base. sporting powder in the Corm of disks and short
After most of the solvent bas been removed tubes ; single-base propellants for-small anQll such

72
U. S Army Photcgrllph Ra;JJord An""'1

Figure 42. Cutting Machine

73
Figure 43. Sweelie Borre/

as IMR; for cannon, including MI, Ml 0, M 12, 50- 1. Fonning operations. The process starts
M6, M14, IX-82; double-base gun propellants in- with the formation of spherical particles of nitro-
cluding M2, MS, M9, the British Cordites CD cellulose. The equipment for this operation com-
and WM; double-base rocket propellant M7. Data prises a closed, steam-jacketed vessel or "still,"
sheels for all of these propellants may be found shown in Figure 46, equipped with paddle-baffle
in the Propellant Manual SPIA/M2. Casting pow- or double turbin_e agitation and an auxiliary sol-
ders used as intermediates in the cast double-base vent recovery system. Nitrocellulose is dispersed
process may be made by solvent extrusion, as are in a nonsolvent (water) and a solvent (ethyl ace-
also the triple-base gun propeUants discussed in tate), a stabilizer (diphenylamine) and perhaps
Chapter 7. other additives arc added Additives introduced at
this point must be insoluble in water and i( crystal-
50. Solvent emulsion (Ball Powder) process. A
line they must have a particle size that is small com-
second and radicalJy different process 5 6 uses a
pared to the size of the finished propellant spheres.
volatile solvent to form propellant as spheres and
When mixed and heated the ingredients form sepa-
related shapes sold as Ball Powder. The ftow-
rate water and lacguer phases. Stabilization of
sheet of this process is shown in Figure 44, and
reclaimed nitroceUulose' or even of incompletely
the product in Figure 45.
stabilized new nitroceOulose still containing smalJ
Trademark of Olin Mathieson Chemical Corporation. amounts of inorganic acid can be accomplished in

74
HE AO$ Ao~ O 1 AILS
SOLV(N7 lO REUSE 10 R(CYCLE

NC
NON SOLV Ef>ll
S0LV EN1 ---~ DISSOLV E
EMULSIF Y SCREEN ORY
ADDIT IV ES - - HARDEN
COL LOI D
SALT I
..'' I I

~
I I

~- L~
I I
ADD t- J ROLL GLAZE
[MUL S lfY
NG Pl A ST IC I Z( R
FU EL Pl AS T1C12R

I I

COAT1NG AGENT
~ (MUl.SlfY
~-1 COAT
~-J
GRl>.P,..ITE

Figure 44, Solvent Emv/sion Process

this low viscosity lacquer phase, using chalk as an by emulsifying at high she a r, heating the emulsion
additive to neutralize the acid, When a smooth to a temperature well above the atmosphenc boil-
lacquer has formed, a protective colloid is added ing point, and flash evaporating che solvent. These
to form an emulsion. The size and size distribution spheres may rhen be plasticized as described
of the lacquer panicles in this emulsion are con- below . They are usually coated with a small
trolled by the kind and degree of agitation. A salt amount o{ casting plasticizer prior to drying to
is then added to draw dissolved and emulsified minimize accumulation of a static charge when
water by osmosis from the lacquer droplets . Omis- dry .
sion of the salt results in a lower density product.
50-2. Incorporation of plasticizers . Screened
The solvent 1s di s tilled off by rai.!ing the tempera-
curs, still in water slurry. are weighed pycnomctri-
ture and is recovered for reuse. When solvent re-
cally and pumped into a second still. The slurry is
moval is complete, the slurry is cooled, dewatered ,
again heated and plasticizers (fuel and / or oxidant)
and washed to remove the salt and proreccive col-
are added. 1 11 If nitroglycerin is use d it is added
loid . The washed product is reslurried and pumped
in the form of solvent solution . The plasticizer, or
to the screening operation.
plasticizer solution, is emulsified before addition
Screening is done wet on a series of vibrating
to the slurry. Penetration of the solvent into the
or rotary screens, yielding one or more sizes for
nitrocellulose spheres is a time-temperature func-
further processing ro different end products. The
tion and may be controlled to leave a plasticizer
grain size range of any cut is within about 10 to
gradient within the granule. When the impregna-
15 percent of the average of the cut.
tion hns been completed the solvent is removed,
Larger spheres and more uniform sizes may be
leaving a controlled amount of solvent in the
produced by a modification ~ of the above proc-
granules to facil itate the coating operation.
ess in which the lacquer is made up in the absence
of nonsolvent, extruded via a metering pump and 50-3. Finishing operations. Coating agents are
orifice plate as strands into a proportionate stream again added as emulsions and the operation of
of nonsolvent containing the protective colloid, coming is performed a1 controlled time and tem-
and cut to square cylinders. The cylinders assume perature .
a spherical shape during transfer w the still where In order to get more closely controlled web, the
density adjustment (salt) and solvent removal are coated propellnnt may next be passed through
accomplished as described above . si2.ing rolls which flatten the ~arger balls. The prod-
Spheres 50 to 75 microns in diamecer suitable uct is then dried and finished in the same way
for slurry casting, described below, are made 16 ' 1 as the corresponding solvent-excruded propellants .

75
Couruay of Olin M~ Ch.r.mical Corpotu1.1on

Figure 45. Bolf Powder

76
ColJ.rldy of Olin Malhinon Chemu:al CorporYJ.t~m

Figure 46. Sfi//

Water-soluble additives, impossible to add during may be dewatered by a centrifuge, or drained off
the slurry operations, may be applied to the sur- through a filter or a nutsch. Further elimination
face of the grains during the glazing operation. of water roay be accomplished by air-drying. Final
elirrunation of water or volatile solvent is usually
St. Rolled shed process. If the propellant is to accomplished during the rolling operation at .the
be used in the form of sheets, strips, cubes, or time that the propellant is consolidated to a sheet,
some other form of rectangular geometry, it may although drying operations may be used between
be suitably made by a rolled sheet process. This is passes over the rolls or after the conclusion of the
basically the process originally used by Nobel, and rolling operation.
is more extensively used abroad than in the United
States . The flowsheet for this process is shown in 51-2. Rolling. The roll mills may be even-speed
Figure 47. (both rolls rotating at the same peripheral speed)
or differential (one roll faster than the other), or
51-1. Mixing. A great deal of fiexibility is pos- a combioatioo of differential and even-speed mills
sible within this process. Mixing may be accom- may be used. Outside the United States most
plished either with or without the use of volatile rolling operations are conducted on even-speed
solvent in a Schraeder mixer or in a sigma blade rolls . In this operation the first pass forms a sheet,
mixer, or it may take place in water slurry. If which is folded and/or rotated for each succeed-
slurry mixing is used, the still fibrous mix, or paste, ing pass . In the United States differential rolling is

77
MIX
1 ROLL
I I FIN IS H
I ""
TRENCH MORTAR
INCREMENT

WATER SLURRY EVEN- SPEED SE:W STRIP

SCHRAEDER DIFFERENTIAL SLIT CUBE

SIGMA BLADE CHOP

PUNCH

Figure 47. Rolled Sheet Process

U S . Army Photograph Sunflower Ordnaue Worka

Figure 48. Roll Mi//

78
U S Army Photog1aph Rad/01d Ar,.~al

Figure 49. Slitter

79
extensively used. The charge adheres to the cooler 52-1. Eirtrusion. The process starts with rolled
roll and passes repeatedJy through the bite until sheet, which is formed into press charges by carpet
it is stripped off. A differential roll cycle is thus rolling (Figure 53) or by stacking disks cut from
properly identified by time and roll temperature the sheet. United States practice is to use carpet
instead of by number of passes. A typical roll mill roUs. The charge is brought to extrusion tem-
is shown in Figure 48. perature before putting into the press (Figure 54)
which is equipped with temperature controls on
Sl-3. Finishing. Strip powder is made by slit- both the press basket and the die. The press basket
ting the sheet using equipment similar to that is evacuated before extrusion starts. The extruded
shown in Figure 49 in which rotating knives bear strand may be cut during the extrusion by a flying
on the sheet as it passes over a feed roller. Cubes cutter which travels with the strand during the
may be formed by cutting packages of strips with cut, or the whole strand may be extruded and cut
a guillotine, or by feeding sheet stock through a to grain blanks between pressing cycles. Th.e por-
dicer in which slitti.ng and chopping are done in tion of the strand remaining in the die between
one operation . Individual shapes such as disks extrusion cycles is known as the neck and is essen-
may be punched from the sheets with a rule die. tially compression-molded. It has different dimen-
During World War II trench mortar increments as sions from the extruded strand due to annealing
illustrated in Figure 50 were made from sheet in the die between extrusions, and ordinarily is
powder by the sequence of operations: sewing reworked. In going to larger . cross sect.ions, one
a package of sheets together longitudinally using a may reach the point where an entire extrusion
sewing machine, slitting parallel to the seams, cut- would be contained within the die. From this point
ting across the seams, and simultaneously punch- on, the whole extrusion would be neck. This should
ing holes with a punch press. result in even better dimensional fidelity than is
attained in conventional extrusion.
52. Solventless extrusion process. Propellants
with a nitrocellulose concentration below l g/cc, 52-2. Finishing. As is the case with the rolled
particularly at webs over 0.4-inch, and in cross sheet process, finishing operations are developed
sections up to about 7 inches diameter may be to meet the requirements of the product. For a
made by the solventless extrusion process, shown gun propellant no fmisbi.ng operations should be
in Figure 51. The ex.istence of installed capacity required other than cooling and equilibrating with
and wealth of experience on the solvent extru- an atmosphere of the standard relative humidity .
sion process has discouraged United States use For a rocket or gas generator grain with tight
of the solventless exuusion process for webs less dimensional tolerances the first finishing operation
than 0.4-inch, aJthough abroad webs considerably is annealing to relieve residual stresses in order to
smaller have been extruded without solvent. The stabilize dimensions. This is done by heating the
upper size limit bas been set by the ability of a die grain blanks to perhaps 120F for several hours.
in a 15-incb press to form a perfectly consolidated lo its relaxation the grain becomes a little shorter
grain. Since World War II work both in the United and a little fatter. Without the annealing opera-
States and abroad has indicated the possibility of tion the same changes would take place slowly,
extruding considerably larger grains, even exceed- causing the finished grain to go off dimensions.
ing the cross section of the powder basket of the After annealing the grain can be machined to
press, by incofl>Orating an expansion chamber be~ length by sawing, and to diameter by using a lathe
tween the basket and the die. As with most ex- or dowel rod machine. Radial boles may be drilled
trusion processes the products have cylindrical through the web or slots miUen as required.
geometry . l.o the case of solventless extrusion the Inhibitor patches to restrict the burning may be
word cylindrical may be very broadJy construed cemented to the grain at the ends or along the
(Figure 52). Since no volatiles are present during lateral surface. lnhibitors that cover the entire cir-
the exrrusion the die has nearly the same shape cumferential surface are usually wrapped. Cellu-
and dimensions as the strand, and cross sectional lose acetate plastic wet with acetone and ethyl
details including sharp angles can be reproduced cellulose plastic wet with a mixture of ethyl lac-
with fidelity. tate and bury! acetate are the common inhibitors

80
U S_ Army Phowgraph Radford Anicnal

figure 50. Trench Marlar Increments

AO LL ED
SH((f CsL1r H CARPET ROLL
r- ~
I
r-
f XTRUOf
H FINiSll
rVARIOUS Sl<APES
ro 1 INCHES

I
I I ANNEAL
MACIJlllE

~-1 PUNCH
H STACI<
~-~ 1,,.tt1e1r

Figure 51. Solventleu Ex1rusion Process

81
LJ_ S _ Nou y P/v:Jt<J8raphi Noool Propel1'1nt P/0111
Figure 52. Solvenlless Ex/ruded Shapes

82
V . S . Army Ph.oJ.LJgraph Sunflo~r Ordr\Anc Worka

Figure 53. Carpet Roll;ng

83
U.S. Army Phologro.ph Sw1flower Ordnanu Wor.06

FiglJre 54. Solvenl/ess EJ(frusion Press

used with solventless extruded grains. The sol- 53. Cast double-base process. The cast double.-
veots are subsequently removed by diffusion and base process is used to form propellants in any
evaporation. geometry and in siz.es from about l inch in diam-
eter up to unlimited size . It uses as intermediates
52-3. Flaws. Any imperfections in the propel-
casting powder, which may be made either by
lant tend to be elongated in the axial direction as
solvent extrusion (short cylinders about 0.03-inch
a result of the extrusion operation. This is usually
in diameter by 0.03-inch long) or by the Ball
not serious when burning of the grain is in the
Powder process (spheres of similar dimension),
radial direction because no great amount of un-
and casting solvent, which is a mixture of plasti-
planned additional surface is exposed when the
burning surface meets the flaw. Inspection oa a sta- cizers. The bulk density of the casting powders is
tistical basis coupled with quality control through- about I g/cc, and the finished propellant occupies
out the operation is adequate to maintain such the same volume as its casting powder. This re-
flaws at an acceptable minimum. When che grain sulrs in a maxim um nitrocellulose concentration
produced is an erid-burner, however, no axial in the cast propel Ian I of about I g/cc. Cast double-
flaws may be permitted. Great care must be taken base propellants are 1hcrefore possible in the same
to reject any grains cootaining such flaws . Flaw range of compositions as solventlcss extruded
detection may be done with X-rays or supersonics . propellants .

84
CAS l 1NO POWD R CuRE O< SASSEMSLE MACMINE CARlRIDOE 8
CAST
CASTING SOLi/ENT CASE BOND TO
l1Nl1"'1TED
S?E & SHAPE

~SSE,..91.E
....01.0

Figure 55. Cast Double-Base Process

The ftowsheet of the process is shown in Fig- the individual grains to coalesce to form a single
ure 55. grain within the mold . Due to the fact that the
casting powder is glazed to dissipate static elec-
53-1. Castiog. The casting powder is first tricity and to facilitate charging, grain boundaries
loaded into the mold and evacuated overnight. are visible in the finished casting, but fractures
The casting solvent, also previously evacuated, is produced in tensile strength testing do not follow
then also introduced inlO the mold, usually by the grain boundaries. This indicates that the cast
air pressure, where it fills the interstices between propellant has become really homogeneous.
the individual casting powder grains. The casting The circumferential inhibitor required of car-
powder imbibes the solvent and swells, causing tridge-type internal burning grains is usually

U. S NoOJ y Pho1011rapll Al/ego"" Ballu ttct Loboroiorv


Figure 56. Mold Ports

85
U S NOJJy Pholl>/Jrap lo Al!.>gony Boll,.lrc Labo1a1ory

Figure 57 . Casting Selup

86
V . S. Nauy Ph.oro1,raph A1lla-a11y Bolliatic Laboratory

Figure 58. Cart Grain

87
prefabricated and known as the beaker. It is used face that is relatively impervious to the liquid
as part of the mold. If a case-bonded grain is called components at the temperatures of mixing and
for, the case is first lined with any required insula- casting and yet readily soluble at curing tem-
tion and with a surface to which the propel:lant perature. At least three such processes have been
1 11
will bond . The case then becomes part of the mold. descnbed.
/

Typical mold parts are shown in Figure 56. /


The assembled mold and accessories are shown / REFERENCES
in Figure 57. The flow of casting solvent may be . !. J. R. Du Pont, "Manufacture of Cellulose Nitrate for
/ Pyroxylin Plastics," Chem . Mer , Eng .. 26, 11 (1922).
upward, downward, or radial through the mold.
2. R. L. Stem (to Hercules Powder C-Ompany), U. S.
As a result of blending giant lots of casting pow- Parent 2,028,080 (l 936).
der and carefully controlling the composition of 3. JAN-N-244, Nilrocellulou (For Use in E.rplosjyes)
casting solvent, large lots of cast grains can be pre- (31 July 1945) with Amendment-1 (27 December
pared with an excellent within-lot reproducibility. 1945).
4. E. Berl, K. R . Andress and C. Escale.s, Beirriige wr
53-2. Curing. The curing operation, during Kenntnis der Mischsiiure, p. 32, L F. Lehmann,
Munich, Germany, 1937. (Summari.ud in J . Barsha,
which coalescence is completed, is done at ele- Derivatives of Cellulose. Section 8. Inorganic Esters,
vated temperatures (about 140F) and requires in E. Ott, et al. [editors), Cellulose und Cellulose De-
about 3 days after the grain has come to curing rivatives, 2ncl edition, Part II, p. 720, Iotencience
Publishers, Inc., New York. New York, 1954 .)
temperature. After the completion of the cure the
5. F. Olsen, G. C, Tibbitts ao~ E. B. W. Kerone (to
mold is disassembled and cleaned for reuse. The Western Cartrid~e Qimpe.ny), U. S. Patent 2,027 ,114
grain is finished by sawing to length and machining (1936),
any designed surfaces not produced by the mold. 6. H. F . Schaefer (lo Western Cartridge Company), U. S.
Patent 2, J 60,626 ( 1939).
53-3. Physical strength. Physical strength of 7. MIL-P-3984, Propellants, for Small Arms A mmuni-
tion, Calibers .30 to 30 MM inclusive, E.rcept Blank
cast double-base propellant is comparable to that und Caliber .45 (30 November 1956).
of propellant of the same composition produced 8. J. J. O'Neill, Jr. aod G . R. Cox. (to Olin Mathie-
by solventless extrusion. Flaws if present are ran- son Chemical Corporation), U. S. Patent 2,740,705
domly distributed and not elongated, so that the (1956).
9. 1. J. O'Neill, Jr. and G, R . Cox (to Oli..o Mathie-
tolerance of flaws for end-burning castings is con- son Chemical Corporation), U. S. Patent 2,830,886
siderably greater than for end-burning extrusions. (1958).
A finished grain is shown in Figure 58. 10. R. L. O>ok and E . A. Andrew (to Olin Mathieson
Chemical Corporation), U . S. Patent 2,888,713 (1959).
53-4. Uses of propeUants made by cast double- 11. E. A. Andrew (to Olin Mathieson Chemical Corpora-
base process. Examples of propellants produced tion), U. S. Patent 2,929, 107 (1960).
12. G. A. McBride (to Wesrem Cartridge Company),
by casting are OGK, OIO, and BPY for cartridge U . S. Palen! J ,955,927 ( ! 934).
applications and BUU, a case-bonded propellant. !3. W. E. Wagner (lo Western Cartridge C.Ompany), U.S.
Note that these compositions must be broken down Patent 2,008,889 (1935).
to a casting powder composition and a casting 14. C. E, Silk (to Western Cartridge Company), U. S.
solvent in order to manufacture them. Patent 2,335,804 ( ! 943).
15. J. J. O'Neill, Jr. (to Olin Mathieson Chemical Cor-
poration), U.S. Patent 2,916,775 ( 1959); E. A. Andrew
54. Slurry casting process. When the total vol- (to Olin Mathieson Chemical Corporation), U. S.
ume of the liquid ingredients exceeds about 30 Patent 2,929,107 (1960).
percent of the volume of the composition it be- 16. A. W. Sloan and D . J. Mann (to A1lan1ic Research
comes possible to suspend the solids, including the Corporation), U. S. Patents 2,931,800 and 2,9J t ,80 1
(1960).
polymer, in the mixed liquids and pour the result-
17. 1. Reinharl, W. E. Stump, M. L. Bovee, B. 0 . Stull
ing slurry directly into the mold. l.n this instance and A. T. Camp, Ni1raso/ Propel/an1s-Compositf'
the solids must be supplied in a shape that has Propel/am Formulations Based on a Plastisol Ni1ro-
good packing density, such as spheres. As the cellulose-Pentaery1hri10/ Trinirrate Binder, N1111al
Ordnance Test Station, Bulletin of The Fourteenth
packing density of the solids decreases, the re- Meeting of The Joint Army-Navy-Air Force Solid
quired volume fraction of the liquid ingredients Propellant Group, Vol. IV, p, 9, CONFIDENTIAL.
increases. lt is further necessary, for the sake of Solid Propellant Information Ageocy, Applied Physics
Laboratory, The Johns Hopkins University, Silver
pot life, that the polymer particles possess a sur- ::Spring, Maryland.

88
CHAPTER 9

FUEL BINDER COMPOSITES

SS. General. The first fuel binder composites rosive under conditions of high humidity, This
in the United States were developed during World condition has proven entirely acceptable for condi-
War II in response to a need for grains for use in tions in rocketry where the engines are expended
aircraft jatos. Smokeless powders had been widely in a single firing. It is less acceptable for some gas
used for gun propellants and had been made generator uses where the combustion gases remain
abroad by solvcntlcss extrusion into grains for in contact with metal parts that will be reused.
artillery rockets, and solventless extrusion was When considerations other than maximum per-
being developed in this country. It was not imme- formance, such as freedom from corrosive exhaust
diately apparent that smokeless powder could be or cheapness and availability of raw materials, t.ake
fabricated into grain cross sections of the size precedence ammonium nitrate may be used in
required for such jato use, such cross sections place of the ammonium perchlorate.
being beyond the capacity of existing or contem- The third major development was the substitu-
plated presses. The black powder art had demon- tion of an elastomeric binder for the hard polymer
strated that a solid propellant need not be a binder. This permitted case bonding of the pro-
monopropellant. pellant and elimination of the inhibitor from in-
Existing black powder manufacturing tech- ternal burning grains. Replacement of the inhibitor
niques would not produce large grains. The exist- by addition.al propellant increases the mass frac-
ing black powder formula was less energetic than tion, or ratio of propellant weight to loaded motor
desired. Substitution of a hydrocarbon for the weight, and thereby the performance of a rocket.
sulfur and charcoal of black powder put all of Continuing need for thermal insulation negates
the fuel into the binder phase, increasing the vol- this advantage of case bonding for end-burning
ume fraction of binder to a point where a casting grains.
operation became feasible. At the same time oxi-
dation of the hydrocarbon led to products (includ- 56. Choice of oxidizer. The differences among
ing H 2 and H 2 0) of lower avernge molecular the three oxidizers that have been widely used
weight than those derived from black powder. Sub- in fuel binder composites, potassium perchlorate,
stitution of potassium perchlorate for potassium ammonium perchlorate, and ammonium nitrate
nitrate increased oxygen content per unit volume are shown in Table 11 . As a matter of interest,
of filler and decreased the weight of solid residue
per unit weight of propellant. The asphalt-potas- TABLE 11. OXIDIZERS FOR FUEL
sium perchlorate interim propellant successfully BINDER COMPOSITES
est.ablisbed the position of fuel binder composites KCI0.1 NH~C10 4 NH.N03 KN Os
in the propellant field and encouraged further
Molecular weight 138.SS I L7.50 80.05 101.10
development. Specific gravity. ,.2.52 1.95 !.725 2.1 !
The first major improvement was the substitu- \.2CI., 0.0036 0.0043
tion of a polymer system for the asphalt. The filler \.2H~ 0.0170 0.0250
was mixed with binder in monomeric or partially 1-2 N.& 0.0043 Q.0125 0,0049
0., 0.0288 0.0340 0.0375 0,0247
polymerized form and cast in that condition. Poly-
. I
merization was completed in the curing operation Specific volume, -p 0.397 0.513 0.580 0.474
in the mold, resulting in a grain that would not
cold flow under moderately warm ambient condi- figures are included for KN0 3 . Following the
tions as would the asphalt. nomenclature of Chapter 2, the items O"" is
The second major improvement was the sub- the number of gram atoms of Cl in one gram of
stitution of ammonium perchlorate for the potas- oxidizer, Hoz, the number of gram atoms of hydro-
sium salt, eliminating inorganic residues and dense gen, etc. In the case of potassium perchlorate part
smoke. The gaseous combustion products, how- of the KO resulting from pyrolysis of the oxidizer
ever, now contained HO which is somewhat cor- is found to be vaporized, and part remains in the

89
condensed phase. For the purpose of the present The potassium nitrate member of this series of
argument it is assumed that half of it is in the gas propellants is capable of producing as much gas
phase. In the case of ammonium perchlorate all
of the chlorine is in the gas phase, and its contri- (~) as the potassium perchlorate member but
bution to the gas volume is 1/2 Cl""". Any hydrogen
will be in the form of either H 2 or H 2 0, so the the total available oxygen is only enough to oxi-
contribution of the hydrogen of the o:x.idizer to dize the carbon to CO. This propellant is badly
the combustion product volume is l/2 Hw The underoxidized, and potassium nitrate has properly
o:x.ygen of the oxidizer will appear as CO, C0 2 , been ignored in the development of fuel binder
or H 2 0 and makes no separate contribution to composites.
the gas volume. ln the case of potassium nitrate
56-1. Potassium perchlorate. Potassium per-
it is assumed that a solid residue of K 2 0 will
chlorate has the considerable disadvantage that
exist under operating conditions. This removes
a major part of the KCI formed in its pyrolysis
one-half atom of oxygen from the quantity avail-
remains condensed under operating conditions, re-
able for oxidizing fuel, and the value of 0.,.,. under
KN0 3 is corrected for this. sulting in a low gas volume(~), Tbe rest of the
A more significant comparison of the oxidizers KCI condenses in the exhaust, and any propellant
appears when they are formuJated with a fuel. As formulated with potassium perchlorate burns with
an example, consider a series of propellants forrnu a dense white smoke . Linear burning rates of
lated at 75 weight percent oxidizers with a hypo- potassium perchlorate propellants tend to be high,
thetical fuel of composition CH 1 ;, and specific 0.8 to 0.9 in/ sec at 1000 psi. Propellant densities
gravity 1.2. Data concerning such a fuel are shown also are high, 1.8 to 2.0 g/ cc, reflecting the high
in Table J 2 and for the propellants in Table 13. specific gravity of potassium perchlorate. Specific
impulses are generally below 200 lb-sec/ lb, re-

TABLE 12. HYPOTHETICAL FUEL


flecting the low ga!. volume, (~) . The pressure
BINDER CH 1 .:; exponent, n (Equation 31 a), tends also to be high.
Molecular weight l 3.5
Due to the low specific impulse and smoky ex-
~H, 0.0556 haust, potassium perchlorate propellants are no
c, 0.0740 longer in general use.
Specific volume . ..!..
p
0.833 56-2. Ammonium perchlorate. Ammonium
perchlorate avoids most of the disadvantages of
potassium perchlorate. Propellants containing am-
TABLE 13. HYPOTHETICAL monium perchlorate bum substantially without
PROPELLANTS residue or smoke, and the oxidizer makes a sub-
stantial contribution to the gas volume. As a resujt
KCIO~ NH.CI04 NH.N03 KN03
-- -- of this, specific impulses have been calculated to
0.r.idiur weigh I 0.75 0.75 0.75 0.75
Binder weight 0.25
about 250 and mea~ured to about 240 lb-sec/ sec.
0.25 0.25 0.25
2:C 0.0185 0.0185 0.0185 0.0185 The (measured) specific impulses and the flame
VlN 0.0032 0.0094 0.0037 temperature5 of selected ammonium perchlorate
'hH 0.0128 0.0188 propellants taken from SPJA / M2 data sheets are
Y.i.H, 0.0139 0.0139 0.0139 0.0139 shown in Figure 59.
~.:rc1 0.0027 0.0032
I
As these propellants were made up with a vari-
0.0351 0.0516 0.0606 0.0361 ety of binders, iL is apparent that specific impulse
M
i:o 0.0216 0.0255 0.0282 0.0185 and flame temperature are largely determined by
~0-~C 0.0031 0.0070 0.0097 the weight loading of the oxidizer. Over the range
Oxidizer volume 0.298 0.385 0.435 O.J55
Binder volume 0.208 0.20&
55 to 81 weight percent oxidizer, the flame tem-
0.20& 0.20&
Total volume 0.506 0.593 0.64J 0.563 peratures seem to be linear and nearly propor-
Sp.:cific gravity, p 1.97 1.69 1.56 l.78 tional to the weight fraction of oxidizer. The
Binder volume,% 41 35 32 J7 specific impulse also rises with increasing weight

90
..D
.......
0 ~
t) 0
I
.a a.
250 2500 I-
0. UJ
~
a:::
::J
I-
w <[
U) a:::
_J w
::> 0..
a. ~
~ w
I-
u 200 2000
w
LL. ~
u <[
w _J
0.. IXl 0 u...
(/)
u WU
-
0 ~
rt')-
<1
N <1 w ll'J
I I') I- N
..,. .... wo ....
u ll'J
-I

1- I-
nN
i'.= ~ t-Cl ~
z
NO:.
C\J u Na:. z
<(
a._

<{ <{

1501-------"""""------....i.--------.....------..i..----------------.....----...... soo 1

50 60 70 80

NH4CI04 OXIDIZER, WEIGHT PERCENT

Figure 59. Specific Impulse, f,P, and Flame Temperature, Tv, of NH.iCIO~-Fuel Binder Composites

fraction of oxidizer but appears to approach a in a given cornpos1t1on . Burning rates of ammo-
maximum of about 240 lb-sec/lb. nium perchlorate propellants have also been in-
Comparing the two examples of potassium per- creased by substitution of potassium perchlorate
chlorate propellants (ALT-161 and AK-14) with for part of the ammonium perchlorate, but at the
Figure 59, it appears that the potassium perchlo- cost of a smoky exhaust. Burning rates may also
rate propellants at about 75 percent oxidizer are be influenced by catalysts.
equivalent in specific impulse and flame tempera- Ammonium perchJorate is a monopropellant.
ture to ammonium perchlorate propellants at ts pyrolysis starts with dissociation according to
about 60 percent oxidizer. the reaction'
Burning rates of ammonium perchlorate pro-
pellants at 1000 psi and room temperature are
NH~Cl0 4 ___,, NH 3 + HCl0 1 (57)
plotted in Figure 60 . They also seem to trend leading to a combustible mixture of NH 3 and
upward with increasing weight percent of oxidizer HCI0.1 in the gas phase adjacent to a NH 4 Cl0 4
but are subject to other influences. l t is recognized crystal.' Subsequent features of tbe combustion re-
that oxidizer grist has an effect on the burning actions are a matter of some disputG. According
rate, coarse oxidizer leading to low burrung rates to the two-temperature theory1 the burning sur-

91

0.50

.,u
"'
...... 0.40
c

....
w
...... 0.30
ct
0:::

~
z
z .0.20
~
:>
m

0
(X) u
O.JO u - - - I - - - - - + CJ)
ro; -
o -, will
C\I <:2' }- {\J
I .., - I
Na:: r--. 'il ua..
o.._______.......I-
______....,________ NU
..._______......._______ N Z 0::2
I- .,!. l!) I-__.________________
<C <( <C
_

50 60 70 BO

figure 60. Burning Role, r, al 1000 psi, Ambienl Temperolure ol NH~ C/0.1 -Fuel Binder Composites

face retreats in a plane, the linear burning rates The reaction products of ammonium perchlo-
of the binder and oxidizer are the same. This rate fuel binder composites are N 2 , CO, C02, Hz,
requires that the surface temperatures of burol.ng H 2 0, and HCl. Of these products only HCl de-
oxidiz.er and binder be different. The thermal layer serves special menlion, the others being common
theory, 3 on the other band, states that the rate- to smokeless powders which have long been used
controlling step is the redox reaction of the mono- in various heat engines. At relative humidities
propellant, in this case berween the NHa and above about 85 percent 1 HC! tends to condense
HC10 4 , that burning surface is not plane, and that to droplets of aqueous HCI, giving rise to smoke
diffusion of binder pyrolytic products into the and to corrosion of metal surfaces. The wide use
thermal layer where the redox reacticn is going on of ammonium perchlorate fuel binder composite
may lead to perturbation depending on the rela- propellants in rockets is an indication that for
tive rates of reaction between the oxidizer-binder rocketry HCl in the exhaust is not a serious...prob-
pyrolysis products and the oxidizer pyrolysis prod- lem. If other atomic species are present in the
ucts alone. binder, their compounds will. of course. appear

92
HO 2~0

.."'
. 2000
,.:

:t
- ~

- ~
!...
~
~ ...
! :I
<t
l!>O ISOO _,
I)
~
...
;::;
"'...
..
...
N

"'
......
..J
z
4.
<.J
100 1000
60 10 40 90

Figure 61. Specific Impulses, l81u and Flame Temperatures, T11 , of NH~N0.1 -Fuel Binder Composites

in the exhaust and may be additional sources of chlorate system . If maximum performance is not
corrosion. required, quite low flame temperatures can be
56-3. Lithium perchlorate. Lithium perchlorate attained by decreasing the ammonium nitrate load-
has received some attention as an oxidizer in these ing, or by incorporating thermally decomposed
composite propellants (e.g ., GCR-300 in SPIA/ diluents such as cyanoguanidine .
M2) . This oxidizer should be superior to potas ~ Burning rates appear to range from 0.05 to
sium perchlorate in that the LiCl should all be 0 .27. The combination of low temperature and
vaporized and form part of the working fluid, with 1ow burning rate is attractive for gas generator
the amount of available oxygen per unit weight of uses. The higher rates are available through the
oxidizer higher due to lower molecular weight. use of catalysts such as Prussian blue (ferric ferro-
Condensation of LiO in the exhaust should lead cyanide),5 6 Milori blue, 1 chromium compounds
to dense smoke as in the case of the potassium such as ammonium dichromate, 8 cobalt com-
salt. Propellants containing lithium perchlorate pounds, 9 or sodium barbiturate. 10 The higher
have higher density but are more hygroscopic than burning rates so produced are useful in sustainer
corresponding ammonium perchlorate propellants. motors and even booster rockets. 11
The burning mechanism of ammonium nitrate
56-4. Ammonium nitrate. The use of ammo- propellants has been extensively investigated. Am-
nium nitrate as oxidizer in fuel binder composites monium nitrate is also a monopropellant, and its
avoids the problem of corrosive exhaust due to first pyrolytic product is a gaseous mixture of NH 3
HCl, at the cost of lowered specific impulse. As and HN0 3 . The rate-controlling reaction is pre-
indicated in Table 13, the volume(~) of prod- sumed 1 to be the redox reaction
uct gas is higher than for a corresponding ammo-
nium perchlorate propellant, so that the lower
NH :1 + N02 ~ NH2 + HN0 2 (58)
specific impulse must result from a lower flame and in the thermal layer theory the reactions of
temperature, Tp. This is indeed the case, as may binder pyrolytic products with the ammonium
be seen in Figure 61. The maximum specific im- nitrate pyrolytic products occur so late (so far
pulse appears to be in the neighborhood of 200 from the burning surface) that they do not com-
lb-sec/ lb, and this is attained at a flame tempera- municate heat to the burning surface. This would
ture some hundreds of degrees lower than for explain qualitatively the slow burning rates. The
the same specific impulse in the ammonium per- mechanism of catalysis has not been explained.

93
The combustion products of ammonium nitrate volume fraction of the continuum may be de-
composites are N 2 , CO, CO:!, H 2 , and H:.10, the creased 10 40 or even 35 volume percent before
same a~ from smokeless powders. and presenc no the presence of the solids is strongly felt in the
new probkrns. They are generally in a compara- fluidity of the system. Beyond that point the vis-
tively high w-1te of oxidlltion, ~o that even the cosity of the system increases rapidly, and a con-
cool formulations burn without producing much cenvation is soon reached where the system will
free carbon. not flow. In the fuel binder composite system,
Ammonium nitrate is hygroscopic and, in addi- casting loses its feasibility when the volume frac-
tion,exhibits phase changes at several temperatures. tion of the binder goes much below 30 percent.
Precautions must be taken to keep ammonium ni- Concurrently even with elastomeric binders the
trate propellants below 40 percent relative humid- discorcion at rupture approaches a low value whe:1
ity during ma nu fact ure and subsequent handling. the volume fraction of the binder decreases below
Processing is preferably done at tern peratures this region. For case-bonded systems, therefore,
above 90F 10 avoid cycling through the phase the fraction of binder must be maintained above
change at that temperature. The higher perform- this minimum in order that the grain maintain its
ance ammonium nitrate propellants are so formu- integrity over a temperature range. This means
lated that their volume fraction of binder is too chat when one is formulating a high performance
low to permit casting. Extrusion or compression grain, which will therefore require a low weight
molding processes are commonly used to fabricate fraction of binder, the preferred binder will be a
~uch propellancs. low density material in order that the volume frac-
tion of the binder be simultaneously kept high.
56-5. Mixed oxidizers. Combinations of oxi-
On the other hand. at low oxidizer loading such
dizers are sometimes used to get burning rates
as is preferred for low flame-temperature gas gen-
outside the normal ranges for single oxidizers.
erator propellants, the binder weight fraction will
The combination of potassium perchlorate 12 with
be naturally higher and one might well choose a
ammonium perchlorate leads to higher burning
dense binder to minimize the envelope. Table 14
rates than the arithmetic mean of the normal rates
of the two oxidizers measured separately. This
TABLE 14. OXIDIZER LOADING VERSUS
combination preserves the high pressure exponent
BINDER DENSITY PER UNIT VOLUME
(e.g., Tl O-E3 in SPIA/M2) of the potassium per-
chlorate propellants; indeed in some proportions Binder dcnsit y 1.0 I 2 1.4
Volume 0.30 0.30 0.30
of these two oxidizers values of n approaching or
Weight 0.30 0.36 0.42
even exceeding l have been observed. Ammonium NH~CI04 volume 0.70 0.70 0.70
nitrate, nitroguanidi ne, or cyclotetramethylene- Weight l.37 1.37 l.37
terranitramine (HMX) may be used as pan of the Propellant density. p !.67 1.73 !.79
NH~C10 4 , weight percent 82 79 76
oxidizer 13 to lower the burning rate of an ammo-
Binder. weight percent 18 21 24
nium perchlorate propellant. Ammonium picrate
comprises part of the oxidizer in the British plastic NH4NOJ volume 0.70 0.70 0.70
propellants. Weight 1.21 1.21 1.21
Propellant density, p l.5) 1.57 1.63
57. Volumetric relation of oxidizer to binder. NH 4 NO~. weight percenl 80 77 74
As shown above, the ballistic properties of a fuel- Binder. weigh! percent 20 23 26
bi nder composite propellant are determined by the
weight fraction of oxidizer. The physical proper- ii lustra le s the effect of binder density on the
ties including fluidity during manufacture are de- weight percent oxidiz.er loading at a constant 30
termined by the volume fraction of binder and on volume percent binder basis.
the choice of binder, with the shape of the oxidizer
particles and their grist playing a supporting role. 58. Choice of binder. End-item use may re-
Roughly spherical solids can be dispersed in liquids quire either a cartridge-type grain, for ease of in-
up to about 50 volume percent without having spection or for repetitive use of the chamber, or
much effect on the fluidity of the system, and a case-bonded grain for high performance. If a
with favorable grist and solid particle shape the cartridge-type grain is called for, the propellant

Q4
MONOMER Oil
PREPOL1"1fJ! - . . . - - - - - - - ;
CATALYST
OEA(llATE CAST CU<I flNIS""
A[)01TIVES

GRIND CLEAN & ASS(M8l


OXIOIZfl; 8 SCREEN MOLi> PARTS

Figure 62. Slurry Costing Proce5S

must have high modulus and some compressive poly(vinyl chloride), used with enough pl<1s1icizer
streng1 h. If the grain is 10 be case-bonded the 10 bring 1he modulus of 1he propdlanl into lh~
stresses to which the grain will be subjected call proper range .
for tow modulus and high elongation .
58-3.L Pol~:sulfide rubber. The first such binder
58-I. Asphalt . Asphalt, tht first binder used in wa~ formulated with polysulfide rubber.'' and
a fuel-binder composite, produced a case-bondable polysulfide rubbers have remained important con-
propellant . As may be seen from the data sheet stituents of case-bonded composite propellants Y
on ,..\ L T-16 l (see SPIA/ M2), the asphalt wa$ The polymer is introduced as a partially polymer-
softened with a plasticizer to decrease the modulus ized prepolymer (liquid polymer) and polymeriza-
so that the propeliant could be used over a suit- tion is completed during the curing operation in
able but restricted temperature range. At tempera- the case or mold at elevated temperature and in the
tures below about - 20f the propellant became presence of a polymerization cntalyst such as
very brittle, leading to fracture and explosion on p-quinonedioxime. ln order to accelerate the cure
ignition. At temperatures above about 120F the or 10 accomplish ic a1 a lower temperature, a pro-
propellant became quite soft and flowed away from moter such as dipheny\guanidine is sometimes also
its design geometry. Asphalt had the advantage of used. Magnesium oxide and ferric oxide may be
being cheap and available. The propellant manu- used to modify the burn ing rate, and other addi-
tacture was simple , the oxidizer was incorporated tives are occasionally used for various reasons .
into the binder at elevated temperature using a Polysulfidc propellants are fairly dense, reflect-
sigma blade mixer and the mixture was poured ing the density of the polysulfide polymer. This
m<o the mold or case and allowed to cool. feature restricts the allowable oxidizer loading . In
the moderate performance range, on the other
58-2. Polyisobutene. Polyisobutene, used in the
hand, a given total impulse can be contained within
British ''pl'lstic propellanr," differs from .asphalt
a smaller envelope than with a less dense propel-
chiefly in having a better temperature coefficient
lant . At temperatures above about 0F the tensile
of physical properties . An example of such pro-
strain at rupture is typica!ly 50 to l 00 percent,
pellant is R .D. 2312 (see SPlA/M2). The oxi-
being lower with che higher loading density . This
dizer ammonium picrate is readily deformable and
level is generally adequate for case-bonded appli-
hence permits a lower rhan normal binder volume
cations.
fraction. Ir also affords a lower burning rate than
In more than 10 years of existence, polysulfide
ammonium perchlorate would give as the sole
propellants have not shown seriously deleterious
ox idizer .
aging effects except for a change on the exposed
58-3. Elastomcric binders. Tensile strength surface of the grains that interferes with ignition .
enough to enable the propellant to withstand It is believed that this property has been over-
handling and firing accelerations is added to the come in later formulations, but this can be demon-
binder properties by incorporation of a polymer, strated only when the newer propellants have been
often cross-linked, into the binder. The polymer aged .
may be one of the rubbers, used with or with- The manufacturing process used for polysulfide
out a plasticizer, or it may be one of the non- propellancs is the slurry casting process, 1 ~ for
ru bbe ry t hermop last i cs such as ce11 ul ose ace ta :e or which the flowsheet is shown in Figure 62.

95
Cour-tt-:sy of Throkol Chern it.al Co111<>rarion H~dsJofle f)wJStO'i

Figure 63. Sigma Blade Mixer (200 Gallon)

Reproducibility of the oxidizer grist is one of from 0.5 pound to 8700 pounds have been rnanu-
the most important quality control measures in the facwred anu flown in rocket motors . Examples of
manufacture .. The mixer rnay be a sigma blade polysul fidi; <1mmoniurn perchlorate composites in
mixer, equipped with bottom outlet, shown in service use are
Figure 63, or, alternatively, a vertical mixer shown
T 14 used in early experimental work with
in Figure 64. The ingredients are added consecu-
large engine~>.
tively to the mixer, starr.ing with the prepolymer.
Tl? used in RVAIO, Sergeant (XM-l2),
At the conclusion of the mixing the charge is de-
XI 7. reentry vehicle (X M20 l, and Vi11io11s 'est
aerated by evacuation or other means and ca~t
vehicles in the Polaris ;ind NASA high altitude
into the motor case . Curing is accomplished by
program-;;
subjecting the loaded case to elevated temperature
in a heated space (a pit is used for large charges) . T24 used in the Hone'>\ John spinner rocl<et
The mandrels are removed after the cured charge (M-7);
is cooled, and the charge is finished by machining TI J EI u~ed in various aerodynamic test
any designed surfaces not produced by the mold. vehicles (T-40);
in general, such surfaces are chietly the aft end of T-22 used in Loki;
the grain. A typical mandrel is shown in Figure 65, GCR-20 IC used in V;rnguard third s'age
and a motor with uise-bonded grain in Figure 66. rocket; and
Poly5ulfide-ammonium perchlorate grains from T27 used in Falcon (XM-46) two-level !hrust
1.5 inches to 40 inches in diameter, and in weights motor.

96
Courusy oJ Thwkol Chemjc.ol Corporatwn , Re~lone Dwuion

Figure 64 . Verlical Mixer (300 Gallon)

97
Figure 65 . Mandrel for Medium Si:ze Rocket Motor

58-J.2. J>oJyurcthane rubber. Apart from lhe simple diisocyanate such as toluene diisocyanalL'.
polysulfides, most syn1hetic rubbers are formed There Me many long chain diols avililable but
by vinyl-lype polymerizulion . vr addition al double only relatively few diisocy<'.lnares are on the m::irkt:l.
bonds. 01her polymerizarion re<'.lcl\on s nol involv- The polymerization reaction must be catalyzed, as
ing produc1ion of vol:111le by-products are known by ferric acetyl ace1ona1e, and acceleraLOrs of the
nnd may be useful in preparation of propellanl polyrneri7.at1on are known. The polymer may be
binders . For example , if an isocyanate is added used wilh or wi1hou1 a plasticizer.
to a compound containing an -OH group, a The physic<il properties an: similar to those of
urethane is formed according ro the rc<iclion polysultide propelbnts at the s<irne binder volume
fraction. The density of ihe polyurethane propel-
R'NCO + HOR" = R'NHCOOR" (59l lant is naturall y lower than 1hat of a polysulnde
Reaction of a diisocyan:-ire amJ a diol thus gives propellant a1 the same oxidizc:r weight fraction .
a long chain linear polyure1hanc, and the presence The manufacturing proce s~ is 1he same as that
of some polyol or polyisocyanate should cause for poly!'-ultide propellant, with one important pre-
the polymer lo cross- link In order lo minimize the caulion. Since the isocyana1es reacl with - OH
he<ll of polymeri zation (luring the cure it is cus- groups, it i<; particularly i mportant that all ingre-
dient~ be quite dry. Addition of water to iso-
tomary 10 use ;1 long chain (1iol such ;1s poly-
propylene glycol , H'O - CH.~ CH L.- OH . with a cyan<11es result ~ in - NHCOOH groups which lend
to tkcompo~c . Polyurethane binders have been
CH ., more extensively u~ed in the aluminum-<imnw-

98
Courtesy of Thwhol Chem1co/ Corpora1 io11 . Red.storie Diuisi<>n

Figure 66. Medium Size Case-Bonded Grain With a 5-Poinl Star Conf)gurolion

nium pi;rchlorate-binder propellanls described in tensile strength, elongation , and modulus as a


OR DP 20- J 76. rubbery polymer with liule or no plasticizer. nus
situation is taken advantage of in the poly(vinyl
58-3.3. Butadiene-acrylic acid copolymer rub-
chloride) propellants such as Arcite 368 used in
ber, PBAA. When butadiene is copolymerized
the Arcon sounding rocket mocor. At a compara-
with acrylic acid and cured with an epoxide, an
ble density to thal of the polyurethane propellants,
clastomeric binder results wirh properties fairly
a poly(vinyl chloride) propellant permits aboul the
similar to those described for lhe polyurethanes.
same weight fraction of oxidizer and develops
This binder system has a comparable density to
about the same specific impulse. Al a lower plasti-
that of the polyurethane binder , tolerates abouc
cizer level a stiffer binder and therefore a more
the same weight percent of oxidizer in a case-
rigid propellant results, with properties of com-
bon<lable propellant, and gives performance in the
pressive strength and high modulus required for
same range. The manufacturing process is essen-
a cartridge-loaded grain . Cross-linking may be ac-
tially that shown in Figure 62 . PBAA binde rs
complished by formula11on with agents that react
are receiving considerable actention in the newer
during the cure.
aluminum-ammonium perchlorate propellants, dis-
A novel feature of the po!y(vinyl chloride) pro-
cussed in ORDP 20-176 .
pellants is their method of manufacture. The poly-
58-3.4. Poly(vinyl chloride). A nonrubbery mer , already complecely polymerized , is suspended
polymer , if, sufficiently plasticized, may develop in in the plasticizer together with the oxidant and
a heavily loaded plastic about the same ultimace additives during the mi xing operation . At ambient

99
Figure 67. 1-lnch Extruder for Poly(Vinyl Chlor ide) Prope llant
C04VlUy CJ/ A1lontic R e.sHrch Corpora/ion
l . Hopper for inert propellant feed 6. Water trough
2. Pressurized Fiiiing pot for Arcite propel/on/ 7. Toke -off rollers
3. "Hot" propellant feed 8. Automatic saw
4. Barrel of extruder 9. Extr uded propellant
5. Die

100
CoL<rtuy of All=t~ Ret~h Corporat1<>n
Figure 68. Extrusion of Wired Grain

temperature, or perhaps at a chilled mixing tem- 58-3.5. Elastomeric binders for cartridge-loaded
perature, the polymer does not imbibe the plasti- grains. Although the case-bondable binders do not
ci.zer, so that good pot life is attainable. The still in general contain so much plasticizer that they
fluid mix, called plastisol, is transferred to the case can be stil'l'ened by eliminating plasticizer, there
or mold and the grain is cured and finished . The are at least three ways that elastomers can be
curing operation is mechanically the same as for adapted to such use . One such way is to bond
the synthetic rubbers, shown in Figure 62, but it is the grain to a relatively rigid mechanical member
chemically quite different. These propellants may separable from the case, which may also serve as
also be extruded. A small extruder is shown in an inhibitor. Another is to cross-link the polymer
Figure 67, illustrating the essentials of this process. to a greater extent than is required for the readily
The extruder is operated at a temperature above deformable case bonds. The third method is to
350F, and curing takes place during the extru- decrease the volume fraction of the binder to below
sion. Grains containing v.>ires strung parallel to 30 percent so that interaction of the crystalline
the a.xis may also be extruded, as shown in Fig- particles carries part of the imposed load and
ure 68. Since no polymerization takes place during helps resist deformation . The first two alternates
the cure, there is no exotherm and little, if any, would still permit fabrication of the grain by cast-
volume change due to curing. On the other hand, ing. The third would require other fabrication
the high temperature of the curing ope.ration en- techniques. In the case of propellant CPN-127 A
tails appreciable thermal shrinkage when the cured (see SPIA/ M2) used in aircraft jatos, the binder
grain is brought to ambient temperature. employed is a butadiene-2-methyl-5-vinyl-pyridine

101
PREPOLYMER
:c,:,~::~;~fA
3r--M-1x_ __.
H BLOC!<
H EXTRUOE
CURE FINISH

GR\NO
OXIDIZER S SCREEN -
Figure 69. Extrusion Process for Fuef Binder Composites

copolymer plasticized with the formal of diethylene curing operatioo in the molds The molds are then
glycol monobutyl ether (Butyl Carbitol formal). disassembled and the grains finished by machin-
The volume fraction of Lhe binder, calculated from ing and/ or inhibiting. Figures 75 and 76 show
the composition and densities of the crystalline completed grains and finished jatos.
ingredients, is about 26 percent. The manufac-
58-5. Cellulose acetate. Cellulose acetate is
turing process for this propellant is outlined in
made from a natural polymer and is not available
Figure 69 . Mixing is done in a sigma blade mixer.
in a monomeric or prepolymer state. Jt has a fairly
The completed mix is blocked in a hydraulic press,
high softening temperature which can be lowered
shown in Figure 70, 10 form a press charge for
by compounding wich a plasticizer, allowing the
extrusion . The extrusion press is shown in Fig-
propeUant to be mixed and formed at a moderately
11re 71. The extruded strand is cut co grain blanks
elevated temperature . ln propellant LFT-3 (see
which are then cured at elevated cemperature to
SPIA / M2 ), used in the GAR 3 Falcon APU,
complete the polymerization. The cured grain
the cellulose acetate is plasticized wich acctyl tri-
blanks are finished by machining to final dirnen-
sions .11, ia ethyl citrate and dinitrophenoxyelhanol, and sta-
bilized with toluenediamine. The oxidizer loading
Still another fabrication process is used for pro-
is fairly low in order to maintain a desired low
pellant CBS-128K (see SPIA / M2), developed for
flame temperature . Mixing is done in a sigma
the Dart and Sky Dare missiles. This propellant
blade mixer, and the grain is formed by compres-
uses GR-I rubber plasticized with di-(2-ethylhexyl)
sion molding . Larger grains may be made by bond-
azelate. and ha s a binder volume fraction even
in~ segments togethe r using a polyurethane layer
lower tl!Cln CPN-12 7A . The ftowsheet for th.is
between the segments as well as for the periph-
process is shown in Figure 72. Compounding and
eral inhibitor. A SO-pound individual segment as
simultaneously curing is done on a roll mill. Disks
molded is shown in Figure 77 and a 1000-pound
are cue from the rolled sheet, stacked, and com-
segmented grain in Figure 78 .
pression molded, as shown in Figrne 73, to grain
blanks . The grain blanks are machined, as shown 58-6. Other binder systems. The above listing
in Figure 74, and then inhibited. is by no means a complete roster of binder sys-
tems that can be used or even of systems that have
been experimented with . A considerable effort
58-4. Thermoplastic synthetic polymer binders has been expended on binders containing acetylenic
for cartridge-loaded grains. The use of thermo- and other endothermic groups which might add to
plastic polymers polymerized in situ predates the the heat of explosion, Q, of the propellant at a
use of the elastomeric polymers. The binder sys- given oxidizer loading. There is stiU room for
tems are selected to give compressive strength and binders with itnproved physical properties such as
high modulus, thereby permitting attainment of the coefficients of expansion closer to the expansion
required physical properties in a grain produced coefficients of the materials used for rocket motor
by the slurry casting process of Figure 62. The case manufacture, tower brittle temperatrnes, and
prepolyrners or monomers are mixed with che oxi- less temperature dependence of modulus, com-
dizers and other additives in a sigma blade or pressive and tensile strength, and elongation at
equivalent mixer and cast into molds. Polymeriza- rupture. le is expected that new binder systems
tion is completed at elevated temperatures in the will continue to appear.

102
CmJrWsv ol Ro~ke1d_vne l>zv~wn o/ Ncrlh Am.,rica11 Aviation. lnr_

Figure 71. Extru:;ion Press

PRE POLYMER
CUT 8 COMPRESSION
PLASTIC\ Z ER FINISH
STACK DISCS MOLD
ADD!T!VES

figure 72. Compression Molding Process for Fuel Binder Composites

104
Couriesy of GN>nd Ce111ra/ Ra<:hl Company

Figure 73 . Compressing Stacked Disks

105
Coiufe~y oj Grand Ccn(ra! Roth.et Cam.pan_v

Figure 7 4. Machining Outside Diameter ol Grain

106
Fi9vre 75. }olo Groins

107
Figure 76. Finished Jatos

108
CourttGy of A 111(>CO C~mv:ot.. C o rporation

Figure 17. lnclividuol Segment (50 Pounds) of 1000-Pound Segmented Grain

10 9
Cour1eay oj Amoco Chem1ca /a Corporat ion

Figure 78. Segmenled Groin (1000 Pounds)

110
REFERENCES

I. R. D. Schultz and A. 0 . Dekker, "Transition-State versity, Silver Spring, Maryland (~PIA Abstract No.
Theory of lbe Lmear Rate of Decomposition of 3719).
Ammonium Perchlorate," Si:xth Symposium (Inter- 10. N. J. Bowman, Development of an Ammonium Ni-
national) on Combustion, p. 618, Reinhold Publishing trate Base Solid Propellant, Standard Oil Company
Corporation, New York, New York, 1957. (Indiana), Quarterly Repon No. 29 (Aug.-Oct. 1956),
2. M . Summerfield, E. S. Sutherland, M. 1. Webb, H . J. 15 January 1957, Contract 33(038)27541, CONFI-
Tabock and K. P. Hall, Burning Meclumism of Am- DENTIAL (SPlA Abstract No. 17,1~21
monium Perchlorate Propellants, paper presented :it I l. Standard Oil Company (Indiana), private communi-
American Rocket Society Dlh Annual Meeting, 17-2 l cation.
November l958, New York, New York.
12. H. W. Ritchey (Thiokol Chemical Corporation), pri-
3. R. F. Chaiken and W. H. Anderson, The Role of
vate communication .
Binder in Compositf! Propel/an/ Combustion, Ae.ro-
jet-General Corporation, Report TN-30, AFOSR 13. A. M. Jacobs and J. H. Godsey, Burning Rute Modi-
TN 59-540, July 1959,. Contract AF49(638)-566 ficaiion o/ Double-Base Propellants, Allegany Ballis-
(SPIA Abstract No. 19,561). tics Laboratory, Hercules Powder Company, Bulletin
4. N. A . Laury, Hydrochloric Acid and Sodium Sulfate, of the fifteenth Meeting of the Joint Army-Navy-Air
p. 16, Chemical Catalog Company, Cnc., New York. Force Solid Propellant Group, Vol. TV , p. 41, CON-
New York, 1927. FIDENTIAL, Solid Propellaot loformation Agency,
Applied Physics Laboratory, The Johns Hopkins Uni-
5. W. A . Proell, Development of Ammonium NitraJe versity, Silver Spring, Marylaod.
Base Solid Propellant, Standard Oil Comp-any (Indi-
ana), Bimonthly Report No. 3, November l95l, Con- 14. C. E. Bartley, A Preliminary lnvesrigarion of the Rub-
tract USAF 33(038)27541, CONFIDENTIAL (SPJA ber-Base Solid Propellant ORDCIT 21, Jet Propul-
Abstract No. 12,468). sioo Laboratory, California Institute of Technology,
CJT/JPL PR 4-18, 26 August !945, CONFIDEN-
6. 1. Linsk and R. W. Todd (to Standard Oil Company
TIAL (SPIA Abstract No. 2990).
[lndtanaj), U.S. Patent 2,936,225 (1960).
7. Phillips Petroleum Company, Development of Com- 15. W. C . Aycock, Design and }nlernal Ballistic Dara for
posile Propellant Jato Units, Final Repon on Supple- Polysul/ide-Perr:hlorate Propellants, Thiokol Chemi-
mental Agreemenr No. l (Report 722-J-54RF), I July cal Corporation, Report No. 24-51, October 195 l,
!954, Contract AF 33(600)6710 (SPlA Abstracr No. CONFIDENTIAL (SPlA Abstract No. 11,287).
14,258). 16. A. T. Guzzo, Development of S1andord Opertrting
8. Pica1inny Arsenal, Basic Research on P/t:Jstic Rocket Procedures for Manufacture oj Po/ysulfide Perchlo-
Propellants. MR June-Dec., 1946, Jan.-Dec., 1947, rate Propellants, Thiokol Chemlcal Corporatioo, Re-
Jan-Dec., 1948, Jan.-May, 1949, CONFIDENTIAL port No. 26-51, November 1951, CONFIDENTIAL
(SPlA Abstract No. J 0,073). (SPlA Abstract No. J l,361).
9. J. L. Jone.5, Progress in the Development of An 17 . C . F . Dougherty, "Processing Rubber-Base Compos-
A mmon_ium Nitrate Smokeless Solid Propellant, Jet ite Rocket Propel!a.ul," Chem . Eng. Progr. 53, 489
Propulsion Laboratory, California Institute of Tixh- ( 1957).
nology, Bulletin of the Foun.h Meeting of Lhe 18 . R. S . Dobyns ond J. A. McBride, Production Prob-
Army-Navy Solid. Propellanr Group, p. 207, CON- lems on Solid Propellant &cket Motors, paper
FlDENTIAL, Sohd Propellant Information Ageocy, presented at American Rocket Society Semiannual
Apphec! Physics Laboratory, The Johns Hopkins Uni- Meeting, 10...13 June 1957, San FrancisC-O, Ca!ifontia.

111
CHAPTER 10

INERT SIMULANTS FOR PROPELLANTS

59. General. Propellants are hazardous mate- duplicate density and another to duplicate other
rials, necessary for functioning in their engines but physical properties required.
undesirable for many uses such as display and The problem is considerably more difficult when
break-in of manufacturing equipment when func- the polymer is itself a propellant as is nitrocellu-
tioning is not contemplated. To meet the require- lose. In this case an inert polymer should be found ,
ment for materials for such nonfunctioning uses, with density and other physical properties dupli-
inert simulants or dummy formulations have been cating the propellant polymer. This has, in general,
developed to represent propellants. The ideal inert not been done . Cellulose acetate is a popular simu-
simulant for any propellant should duplicate the lru1t for nitrocellulose, but it is not very good. The
propellant in all physical properties-appearance, difference is appreciable in density, appearance,
density, texture, hardness, physical strength, and and feel, even with the best available plasticizers.
plasticity over a temperature range-without being In order to reproduce density it appears necessary
a propellant. Considerable compromise with the to use crystalJine fillers which worsen the match
ideal is permi&Sible and usual to save time and between dummy and live propellant in other
development expense, depending on the use to properties.
which the dummy is to be put. An inert simulant for 010 cast double-base
propellant (see SPIA/ M2) was formulated as
60. Mock-ups. Where geometry is the only con-
follows:
sideration, as for illustration of the spatial rela- Casting Casting
tionship of the propellant to other parts of the Powder Solvent
engine or for assurance that the engine complete Cellulose acetate 0.57
with propellant can be assembled, the dummy may Triacetin 0.10 0.962
be built of wood and painted the proper color. Graphite 0.03
Coal is an admirable mock-up for black powder. Red lead 0.30
2-Nitrodiphenylamine 0.038
61. Simulants to reproduce physical properties. 1.00 1.00
In order to demonstrate the physical properties of
Comparison of the inert with live 010:
a propellant by the use of an inert simulant, one Inert Live
needs something more closely akin to the propel-
Casting Powder
lant than a wood mock-up . Most modem pro- Density, p, g/cc 1.75 1.5
pellants are plastics, and a plastic dummy will Packing density, g/cc 1.02 1.01
look, feel, and handle more like its live counter- Cast Powder
part. Most of the physical properties of propellants Density, p, g/cc 1.60 1.55
are traceable to the polymer content. In the case Tensile strength, psi 465 900
Elongation, percent 8 49
of fuel binder composite propellants the same Volume coefficient of
volume percent of the same binder together with expansion, per degree F 6.2 x 10-4
a suitable filler should result in a reasonable dupli-
cation of the physical properties. The filler should, 62. Simu)ants to reproduce manufacturing
if possible, have the same specific gravity and properties. In the development of new manufac-
crystal structure as the oxidant used in the live turing equipment, for checking out extruders and
propellant. For example, potassium chloride is a other types of processing machinery after main-
good replacement for ammonium perchlorate. If tenance or prolonged inactivity, ru1d to displace
the specific gravity of the filler cannot be precisely live propellant preparatory to disassembly of proc-
matched and density of the dummy is important, essing equipment, it is necessary to have a dummy
as in locating the center of gravity of the engine, formulation that behaves like live propellant in
the volume percent of binder can usually be com- process. In general this requires matching mechan-
promised safely. Alternatively, two inert sirnu- ical properties not only dry and at ambient tem-
Jants for a propeliant may be developed, one to perature but also over a temperature range and

112
perhaps admixed with volatile wlvenls. Since it is in the live propellant. With these inilial criteria
the polymer which largely determines manufac- the composition of the semilive propellant can be
turing properties as well as product physical prop- readily developed empirically .
erties, substitution of filler is generally adequate The composition and physical properties of N-5
in fuel binder composites. It must be verified that and its sem ilive analog are shown below :
the replacement filler will not affect the reaction N-5 Sernilive
rate of any chemical changes involved in the Nitrocellulose , 12.6% N 50.00 54.19
manufacture . Nitroglycerin 34.90
There are no good manufacturing dummies for Di-n-butyl pblhalate 30.97
nitrocellulose-base propellants . Wax, 1 with or Di-(2-elhyl b.exyl) phlhalate !0.90
without sawdust, or similar carbonaceous material Diethyl phtbalate to.so
and cellulose acetate compositions, respectively, 2-Nitrodiphenytamine 2.00 2.11
have been used successfully for clean out and to Lead salts 2.40 2.10
put Loads on machinery, but they do not duplicate Candeli\ta waJC 0.20 0.21
che operating mechanical loads, nor do they dupli- Specific graviry, p t.56 1.31
N itrocel lu lose cooce nl.ra lion, g I cc 0.78 0.71
cate the dimensional changes in the product during
Tensile strength, cro~wise, psi 320 210
manufacture.
Tensile streogtb. leogtbwise, psi 480 330
Elongation, perceo! 47 73
63. Semilive. In order to overcome the dis-
advantages of a completely inert dummy in The lower tensile strength and greater elonga-
studying manufacturing problems of nitroceUulose tion of the semilive propellant are seen to follow
system propellants, semilive simulants have been the lower nitrocellulose concentration as predicted.
developed, in which the nitrocellulose is retained Extrusion pressure with the semilive was also con-
as the polymer but al! plasticizers used are fuel siderably Lower than with live N-5. In spite of the
plasticizers. This results in compositions of low or fact that the semilive appears to be somewhat
negative calorific value. lf ignited these simulants deficient in nitrocellulose it has been used success.-
will burn slowly and incompletely, allowing oper- fully to break in extrusion equipment of experi-
ating personnel to escape safely but emphatically mental design.
demonstrating any mechanical situations that The measured calorific value, 435 cal/g, is well
could cause destructive damage with live propel- above the calculated value, demonstrating again
lant. In formulating a semilive propellant, the con- the lack of equilibrium in calorimetry of cool
centration of nitrocellulose should be about the prop<..:lants disc.ussed in Chapter 2. The burning
same as in the live counterpart and the viscosity rate, about 0.07 in/sec at 70F, 1000 psi, is low
of the fuel plasticizer should be as close as pos- enough to prevent destruction of extrusion equip-
sible to the viscosity of the combined plasticizers ment in case of fire.

REFERENCE

l. Hercules Powder Company, unpublished data.

113
GLOSSARY

The terms below, as used in this Kand'OOOk, critical diameter. Diameter of an explosive col-
are Ordnance terms or are us~ in a spec i a I l zed umn below which detonation will not propagate.
sense. Other terms are as defined in AR 320-5, deftagration. Burning process in a solid system
Dictionary of United States Army Terms; Mil comprising both oxidant and fuel in which
the reaction front advances at less than sonic
STD-~qq, Homenc1ature and Definitions in the
velocity and gaseous products if produced move
Allll\un l ti on Area; Merri am--Webste r's unabridged away from unreacted material. A deftagration
dictionary, or cQllTll()n usage, may, but need not, be an explosion.
degressivity. Decrease of weight rate of burning
as web is consumed.
ABL. (abbr) . Allegany Ballistics Laboratory . deterrent. A material added to a propellant com-
ARP A. (abbr) . Advanced Research Projects position or applied to the surface of a grain to
Agency. decrease the flame temperature or rate.
bazooka rocket. Shoulder fued rocket, specifi- detonation. An explosion characterized by propa-
cally the 2.36-inch . gation of the reaction front within the reacting
binder. Continuous phase in which some other medium at supersonic velocity and motion of
material is embedded. the reaction products in the same direction
burning rate 1 linear. The rate of burning of a as the reaction front.
propellant measured normal to the burning double-base propellant. A propellant with two
surface. explosive ingredients, such as nitrocellulose and
caliber. The diameter of a projectile or the diam- nitroglycerin.
eter of the bore of a gun or launching tube. erosiv~ burning. Burning at a rate higher than
Axial distance equal to the caliber. normally associated with existing pressure, due
cannon. A complete assembly , consisting of a to velocity of combustion products over the
tube and a breech mechanism , firing mech- burning surface.
anism or base cap, which is a component of a expansion ratio. The ratio of the nozzle exit sec-
gun, howitzer, or mortar . May include muzzle tion area to the nozzle th.roat area.
appendages . The term is generally limited to explosion. A very rapid chemical reaction or
calibers greater than 1 inch. change of state involving generally production
catapult. An engine which accelerates a load by of a large volume of gas and resu \ting in rup-
means of a piston driven by high pressure gas ture of the container if present and generation
such as may be generated by the burning of a of a shock wave i.n the surrounding medium .
propellant. filler. Discrete material dispersed in substantial
quantity in the continuous or binder phase of a
characteristic velocity. A figure of merit of a
composite propellant.
rocket propellant, defined as Pc~ ,g. fiow, equilibrium. Condition of continuous chem-
w ical equilibrium during expansion in the nozzle.
composite propellant. A propellant system com-
prising a discrete solid phase dispersed in a flow, frozen. Condition of no chemical reaction
continuous solid phase. during expansion in the nozz.ie .
ce>volume. Volume occupied !>ya gas when com-
Differs significantly from definition given in MIL
p ressed to its limit of compression . STD-444.

114
GLOSSARY {Continued)
force. A ngure of merit of a gun propellant. mesa propellants. Pr0pe!lants which show nega-
RnT, tive values of n over short pressure ranges on
de fi ned as ---,;f .
a plot of log r versus log P for r = b'P".
fuse. An igniting or explosive device in the form monopropellant. * A single physical phase com-
of a cord, consisting of a ftex ible fabric tube prising both oxidizing and fuel elements.
and a core of low or high explosive. Used in mortar. A complete projectile-firing weapon,
blasting and demolition work, and in certain rifled or smooth bore, characterized by shorter
ammunition. barrel, lower velocity, shorter range, and higher
fuze. A device with explosive components de- angle of fire than a howitzer ora gun.
signed to initiate a train of fire or detonation
plastisol. A ftowable suspension of a polymer in
in an item of ammunition by an action such as
a plasticizer which the polymer may later imbibe
hydrostatic pressure, electrical energy, chem-
to produce gelation.
ical action, impact, mechanical time, or a
plateau propellant. Propellant showing a region
combination of these. Types of fuzes are dis-
of markedly reduced slope on a plot of log r
tinguished by modifying terms forming part of
the item name. (In some cases the explosive
=
versus iog P for r bP1'.
?Ort area. The area of any opening through which
components may be simulated or omitted.)
gas generator. A device for producing gas, ~v gas moves. Specifically the area of a d)scharge
burning of solid propellant, to pressurize a tank. end of a grain perforation.
drive an engine, or actuate a mechanism. pot life. Length of time a temporarily fluid sys-
grain. A single piece of solid propellant, regard- tem can be held or worked before setting up to
less of size or shape, used in a gun or rocket. a solid.
"green." Wet with solvent during the manufac- primer. An assembly which ignites a propelling
turing process. charge, especia~ly in gun ammunition.
grist. Particle size distribution, especially tha.1 progressi"it)' Increase of weight rate of burning
produced by grinding. as web is consumed.
gun. A piece of ordnance consisting essentially resonance rod. A rod inserted into the perfora-
of a tube or barrel for throwing projectiles by tion of a rocket groin to depress the tendency
force, usually the force of an explosive but toward unstable burning.
sometimes that of compressed gas, spring, etc. rocket motor. A nonairbreathing reaction pro-
heat of explosion. Heat evolved in burning (ex- pulsion device that consists essentially of a
ploding) a sample in a combustion bomb in an thrust chamber and exhaust nozzle, and that
inert atmosphere under standardized conditions carries its own solid oxidizer-fuel combination
of pressure and temperature. from which hot gases are generated by com-
igniter. A specially arranged charge of a ready bustion and expanded through a noz1.le .
burning composition, usuaJly black powder, shelf life. The storage time during which an item
used to assist in the initiation of a propelling remains serviceable.
charge.
single-base propellant. Propellant comprising onJy
impulse. Product of thrust x time.
one explosive ingredient, e.g., nitroceUulose.
inhibitor. A material applied to surface(s) of pro-
slivers. Portions of the grain remaining at burn-
pellant grains to prevent burning on the coated
chrough.
surface(s).
JANAF. (abbr). Joint Army-Navy-Air Force. small arms. A gun of small caliber. Within the
jato. let-assist take off, a rocket motor used to Ordnance Corps 1he term is presently applied to
supplement the engines of an aircraft or missile guns of caliber up to and including I inch. Such
at takeoff. hand and shoulder weapons as pistols, carbines,
M & V. (abbr). Moisture and volatiles. rifles, and shotguns.
mass ratio. Ratio of the weight of the propellant Differs significanrly from definition given in MIL-
to the weight of the loaded rocket. STD-444.

11 s
GLOSSARY (Continued)

smokeless powder.* Solid monopropeUant com- thennochemistry. The derivation of the compo-
prising nitrocellulose, with or without oxidizing sition, temperature, and derived parameters of
and/or fuel plasticizers. the combustion products from the composition
SPIA. (abbr). Solid Propellant Information of the propellant, the heats of formation of the
Agency. ingredients and the thermodynamic properties
SPIA/M2. Propellant Manual SPIA/M2, issued of the products.
by Solid Propellant Information Agency.
triple-base propellant. Propellant with three ex-
specific impulse. A figure of merit of a rocket
plosive ingredients, such as nitrocellulose, nitro-
F
propellant, defined as --:- . glycerin, and nitroguanidine.
w
web. Thickness of propellant wall consumed by
*Differs significantly from definition given in MIL-
STD-444 . burning.

116
INDEX

A Calorimetry, 53
Abel equation. See Noble-Abel equation Cannon propellant, 27, 54, 74
ABL short calculation for specific impulse, 10 Carbon black, 50
Acceleration, 20, 56 Carpet rolling, 80
Acetone, 46 Case bonding, 28, 45, 52, 88, 89, 94, 95, 99
Aircraft starter, 45 Casting, 88, 89
Aluminum, 17 Cast double-base process, 74, 84
Ammonium nitrate, 44, 58, 89, 93 Casting powder, 74, 85
Ammonium perchlorate, 14, 44, 89, 90 Casting solvent, 85
Ammonium picrate, 94, 95 Catalyst, polymerization, 95, 98
Annealing, 80 Catalyst, burning rate, 15, 95
Asphalt, 89, 95 Catapult propellant, 20
Autoignition test, 53 Cellulose acetate, 46, 52, 95, 102, 112
Cellulose nitrate. See Nitrocellulose
8
Centralite
Bachmann-process (ROX), 43 ethyl, 48, 49, 58
Ball Powder, 74 methyl, 49
Barium nitrate, 50 Centrifugal wringer, 62, 65
Barrel life. See Erosion Characteristic velocity
Baz.ooka, 56
Beaker, 88
c:,
calculated, 4, 7, 50
measured, c, 11
Binder, 16, 58, 89 Charcoal, 33
fuel, 89-111 Chromium, 93
monopropel!ant, 58 Coating, 19, 72, 75
volume fraction, 59, 89, 94, 98, 101, 102, 112 Cobalt, 93
Black powder, 33-41, 89
Cold flow, 52, 89
Blasting powder, A, 33
Colloid, protective, 75
Blasting powder, B, 33
Composite
Blending, 46, 65, 72, 88
fuel binder, 27, 59, 89- 111
Block breaker, 68
Boiling (nitrocellulose), 62 monopropellant binder, 58-61
Brittle temperature, 31 propeUant, 13, 16-17, 27
Burning Composition dust, 36
area, or surface, S, 13, 16, 17 Compression molding, 44, 94, 102
distance , 17 Compressive strength, 31, 94-95, 102
of propellants, 12-17 Configuration, 17
rate, linear, r, 3, 12, 13, 15, 36, 56, 90, 94, 95 Conservation equations, 6
rate, weight or mass, W, 13, 19, 20 Corning mill, 33
unstable, 17 Corrosion, 37, 93
Bursting charge, 40 Covolume, er, 3
Creep, 31
c Critical diameter, 17
Calorific value, Q, 6, 1O, 45, 50, 53, 67 Cross-linking, 52, 95, 99, 101
Calorimeter, Boas, 10 Curing, 88, 89, 96, 99, 101
coal, 10 Cutting machine, 73

I 17
INDEX (Continued)

D Flame temperature at constant pressure, Tp, 5, 6,


Deftagration, 17 7, 10, 93
Deformation, 31, 52 temperature at constant volume, T., 5, 6, 7, 9,
Degressivity, 18, 19 20, 45, 50, 53, 58
Denitration, 66 zone, 12
Density, p, 13, 27, 52, 90, 93 , 99 Flash, 37, 50, 54, 58
bulk, 72 Flaws, 84, 88
gravimetric, 27 Flow
de Saint Robert equation (burning rate), 13 equilibrium, 7
Desiccant, 27 frozen composition, 7
Detonation, 17, 27, 40 laminar, 15
Dextran, 66 turbulent, 15
Die, 66, 72, 80 Flying cutter, 80
Diethylene glycol dinitrate, 49, 59 Foam zone, 12
Diffusion, 16, 27, 61, 92 Force
Diisocyanate, 98 See Specific force
Dinitrotoluene, 50
relative, RF, 10, 11
Diphenylamine, 48, 49, 74
Free radical, 48
Double-base propellant, 45, 46, 53, 67, 68
Fuel, 16
Dowel rod machine, 80
Dummy. See Inert simulant Fuse, safety, 40
Du Pont mechanical dipping process, 62 Fuze, 40
Dust, 72 G
E
Gas
Elongation (tensile), 28, 95, 99 generator propellant, 24, 50, 54, 56, 58, 80,
Emulsion, 75 89, 93
Endothermic groups, 102 horsepower, Ghp, 4, 5
Enthalpy, 6 1
Envelope, 23, 27, 94, 95 volume, M' 6, 7, 90
Equation of state, 3 Glazing, 72
Erosion, 45 Grain, 17
Erosive burning, 15, 23 cord, 20
Erosivity constant, 15 cruciform, 23
Ether-alcohol (solvent), 46, 66 dual composition, 19
Ethyl acetate, 7 4 multiple-perforated, 19
Ethyl centralite. See Centralite, ethyl
rod and shell, 18, 23
Expansion ratio, 11, 23
segmented, 102
Explosive, high, 40
slotted-tube, 18, 23
Explosive, primary, 42
star-perforated, 18, 23
Extruder, 101
Extrusion, solvent, 61, 66 st.rip, 20, 80
solveotless, 66, 80, 94 Granulation, 17
Grist, 58, 91, 94, 96
F Gun, 19
Filler, 16, l 12 Guncotton, 46, 66
Firedamp, 40 Gunpowder, 33
Fizz zone, 12 Gun propellant, 37. 53, 58, 67, 80

118
INDEX (Continued)

H Melting point, 42, 6 1


Heat Mesa propellants, 14
capacity, CP , 6 Metal fouling, 45
loss , 22 Military blend (nitrocellulose) , 46
of ex.plosion , Q, 6, 10 Milori blue, 93
of formation, t:.E, 6 Mineral jelly, 49
test, 52 Mixer
H irschfelder-Sherman Schraeder, 68, 77
calculation, 7, 9, 10. 53 sigma blade, 67. 77 , 95 , 96, 102
constants, 7 vertical , 96
HMX, 43, 94 Mixing, 67
Humidity, relative, 27, 92 Mock-up, 112
Hydrogen chloride, 89, 92 Modulus (Young's) , 28 , 31, 45 , 52, 95, 99
Hygroscopicity, 27 , 36, 44, 46, 48 , 52, 93 Mold, 88, 96
Molecular weight. 6, 48
Monopropellant, 1, 12, 16, 17, 42, 44 , 5 8, 93
igniter, 40 Mortar propellant, 54
Ignitibility, 45 Multiple-grain charge, 20
Ignition, 95 Muraour equation (burning rate), 13
Impact strength, 31 Muzzle
Impetus . See Specific force energy, 54
Impulse, total, 22, 95 velocity, 59
Incorporation, 37
Inert simulant, l 12-113 N
Inhibitor, 17, 28, 52 , 80, 85, 101 Neck , 80
Interior ballistics, 3 Neutrality, 17, 19
Nitrator (nitrocellulose), 62
J Nitrocellulose, 45, 58 , 62, 112
JAN AF boiling, 62
Physical Properties Panel, 28 military blend, 46
Static Test Panel, l 1 nitrator, 62
Thermochemical Panel, 7
nitrogen content, 46, 65
Jerk, 20
poaching, 65
Jordan engine , 65
reclaimed, 74
L solubility, 46 , 66
Lacquer, 75 viscosity, 46, 48, 66
Lead, 14, 50 wood , 66
Lith ium perchlorate, 93 2-Nitrodiphenylamine, 48
Nitrogen content (nitrocellulose), 46, 65
M
Nitroglycerin, 45 , 46 , 48, 49 , 52, 68 , 75
Macerator, 68 Nitroguanidine, 37, 42, 58, 94
Mandrel, 96 Noble-Abel equation, 3
Mannan, 66 Noz.zle half-angle, 11
Mass
fraction. See Mass ratio 0
rate of discharge, 22 Opacity, 50
ratio, 89 Oxidizer, 16, 89 , 102

119
INDEX (Continued)

p Pycnometer, 27
Perfect gas equation, 3 Pyrocell u lose ( ni trocell u Iose), 46
PETN, 44 Pyrolysis, 12
Phase changes, 44
Q
Phthalates, 49
Piobert's Law, 13 Quality assurance or control, 11, 20, 28, 84
Pistol propellant, 50 Qu ickness, relative, RQ, 20, 43
Plasticity, 52, 66
R
Plasticizer, 46, 52, 75, 95, 98, 99, 102, 113
fuel, 45, 50, 68 RDX, 43, 58
oxidant, 45, 48, 49, 58, 68 Reduced
Plastisol, I 0 l characteristic velocity, 4
Plateau propellants, J4 specific impulse, 4
Poaching, nitrocellulose, 65 Reel, 36
Polyisobutene, 95 Resonance rods, 17
Polymer, 45, 89, 95, 112 Roberts process (nitroguanidine), 43
concentration, SI, 52, 54, 67, 84, l 13 Rocket propellant, 22, 37, 40, 54 , 56, 58, 74, 80,
Poly(methyl methacrylate) , 48 89, 93
Poly(perrin acrylate) , 48 Roll mills, 77
Polypropylene glycol, 98 Rolled sheet process. 77
Poly(trinitroethyl acrylate), 48 Rolls
Poly(vinyl chloride), 95, 99 cutting, 37
Poly(vinyl nitrate), 48 sizing, 75
Porosity, 17 Rubber, 95
Port-to-throat ratio, 23 butadiene--acrylic acid copolymer (PBAA), 99
Pot life , 88, I 0 I butadiene- 2-methyl-5-vinylpyridine
Potassium copolymer, 10 I
n itrate, 33 GR-I, 102
perchlorate, 56, 89, 90 polysulfide, 95
salts, 50, 58 polyurethane, 98
Premixing, 67 Rule d ie, 80
Prepolymer, 95 s
Press
blocking, 72, 102 Saltpeter, 33
dehy, 67 Screeniog, 72, 75
extrusion, 80, 102 Second order transition temperature, 31
finishing, 72 Semilive, 113
macaroni, 72 Shear, 31
Shelf life. See Stability
screening. See Press, macaroni
Shock, 17
Pressure
Single-base propellant, 45 , 53, 68, 72
chamber, P, 11, 13
Slivers, 19
maximum, 19
Slurry
index, n, 13, 45, 94 casting, 75, 88, 95, 102
Primer, 40 mixing, 68, 77
Progressivity, 18, 19, 20 Small arms propellant, 27, 54, 67, 72
Prussian blue, 93 Smoke,40,50, 89,90,92, 93
Pulverizer, 36 Smokeless powder. 45

120
INDEX (Concluded)

Sodium nitrate, 33 Thermal


Solubility (nitrocellulose), 46, 66 conductivity, 28
Solvent decomposition, 48, 52
removal, 72 expansion coefficient, 28, 52
residual, 27, 50, 53, 66 insulation, 89
volatile, 27, 52, 54 layer theory, 92
Specific Thermochemistry of propellants, 3, 5, 33, 42
force, F. 4, 7, 10, 20, 37, 46, 50, 53, 58 Thermoplastic, 95, 102
heat ratio, 1 , 6, 7, 11 Thiocyanate process (nitroguanidioe), 42
impulse, /,0 , 4, 11, 22, 45, 56, 90, 93, 99 Thrust, 11
calculated, /~P 4-5, 7, 50 coefficient, 11, 23
measured, l 1 coefficient and expansion ratio tables, 11
volume, 5 Triacetin, 50
volume, 31 Triethylene glycol dinitrate , 49
SPIA Jato Manual, 24 Triple-base propellant , 58, 74
Sporting propellant , SO, 67, 72 Two-temperalure theory, 91
Stability, 36, 42 , 52, 61 v
Stabilizer, 45, 48
Vapor pressure, 49, 50, 52
Static electricity, 72 Velocity, burned, 56
Static lest, 23 Vibration modes, 17
Slill, 74 Viscosity, 94, 113
Stress relaxation, 28 of nitrocellulose, 46, 48, 66
Sulfur, 33 Volumeter, 27
Summerfield equation (burning rate), 13 Volumetric efficiency, 27
Supersonics, 84
w
Surveillance test, 52
Sweetie barrel, 72 Water gas equilibrium, 6
Web, 18, 53, 54, 67, 72
T Wheel mill, 37
Tailings, 27, 72 Wire, 50, 101
Woolwich process (RDX), 43
Ta)iani test, 52
Temperature coefficients of burning, 14, 15 x
Temperature, initial, 14 X-rays, 84
Tensile strength, 28, 51, 99 Xylan, 66

121
~u. s. cover-NMl:IH Pl\rt<TNG OF'F'ICe . IS 6G 0 llO SS>
ENGINEERING DESIGN HANDBOOK SERIES
Listed below are the Handbooks which have been pubhshed or submitted for publication. Handbooks with publica-
tion dates pnor to I August 1962 we re published as 2.0- series Ordllanc e Corps pamphlets. AMC Circular 310-36, 19
July 1963, redesignated those publications as 706-series AMC pamphlet3 (i.e., OROP 2.0-138 was redesignated AMCP
706- l 3 8). All new, reprinted , or revised Handbook& are being published as 706- series A MC pJ.mphl ets.

General and Miscellaneous Subjects Ballistic Missile Series

Number Title Number Tit!~


106 Elements of Ar;;ament Engineering, Part One, Z.81(5-RDJ Weapon Sys Lem [f ectivenes a ( U)
Sources of Energy 2.82 Propu.l sion and Propellant3
l 07 Elements o{ Armament Engineering, Part Two, 2.S4(C) Trajector1e3 [U)
Ballistics ~86 Structures
108 Elemen~~ of Armament Engineering, Part Tl\r ee,
Weapon Systems and Components Balh sci cs Sen es
110 E:xper;mental Statistics, Section l, Basic Con- 140 Trajectories, Differenttal Effects, and
cepts and Analy&i of Measurement Data Data !or Projectiles
111 Experimental Statistics, Sectton 2., Analysis of I '>0 Interior Ballistics o( Guns
Enumerative and Classificatory Data 160(S) Elements of Terminal Ba:listics, Part
112 Experimental Sta us t ics, Section 3, Planning One. lntroductton, Kill Mechanisms,
and Analysis of Com pa rat1 ve Experiments and Vulnerabihty (U)
113 Expe nmental Statis hcs , Section '\, Special 161[5) Elemenu of Terminal Ball1stics, Part
Topics Two , Collection and Analysis of Data
114 Expe r>mental Statistics, Section S, Tables Concerning Targets (U)
121 Packaging and Pack Engineering 162.(S-RO) Elements of Terminal Ballistics, Part
134 Maintenance Engineering Guide for Ordnance Three, Application to Mi ss ile and
Design Space Targets (U)
135 Inventions , Patents, and Rela.ted Matte rs
(Revised) Carnagea and Mounts Sene3
136 Servomecha.nis ms, Section l, Theory .340 Carriages and Mounts--General
l 37 Servomechanisms. SectJon Z., Measurement 34 l Cra.d.les -
a.nd Signal Convc rt er" 342 Recoil System~
138 Servomechanisms, Section 3, Amplificalion .343 Top Carriage6
139 Se rvomechanisma, Section 4, Power Elements .344 Bottom Carriages
and System Design .345 Equ11lbrator s
l 70(C) Armor and Its Application to Vehicles (U) .346 Elevahng Mechanis:ns
2SO Guns--General (Guns Series) 347 Traversing Mechiul)~ms
2.52 Gun Tubes (Guns Series)
Z.70 P rope II ant Actuated Oevic es Mate rials Handbooks
290(C) Warheads--General (U) JOI Aluminum and Aluminum Alloys
331 Compenaatrng Elements (Fi re Control Series) 302 Copper and Copper Alloys
3SS The Automotive Aas.embly{Autornotive Serie&) 303 Magnesium and Magnesium Alloys
305 Titanium and Titanturn Alloys
Ammunition and Explosives Series 308 Gla6s
175 Solid Propellants, Part One 309 Pia1>tics
l 76(C) Solid Propellants, Part Two (U) 310 Rubber and Rubber-L..1ke Materials
177 Properhea of E><plosivea of Military lnterest,
Section I Military Py roteduucs Series
l 76(C) Pl:'operties o( Explosivea o( Military Interest, 186 Par\ Two, Safety, Procedures and
Section 2(U) Glossary
2.10 Fuzes, General and Mechanical 187 Part Three, Properties of Materials
Z.l l(C) Fuze s , Prox:irruty, El.,ctrical, Pa rt One ( U) Used 1n Pyrotechnic Compositions
Z.l2(S) Fuzes, Pr<>X1m1ty, El ectrical. Pa rt Two ( U)
U3(S) Fu:r.e s, Prox..imuy, El ect ncal, Pa rt Three ( U) Sul:'face-10-Air Missile Series
214lS) Fuzes, Proximity. El eel rical, Pa rt Four ( U) Z.91 Par\ One, Sy3tem Integration
Z.IS(C) Fuzes, Prox.imity, Electrical, Part Ftve (U) .l92 Par\ Two, Weapon Control
244 Section I, Artillery Ammunition- -General, 293 Pa rt Three, Computers
with Table o( Contents, Gloasary and l94{S) Pa rt Four, Miasde Armament (U)
Index for Se des .29S(S) Pa rt Five, Countermeasures (U)
2.4S(C) Section Z, Design for Tel:'minal Effects (U) l96 Pa rt Six, Structures and Power Source1>
246 Section 3, Design for Control o! Fhght 297(5) Pal:'t Seven, Sample Problem (U)
Cl\aracteristic:s
247 Section 4, Design for Projecuon
2.48 Section S, Inspection Aapects of ATtill~ry
Ammunition Design
249 Section 6, Manufacture of Metalhc Components
of Artillery Ammunition

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