Текст
                    AMC PAMPHLET
АМСР 706-175
ENGINEERING DESIGN HANDBOOK-
EXPLOSIVES SERIES
SOLID PROPELLANTS PART ONE
STATEMENT #2 UNCLASSIFIED
This document is subject to special export
controls and each transmittal to foreign
governments or foreign nationals may be made
only with prior approval of: Army Materiel
Command, Attn: AMCRD-TV, Washington, D.C.
20315
HEADQUARTERS, U. S, ARMY MATERIEL COMMAND
SIPTIMBIR 1964
/ЗС

f ENGINEERING DESIGN HANDBOOK SERIES Listed below are the Handbooks which have been published or submitted for publication. Handbooks with publics- tion dates prior to I August 1962 were published as 20-series Ordnance Corps pamphlets, AMC Circular 310-36, 19 July 1963, redesignated those publications as 7 06-series AMC pamphlets (i. e ., OR DP 20-138 was redesignated AMCP 706-138), All new, reprinted, or revised Handbooks are being published as 706-series AMC pamphlets. General and Miscellaneous Subjects Number Title 106 Elements of Armament Engineering, Part One, Sources of Energy 107 Elements of Armament Engineering, Part Two, Ballistics 108 Elements of Armament Engineering, Part Three, Weapon Systems and Components 110 Experimental Statistics, Section 1, Basic Con- cepts and Analysis of Measurement Data 111 Experimental Statistics Section 2, Analysis of Enumerativs and CLassificatory Data 112 Experimental Statistics, Section 3,Planning and Analysis of Comparative Experiments 113 Experimental Statistics. Section 4, Special Topics 114 Experimental Statistics, Section 5, Tables 121 Packaging and Pack Engineering 134 Maintenance Engineering Guide for Ordnance Design 138 Inventions, Patents, and Related Matte rs (Revised) 136 Servomechanisms, Section 1, Theory 137 Servomechanisms, Section 2, Measurement and Signa) Converters 138 Servomechanisms, Section 3, Amplification 4139 Servomechanisms, Section 4, Power Elements I and System Design 170(C) Armor and Its Application to Vehicles (J) 250 Guns--Genera) (Guns Series) 252 Gun Tubes (Guns Series) 270 Propellant Actuated Devices 290(C) Warheads--Genera) (U) 331 Compensating Elements (Fire Control Series) 355 The Automotive Assembly (Automotive Series) Ballistic Miseile Series Number 281(S-RD) 282 284(C) 286 Title Weapon System Effectiveness (U) Propulsion and Propellants Trajectories (U) Structures Ballistics Series 140 150 160(S) 161(S) 162(5-RD) Trajectories, Differential Effects, and Data for Projectiles Interior Ballistics of Guns Elements of Terminal Ballistics, Part One, Introduction, Kill Mechanisms, and Vulnerability (U) Elements of Terminal Ballistics, Part Two, Collection and Analysis of Data Concerning Targets (U) Elements of Terminal Ballistics, Part Three, Application to Missile and Space Targets (U) Carriages and Mounts Senes 340 Carriages and Mounts--Qeneral 341 Cradles 342 Recoil Systems 343 Top Carriages 344 Bottom Carriages 345 Equilibrators 346 Elevating Mechanisms 347 . Traversing Mechanisms Materials Handbooks Ammunition and Explosive* Scries 175 Solid Propellants, Part One 176(C) Solid Propellants, Part Two (U) 17? Properties of Explosives of Military Interest, Section I 301 Aluminum and Aluminum Alloys 302 Copper and Copper Alloys 303 Magnesium and Magnesium Alloys Titanium and Titanium Alloys 308 Glass 309 Plastics 310 Rubber and Rubber-Like Materials 178(C) 210 211(C) 212(S) 2B(S) 214(S) 215(C) 244 Properties of Explosives of Military Interest, Section 2 (U) Fuses, General and Mechanical Military Pyrotechnics Senes 186 Part Two, Safety, Procedures and Glossary 187 Part Three, Properties oi Materials Used in Pyrotechnic Compositions Section 1, Artillery Ainmunition--Goneral, 245(C) 246 247 242 249 with Table of Contente. Glossary and Index for Series Section 2, Design for Terminal Effects (U) Section 3, Design for Control of Flight Characteristics Surface-to-Air Missile Series 291 Part One, System integration 292 Part Two, Weapon Control 293 Part Three, Computers 294(S) Part Four, Missile Armament (U) 295(S) Part Five, Countermeasures (U) 296 Part Six, Structures and Power Sources 297(S) Part Seven, Sample Problem (U) Section 4, Design for Projection Section 5, Inspection Aspects of Artillery Ammunition Design Section 6, Manufacture of Metallic Components of Artillery Ammunition
HEADQUARTERS UNITED STATES ARMY MATERIEL COMMAND WASHINGTON, D. C. 20315 30 September 1964 AMCP 706-175, 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: Chief, Administrative Office SELWYN D. SMITH, JR. Major General, USA Chief of Staff DISTRIBUTION: Special
EXPLOSIVES 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. \ “ГЦ ' -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, Chambe'rsburg, Pennsylvania 17201. 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, Durham, North Carolina 27706.
TABLE OF CONTENTS Paragraph Page PREFACE............................................. ii LIST OF ILLUSTRATIONS............................. viii LIST OF TABLES...................................... x LIST OF SYMBOLS..................................... xi СНАРП» 1 INTRODUCTION 1 PURPOSE............................................. 1 2 DEFINITIONS........................................... I 3 PLAN.................................................. 1 REFERENCES......................................... 2 CHAPTBt 2 EVOLUTION OF OASES BY PROFBIANTS 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 7-1 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 Hinchfelder-Sherman Calculation.......................... 7 7-7 Example Calculation ofF, cf, by the Hirschfelder-Sherman Method....................................................... 9 7-8 ABL Short Calculation for Specific Impulse.............. 10 8 MEASUREMENT OF BALLISTIC PARAMETERS....................... 10 8 -1 Measurement of Heat of Explosion.................... 10 8-2 Measurement of Specific Force...................... 10 8-3 Measurement of Characteristic Velocity............ 11 8-4 Measurement of Specific Impulse..................... 11 fi-5 Example Calculation of I* from Measured (del) at Non* standard Conditions......................................... 11 9 BURNING OF PROPELLANTS.................................... 12 9-1 Effect of Pressure................................ 13 9-2 Effect of Temperature............................... 14 9-3 Effect of Ou Velocity. Erosive Burning.............. 15 9-4 Effect of Composition............................... 15 Ш
TABLE OF CONTENTS (Continued) Paragraph Page 9-5 Burning Rate of Composite Propellant*............ 16 9-6 Problem of Unstable Burning...................... 17 9-7 Transition from Deflagration to Detonation....... 17 10 PROPELLANT GkAlN............................... 17 11 SCHEDULING OF MASS RATE.......................... 19 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 CHAPTSt 3 PHYSICAL PftOPStTIES UQUIUMENTS 12 GENERAL........................................ 27 13 DENSITY.......................................... 27 14 GRAVIMETRIC DENSITY.............................. 27 15 HYGROSCOPICITY................................... 27 16 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 18-8 Modulus in Compression......................... 31 18-9 Shear Properties................................. 31 18-10 Brittle Temperature............................ 31 REFERENCES....................................... 31 CHAPTBt 4 MACK POWDBt 19 GENERAL.......................................... 33 20 APPEARANCE....................................... 33 21 COMPOSITION...................................... 33 22 GRANULATION...................................... 33 23 THERMOCHEMISTRY.................................. 33 24 HYGROSCOPICITY................................... 36 25 SHELF LIFE....................................... 36 26 MANUFACTURING PROCESS............................ 36 27 USES............................................ 37 REFERENCES....................................... 41 iv
TABLE OF CONTENTS (Continued) Paragraph Page CHAPTER 5 CRYSTALLINE MONOPROPWANTS 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 CHAPTBt « PLASTIC MONOPROPWANTS 35 GENERAL.............................................. 45 36 FORMULATION.......................................... 45 36-1 Polymer.................................................. 45 36-1.1 Nitrocellulose....................................... 46 36-1.1.1 Nitrogen Content..................................... 46 36-1.1.2 Solubility....................................... 46 36-1.1.3 Hygroscopicity................................ 46 36-1.1.4 Viscosity....................................... 48 36-1.2 Other Polymers..................................... 48 36-2 Stabilizer............................................... 48 36.2.1 Diphenylamine.................................... 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 40-1.1 Propellants for Cannon............................. 54 40-1.2 Propellants for Small Arms..................... 54 40-1.3 Propellants for Mortars........................ 54 v
TABLE OF CONTENTS (Continued) Paragraph Page 40-2 Rocket ant*. Gas Generator Propellants.................. 54 40-2.1 Propellants for Rockets........................ 56 40-2.2 Propellants for Gas Generators................. 56 REFERENCES.......................................... 56 CHAPTHt 7 COMPOSITES COMPRISING CRYSTALLINE MONOPROPEUANTS IN PLASTIC MONOPROPEUAKT BINDERS 41 GENERAL............................................. 58 42 FORMULATIONS........................................ 58 43 BALLISTIC CHARACTERISTICS........................... 58 43-1 Nonflashing Nitroguanidine Propellants.............. 58 43-2 High Force Nitroguanidine Propellants............... 59 44 PHYSICAL PROPERTIES................................. 59 45 THERMAL PROPERTIES.................................. 61 46 MANUFACTURING PROCESS............................... 61 REFERENCES......................................... 61 CH APTER 8 MANUFACTURING PROCESSES FOR SMOKMESS POWDBt 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 49-1.1 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 50-1 Forming Operations.................................. 74 50-2 Incorporation of Plasticizers....................... 75 50-3 Finishing Operations................................ 75 51 ROLLED SHEET PROCESS................................ 77 5I-I Mixing.................................................. 77 51-2 Rolling.......................................... 77 51-3 Finishing........................................... SO vi
TABLE OF CONTENTS (Continue?} Paragraph Page 52 SOLVENTLFSS EXTRUSION PROCESS........................ 80 52-1 Extrusion........................................ 80 52-2 Finishing.......................................... 80 52-3 Flaws.............................................. 84 53 CAST DOUBLE-BASE PROCESS............................. 84 53-1 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 CHAFT3». 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 Ptrchlcrate........... ........................ .. 93 56-4 Ammonium Nitrate................................... 93 56-5 Mixed Oxidizers.................................... 94 57 VOLUMETRIC RELATION OF OXIDIZER TO BINDER.............. 94 58 CHOICE OF BINDER..................................... 94 58-1 Asphalt............................................ 95 58-2 Polyisobutene...................................... 95 58-3 Elastomeric Binders................................ 95 58-3.1 Polysulfide Rubber................................. 95 58-3.2 Polyurethane Rubber................................ 98 58-3.3 Butadiene-Acryiic Acid Copolymer Rubber, PBAA..... 99 58-3.4 Poly(vinyl Chloride)............................. 99 58-3.5 Elastomeric Binders for Cartridge-Loaded Grains... 101 58-4 Thermoplastic Synthetic Polymer Binders for Cartridge-Loaded Grains........................................ 102 58-5 Cellulose Acetate................................. 102 58-6 Other R-ider Systems............................ 102 REFERENCES......................................... Ill CHAPTH 10 INERT SIMULANTS FOR PROPELLANTS 59 GENERAL.................................... 112 60 MOCK-UPS............................. 112 61 SIMULANTS TO REPRODUCE PHYSICAL PROPERTIES. ..112 62 SIMULANTS TO REPRODUCE MANUFACTURING PROP- ERTIES 112 63 SEMILIVE............................. 113 REFERENCES............................ 113 GLOSSARY......................................... 114 INDEX................................. 117 vii
LIST OF ILLUSTRATIONS Figure Title Page 1 Reduced specific impulse versus area ratio and gamma.......... 5 2 Burning of solid monopropellant................................... 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............... 14 6 Burning of composite propellants—filler 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 10 Star-perforated grain............................................ 18 11 Slotted-tube 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 magnify-uvii........................ 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 IMR smokeless powder for small arms, photographed in ultraviolet light, 112X magnification........ 47 28 Physical properties versus polyi er concentration................. 51 29 Relationships among T„ F, ana Q for gun propellants........... 53 30 Specific impulse of double-base rocket propellants as a function ofT,.................................................... 54 31 Burning rates of double-base rocket and gas generator propellants 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 tub*..................................... 65 37 Solvent extrusion process......................................... 67 38 Sigma blade mixer................................................. 68 39 Schraeder mixer................................................... 69 40 Macerator..................................................... 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 Bail 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 Solventless 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, /„, and flame temperature, of NH^CiO^-fuel binder composites................................................... 91 60 Burning rate, r, at 1000 psi, ambient temperature of NH^lO^-fuel binder composites..................................................... 92 61 Specific impulses, I„, and flame temperatures, of NH^NOj-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 1-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 1000-pound segmented grain.. 109 78 Segmented grain (1000 pounds)................................,,,,110 ix
UST OF TABUS Table 1 2 3 4 5 б 7 8 9 10 11 12 13 14 Title Page Reduced characteristic velocity.............................. 4 Thermochemical constants for Hirschfelder-Sherman calculation.. 8 Nominal compositions of biack powder available in the United States....................................................... 33 Granulations of potassium nitrate black powders................ 33 Granulations of sodium nitrate black powders................... 36 Consumption of black blasting powder (all types) in the United States....................................................... 40 Physical and ballistic parameters of crystalline monopropellants.. 42 Hygroscopicity of nitrocellulose............................... 48 Nonflashing propellants........................................ 39 High force propellants......................................... 59 Oxidizers for fuel binder composites......................... 89 Hypothetical fuel binder СН|Л.................................. 90 Hypothetical propellants..................................... 90 Oxidizer loading versus binder density per unit volume........ 94 x
UST OF SYMBOLS a = a constant a = acceleration i — time rate of acceleration a (subscript) = atmospheric m (subscript) = average Л» = area of burning surface = S A, = area of nozzle exit A, = port area At = nozzle throat ares b = a constant b' = a constant h" = a constant c (subscript) = chamber c* = characteristic velocity c* —. calculated thermodynamic characteristic velocity С ® concentration of polymer in solution Cd — mass flow factor = -r c* Cr = thrust coefficient C< = number at weight atoms of carbon m unit weight of ingredient I in propellant composition Ct = molar heat capacity at constant 1'ressure C, = molar heat capacity at constant volume d = grain diameter Dt = diameter of nozzle exit Dt = diameter of nozzle throat e — base of natural logarithms e (subscript) — exit E — internal energy aE = heat of formation = Ht / (subscript) = partial value contributed by fuel F = specific force or impetus F — thrust g = acceleration of gravity g (subscript) = gaseous state G = mass velocity of the gases in the port Ghp = gas horsepower H = moisture content Hf = heat of formation = A£ = heat of explosion = Q AH = enthalpy change i (subscript) = partial value contributed tr ingre- dient/ I = ingredient in propellant composition I = total impulse = specific impulse /Д = calculated thermodynamic specific im- pulse Z„ (del) = measured specific impulse at nonstand- ard conditions / (subscript) = partial value contributed by product J = product gas constituent к = erosion constant К = a constant К = Kelvin (temperature) К = ratio of initial propellant burning surface to nozzle throat area = = erosivity constant / (subscript) = liquid state L = distance downstream from the stagna- tion point L = grain length M — molecular weight of combustion gases = specific gas volume = average molecular weight of combustion gases at isobaric adiabatic flame tem- perature = average molecular weight of combustion gases at isochoric adiabatic flame tem- perature n = exponent in de Saint Robert burning rate equation, r = bP* n = gas volume in moles produced from unit weight of propellant = ± nt n> — moles per unit weight of gas at isobaric adiabatic flame temperature n, = moles per unit weight of gas at isochoric adiabatic flame temperature a (subscript or superscript) = calculated thermo- dynamic value a (subscript) = initial condition ox (subscript) = partial value contributed by oxi- dizer p (subscript) — constant pressure conditions P = pressure P, — chamber pressure xi
LIST OF SYMBOLS (Continued) — heat of explosion = H„ = linear burning rate = Rankine (temperature) R = specific gas constant = -rj R, = universal gas constant RF = relative force RH = relative humidity RQ = relative quickness j (subscript) = solid state S — area of burning surface S = tensile stress 5, = tensile stress at break Sf = final area of surface after burning St — initial area of surface S» = maximum stress t = time X» = burning time t (subscript) = throat condition T = absolute temperature Tt = initial temperature T< = pyrolysis temperature T« = reference temperature 7, = isobaric adiabatic flame temperature Tt = temperature at throat T, = isochoric adiabatic flame temperature к = a constant v (subscript) = constant volume conditions V = velocity V = volume Vt = volume of propellant W = weight dW W = weight burning rate = x s weight fraction у = volume fraction ------(overline) — average a = a constant a = covolume a = nozzle divergence half-angle fl = a constant fl = volumetric coefficient of thermal expan- sion C. у — ratio of specific heats = -£ c = nozzle-expansion area ratio ~ y = viscosity of solution = viscosity of solvent = relative viscosity = nozzle divergence loss factor = propellant mass ratio, ratio of propellant mass of any stage to gross mass of that stage = temperature coefficient of pressure at constant pressure-rate ratio = temperature coefficient at pressure at constant К value = density 1 P = specific volume = temperature coefficient of burning rate at . . /Э1пг\ constant pressure = ("gy) — temperature coefficient of burning rate at constant К value = () * (superscript dot) = time derivative
SOLID PROPELLANTS FAM ONI CHAPYM 1 INTRODUCTION 1. Purpose. Thb Handbook b intended to pro- vide a general description of solid propellant* wed in «mall arnu, artillery, rocket*, and кипе other devices. It is assumed that the reader has as background the equivalent of an undergraduate degree in engineering or physical science, but no previous experience in propellants or ballistics. X Dadnitions. A solid propellant is a chemical or a mixture of chemical* which when ignited burns in the substantial absence of atmospheric oxygen at a controlled rate and evolves gas capable of performing work. In order to discuss certain phenomena, notably burning and detonation proc- esses, it b necessary to define certain term* that are used with meanings differing significantly from those given in MIL-STD-444.1* The more im- portant of these are: A (solid) monopropellant b a single physical phaae comprising both oxidizing and fuel ele- ment*. This is analogous to common usage in the liquid propellant field describing a single- phase liquid propellant. A filler b a discrete material dispersed in substantial quantity in the continuous or binder phaae <Л a composite propellant Deflagration b a bunting process in a solid system, comprising both oxidant and fuel, in which the reaction front advances at les* than sonic velocity and gaseous products if produced move away from unreacted material. Whether or not explosion occurs as a result of deflagra- tion depends on confinement. None of these definitions b used for the first time in thb Handbook. Other definition* are intro- duced in the text at appropriate places. Unless otherwise noted, definitions are in accord with * Number* refer to items lined a* Betances at the end 0^ MCb сйяриг* MIL-STD-444, Merriam-Webster's unabridged dictionary, or common usage. 3. Plan. In Chapter 2 b described how the figures of merit—specific force for gun propel- lants and specific impulse or characteristic velocity for rocket propellants—are derived from therm», chemical data and empirically verified. Abo in Chapter 2 b discussed the mechanism of burning of propellant* and the scheduling of gas evolution to meet the requirements of various engine* in which propellants are used, such a* guns, cata- pults, rockets, and gas generator*. A few simple numerical example* are given by way of illustra- tion, but detailed discussion of the ballistics of such engines b omitted as being beyond the scope of thb work and available elsewhere. In Chapter 3 appear* a discussion of certain physical properties of propellants as related to system requirement*. In Chapters 4-9 conventional propellant* are dis- cussed, arranged according to their physical struc- ture. Black powder b presented in Chapter 4. Crystalline monopropellants appear in Chapter 5. Plastic monopropellant*, commonly known as single-base and double-base propellants, appear in Chapter 6. These common terms can be somewhat confusing, since the class contains propellant* comprising, for example, cellulose acetate and nitroglycerin winch are difficult to assign to either single- or double-base. Composites comprising mcnopropellaiit binder and monopropellant filler, commonly known as triple-base, appear in Chap- ter 7. Apia the common term can be confusing, as when a nitroguanidlne propellant with a single- base (nitrocellulose) binder is to be described. Manufacturing processes for the propellants of Chapters 6 and 7 are given in Chapter 8. Fuel binder composites are discussed in Chapter 9. A discussion of inert simulants, or dummies, for pro- pellants b given in Chapter 10. Higher energy 1
systems are discussed in ORDP 20-176, Solid Pro- plants. Part Two (C). literature consulted in the preparation this Handbook includes publications early in 1960. The reader is referred to SPIA/M2,’ in which will be found data sheets for all of the propellants developed and used within the Department of De- fense including those that win appear subsequent to the publication of this Handbook. ummui 1. MIL-STD-444, Military Standard. Nomenclature and Definitions in the Ammunition Area, Department of Defense, 6 February 1954. 2. SPIA/M2, Propellant Manual, Solid Propellant In- formation Agency, Johns Hopkins University, CON- FIDENTIAL. 2
СМАРТ* 2 EVOLUTION OF GASES BY PROPELLANTS 4. GcmmL The devices in which propellants are commonly used, be they devices, such as guns that comprise moving pistons, or vented vessels acquiring momentum by discharge of gas, .are de- vices that convert heat energy into mechanical energy. They thus fall into the general classifica- tion of beat engines. The propellant gas is then the working fluid that actuates heat engines. In solid propellant heat engines the working fluid is generated in situ by burning the propellant within the engine. The general problem in fitting a solid propellant to a heat engine is the generation of gas of specified properties at a specified rate which is a function of time. The specifications of gas prop- erties and rate of generation are not usually inde- pendent of each other. Thus a given problem may be solved by using gas with one set of properties at one rate schedule or, alternately, by using a dif- ferent set Gt gas properties on a correspondingly different rate schedule. The properties of the gas are determined by the composition of the propel- lant The derivation of the gas properties from the composition is known as thermochemistry of pro- pellants. The rate of gas generation is determined by the linear rate of burning and charge geom- etry. Of these, the linear burning rate as a func- tion of pressure is a propellant property. System pressure and charge geometry are controlled at least in part by the end-item specification. The overall problem of selecting a propellant formula- tion and geometry to meet a given end-item per- formance specification is an exercise in interior ballistics. Because the propellant developer owes tire ballistidan both thermochemical data and rate versus pressure data, he should have a qualitative knowledge of interior ballistics in order to perform his function intelligently. 5. Equation of state. The classical equation of state used by ballisticians is known as the Noble- Abel equation. For unit mass of propellant it is usually written P(V- a) = RT where К is the gas constant per unit mass of pro- pellant, or more generally (1) tn where Я. is the universal gas constant The term a is known as the covolume and may be thought of as the space occupied by the gas when com- pressed to the limit. It has the empirical value of about 1 cc per gram for most propellants.1 The significance Gt the covolume correction may be shown by some simple numerical examples. Under standard conditions of temperature and pressure (273°K, 1 atm), 1 gram of gas of molecular weight 22.4 occupies 1000 cc. A temperature of 2730‘K and a pressure of 68 atm (1000 psi) are conditions typical of rocket ballistics. Under these circum- stances TIKI 1 V - a = 1000 X x ~ = 147 cc 273 Oft For 1 percent accuracy, V — a does not differ significantly from V. It is customary, 'berefore, in rocket ballistics to ignore the covolume correction and use the perfect gas equation (la) as the equation of state. On the other hand, whereas we encounter similar temperatures in gun ballistics, the pressures are higher. Taking 3000 atm (44000 psi) as typical, for 1 gram of gas 2730 1 V - « = 1000 x X = 3.3 cc 273 3UUU Under these conditions, V — a differs significantly from V, and the covolume correction must be made. For precise calculations, other equations of state of greater precision than Equation 1 are used. These equations are more complex and contain constants the physical significance of which is more difficult to understand. In such calculations the departure from the perfect gas law is still called the covolume correction. The covolume if evalu- ated is no longer a constant but is a variable with a value stin in the neighborhood of Noble-Abel's a. 6. Ballistic parameters. Different systems’ * of interior ballistics have been developed by gun bal- listicians on the one hand and by rocket ballis- ticians on the other. Both typer of system depend on the same primary thermochemical properties of propellant gases, but use different parameters as 3
working tools. Thus, as a measure of the ability cf the combustion products of propellants to per- form in their respective heat engines, gun ballis- tioans use the parameter specific force (often abbreviated to force), or impetus, F. Rocket bal- Mstirians use for the same purpose characteristic velocity, c*, or specific impulse, l„. Auxiliary power unit engineers sometimes use gas horse- power, Ghp. Ы. fiperific tare. Specific force, F, is a meas- ure of the ability of the propellant gas to perform work. It is defined by the equation F = ^ (2) sad is expressed in terms of foot-pounds per pound* iW* ОмнгмОокЪЙс TaKeeSt^» Characteristic ve- locity, c*, is not a significant physical quantity. It is defined as where Pt is chamber pres- sure, /It is nozzle throat area, and W is burning rate in pounds per second. Mathematical analysis* shows that it can be computed* from the thermo- dynamic properties of the gas as TABLE 1. REDUCED CHARACTERISTIC VELOCITY 1.15 1.566 1J0 1342 1.25 1320 1.30 1.499 1.35 1.479 1.40 1.461 characteristic velocity with changing у points out that the characteristic velocity to a stronger func- tion of than of y. 4-4. Specific impulse. Specific impulse, to defined as the impulse (force x time) delivered by burning a unit weight of propellant in a rocket chamber. From rocket ballistic theory1* can be derived the equation VgM(y- 1) (4) Note that this parameter becomes a thermo- dynamic fonction of the propellant only when the M, Redteed tbaratterisllt viintMy, Equation 3 may be rewritten (3a) The quantity dnced characteristic velocity; it to dimensionless sad to a function only of the specific beat ratio, y. In Table 1 are shown the values of the reduced characteristic velocity for different values <Л у. The characteristic velocity is obtained by multiply- ing the reduced characteristic velocity by The comparatively small change of the reduced •Computed thermodynamic vahtee an denoted by sub- script or aupencript o, to diServatiate from values de- yiwlina oa direct measurements. See stoo Paragraph S-3. p ratio p is specified. The current United States convention to to consider P, as one atmosphere (14.7 psi) and P, as 1000 psi unless otherwise specified. Implied in this formula to the assump- tion of zero half-angle of nozzle expansion. See also Paragraph 8-4. 43. Reduced specific «aputa. Equation 4 may be rewritten (4a) The quantity «/—V/ is known as the reduced specific impulse; it is dimensionieu. and depends /> only on the pressure ratio, -jp, i 4 the specific heat ratio, y. A plot of the reduced cific im- 4
mstric units< Figun 1. fiadueed Spedtic Impuin Yunus Ana Katie and Gamma pulse as a function of pressure ratio for various y's is shown in Figure 1. The use of this chart in calculating specific impulse is illustrated in the numerical example, Paragraph 7-7. 6-t Vohme specific impulse. The product of specific impulse and density, expressed in unit* of pound-seconds per cubic inch, is known as the volume specific impulse. If a proposed rocket motor has a fixed propellant envelope, it will gen- erate impulse roughly in proportion to its volume specific Impulse. Thus a propellant. with lower spe- cific impulse but higher density may sometimes outperform one with higher specific impulse and lower density. If the proposed rocket motor re- quires a given total impulse but has no envelope requirement, the volume of the propellant, and hence the size and weight of the (inert) cham- ber, will be lower the higher the volume specific impulse. Here again is a parameter that does not become a thermodynamic function of the propellant unless the ratio is specified. There appears to be no 1 P- United States convention with respect to -=*. Gas “i horsepower is therefore not purely a propellant property. 7. Thcsmochcarisfry. Thermochemical data re- quired for the determination of the abov»- param- eters are the burning temperatures ы. constant volume and at constant pressure, Г, and T„ re- spectively, specific gas volume, and, ratio of specific heats, y. The burning temperatures and composition of the product gas are also impor- tant from the standpoint of compatibility with the surroundings. In propellants the surroundings in- clude the inert parts of die heat engine which must remain intact through the cycle or even have a service life of many cycles. 7-1. Specific gas volume. Specific gas volume, is the number of weight moles of gas pro- duced in the burning of a unit weight of propel- 5
lent. In ыП cases where only gaseous products result, M is the avenge molecular weight of the product gas. The gas volume is determined from the conservation equations for the elements SC = [CO,] + [CO] (6a) SH = 2[H,] 4 2[H,O] + [HC1] (6b) XN = 2[N,] (6c) SQ = [HC1] (6d) SO = [CO] + 2[CO,] + SH,O (6e) (CO,] + [CO] + [H,] + ГЯ,О] + (N,] + [Ha]=^ (7) n = SC + HSN + V4SH + WSCI (8) Лж In these equations, sC, e.g., is the total number of weight atoms of carbon in a unit weight of pro- pellant and [CO,] is the number of weight moles of CO, in the gas from the unit weight of pro- pellant. If is the weight fraction of ingredient I in the propellant composition and C, the number of weight atoms of carbon in unit weight of I, then SC = S(a«C<) (9) SH, sN, and SCI are derived in the same way. 7-2. Flame tanperatare at constant volume. The flame temperature at constant volume is de- termined by solving the equation 1 Г * T c; L J 1 о dT (10) where is the mole (volume) fraction of a prod- uct gas constituent J, e.g., CO,, in the gases formed from the propellant and C(/ 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, be- tween the heat of formation of the products and the heat of formation of the propellant. ~Q ~ AEfntoeb — (11) Assuming no heat effect of mixing nniuit = SfxiAfr) (12a) where &Et is the heat of formation of ingredient J per gram. &Ernt^t, = ^2(УуД£,) (12b) where ДЕ/ is the heat of formation of product J per mole. The quantities yj are derived from Equations 6>-6c and various gas equilibrium equations, of which the most important is the water gas equi- librium [CO][H,O] ICO,][H9] “ (13) In actual systems there may be found small quantities of constituents other than those dis- cussed above, such as CH4, NHa, NO, OH, H, O, and N, as well as products of other atomic species if present in the propellant For each such constituent there is available an equilibrium con- stant ЩТ) similar to K.(T) (Equation 13) and an estimate of its molar heat capacity. ’ The constants Kt(T) and the various C/s and AE*s have been quite precisely evaluated as func- tions of temperature, T.“ 7-3. Flame temperature at constant pressure. The calculation of T, is similar to that of Tv, except that instead of Equation 10 we must use the following С = ]^ь У/ fT, ' Ctj dT T. . (14) where Cfj is the heat capacity at constant pres- sure of gas constituent J, Since burning is now at constant pressure, en- thalpy instead of heat of formation must be used. Q — AZ/p^uct, — AHpH^ibata (15) = S(X(AH4) (16a) ~ (16b) 7-4. Ratio of specific heats. “The value of у for a propellant is the weighted average of the y's of tlx дм constituents 7 XxA (17) The values of у used are not the ratios of heat capacities at room temperature, but the ratios at operating temperatures of the heat engines con- cerned. 6
7-5. Exact calculation of flame temperatare and product composition. The calculation of the flame temperature and product gas composition is done by trial, starting usually with an assumed tempera- ture. This is an iterative process and is profitably done with a machine calculator, particularly when gas equilibria other than the water gas equilibrium must be considered. Programs11*14 have been worked out for such calculations, assuming essen- tially only adiabatic conditions and chemical and thermodynamic equilibria, to give results of accu- racy limited only by the thermodynamic data of the individual species considered. These programs also are used for calculated specific impulse on the basis of either frozen composition flow or equilib- rium flow through the nozzle. A JANAF Thermo- chemical Panel exists for the coordination of thermochemical data and calculating procedures. The exact calculation, even with a sophisticated machine calculator, is time consuming. Conse- quently nearly every propellant development facil- ity has for internal use a short-cut calculation yielding approximate results useful for screening and program guidance. Many of the data reported in the literature, including some SPIA/M2 data sheets, are the results of such approximate calcu- lations and should be confirmed by exact calcula- tions before important decisions are based on them. Two approximate calculations that have been used by more than one facility are described in Paragraphs 7-6 ana 7-8. 7-6. Hirschfelder-Shennan calculation.11 It L possible1* to calculate Q from additive constant; Qi which are defined as the contributions of ingre- dients I to the heats of explosion of propellants containing them. The Hirschfelder-Shennan calcu- lation takes as the reference temperature 2500°K, The heat of explosion, Q, at the propellant differs from the heat required to bring the combustion products to 2500° К by an amount E, which can also be calculated from additive constants E, which are properties of the ingredients I. Finally, the heat capacity of the product gas at 2500°K is estimated from additive constants C„t which are properties of the ingredients I. These heat capaci- ties are assumed constant for the interval from 200C°K to 3000°K. The burning temperature at constant volume, Tv, is the*1 given by the equation T, = 2500 + (18) The gas volume, is calculated by Equation 8, M and the force, F, by Equation 2. If T, is above 3000°K, a better approximation of T,. is given by the relationship Tr = 3000 + 6046/ - (C, + 0.01185) + [(C„ + 0.01185)2 4- 3.308(10" 4)(E - 5OOC,.)]2 In order to calculate characteristic velocity from Equation 3 or specific impulse f om Equa- tion 4 (see also Reference 17) we need the flame temperature at constant pressure, Tp. and the ratio of specific heats, y, at the working temperature. The value of у is given by the relationship1 * - t i 1987 y ~ 1 + CrM (20) from wl ich T, is calculated by the equation T, = — (21) У Additive constants for a number of prooellant ingredients are given in Table 2. Constants for other organic ingredients can be estimated from the relationships1' M) , = Ct 4- HNt + ^Hi (8) CVf = 1.620C, 4- 3.265H, + 5.1930, 4- 3.38417, (22) Qi = (-nF), - 6742Ц2С, + йЛ', - О,] (23) Е( = (-ДЕ), - 132771С,— 40026H, + 518190, — 67241V, where (—AE), is the heat of combustion of ingre- dient I. Within the range 2000° to 4000“K for Tv this method gives results within a few percent of the exact method. The method should not be used for propellants with 7\. over 4000°K as it does not allow for dissociation to free radicals, such as H, OH, and Cl. It should also not be used for propellants yielding a substantial amount o;' con- densed exhaust. 7
TABLE 2. THERMOCHEMICAL CONSTANTS FOR HIRSCHFELDER-SHERMAN CALCULATION** e< __E1_ 4 /1\ Acetone -1938 0.5104 —284X5 0.10331 Ammonium dichromate 1290 0.2700 610 0.0200 Ammonium nitrate 1450 0.4424 405.1 ООЭ748 Ammonium perchlorate 1603 0.3167 80022 0X128 Ammonium picrate 539 0.3213 -117 0.04470 Aephalt -2302 0.2179 -2305 0.09450 ЯЛ-МУР cefofyiatt (90% butadiene, ’0% 2-nrjthyl-5-tinylpyridine -2711 04132 -3183 011344 Butyl carbitol adipate -1836 0.4923 -2629 009099 Butyl cartdtol formal —1802 0.5229 -2652 0.10403 VMIXU ВИИ —3330 0.1349 -31874 008326 ChfinlOBt -1243 0.3953 -1971 006929 iubUyl maleate —1338 0.3872 -195? 008155 Di-a-butyl phthalate -2071 0.4258 -2656 009701 Dibutyi eebacate -2395 0.5108 -3139 01113 DH2-ethy&M>yl) aadate —2612 0.5272 -2272 011876 Diethyl phthalate -1760 0.3166 -2348.7 0.08550 Diglycol dinitraie 1073 0.3837 23X4 0.04389 Dinirropheamyethanol -15 0.3369 -633.4 005693 DJoctyl phthalate -2372 0.4650 - 3020 0.11086 Diphenytamine -26M 0.3471 -3010 0.10637 Diphecylguanidine -2270 0.3476 -2626 0.09941 Ether -2007 0.5970 -2958 0.12143 Ethyl alcohol — 1716 0.6083 -2785 010334 Ethyl ceutralltc -2412 0.3905 -2766 0.10434 Graphite -3370 0.1349 -3234 0.08326 GR-I rubber -3257 0.5779 -4006 0.14235 HMX, CydotctramethylcnetetranitramiDe 1321 0.3414 575 0.0405 Load «tearate -2000 0.3976 -2440 0.09180 M4V -1827 0.3976 —24ОД 0,09180 N-MethyJ-p-nitroamline -1095 0.35308 -1625 0.07887 Metriol trinitrate 1139 0.3052 377 004313 Mineral jelly -3302 0.5811 -475 0.1426 Nitrooelluloee, 1X2% N 900 0.3478 137.7 004127 NitroesHuloee, 12.6% N 956 0.3454 198.9 004040 Nitocafluloee, 13.15% N 1033 0.3421 283.1 003930 8
TABLE 2. THERMOCHFALCAL CONSTANTS FOR HIRSCHFELDER-SHERMAN CALCULATION” (Cnuttmaed) A <4 2-NitrodiptMnyUmine -1813 0.3226 -2201 0.08411 NStfOgiyccriii 1785 0.3438 951.9 0.03082 Nitrojuanidine 713 0.3710 —68.6 0.04806 гк1Л» лигамусплии wnmitrnw 1531 0.3424 727 0.0348 nm 1202 0.3703 374 0.04109 PoiywtK* -2184 0.3552 -2620 039123 MyiaotateM -3228 05798 -3981 0.14259 My (methyl acrylate) -1404 0.4231 —2111 008140 Myrtjmne -2983 03739 -3309 0.11523 Myurcthaae -3296 0.4073 -3773 0.10796 My(vinyl chloride) -1614 03080 -1851 OjOMOO FotaeiiBn nitnte 1434 03138 243 0ЛО9О9 Masefam perchlorate 1667 03000 800 0.00722 Pot**hnn tutthte 300 0.1250 -800 0.00574 RDX, CydotrimethyienetrinitnuaiM 1360 0.3416 615 0.0405 Sucrose octucctkte -1121 0.3941 -1825 0.06922 Triacetin -1284 0.4191 -1973 0.07333 Triethylene glycol dinitrate 750 0.40430 -8934 04)5412 Trinitrotoluene 491 03037 -110 0.04843 7-7. Example caknlatton of F, cf, Z£ by Ae Hbrschfelder-SberauB method. Consider a propel- lant of composition: Nitrocellulose, 12.6% N 0.50 Nitroglycerin 0.49 Ethyl centrallte 0.01 From the composition and Table 2, we have Wettbt Inredtait tractkn a«<2> *,c. 1 хД xi/M, NkrooeUnlcrc 030 471 0.1727 993 0.020И ГШгСффСвПЕ! 049 875 0.1685 4664 0.01510 Bthyt centralite 0.01 -24 0.0039 -274 0.00104 8шммй1иш 1Л0 1329 03431 5383 0.036*4 Isochoric flame temperature: T9 by Equation 18: 2500 + = 4060°K Since this is higher than 30C0°K, we must calcu- late by Equation 19 T, = 3000 + 6О4б|- (0.3451 + 0.01185) + [(0.3451 + 0.01185)» + 3.308 X 10~* X 1) (538.3 - 500 X 0,3451)]® | = 3855’K or 6940dR Force: F 1543 X 694 X 0.03634 = 389,000 ft-Ib/lb 9
Specific heat ratio: _ , , 1.987 X 0.03634 _ - y = 1+—o3Si--------------= 12092 isobaric flame temperature: T, = = 3188°K or 5738eR Characteristic vetocity, cf: From Table 1, the reduced characteristic velocity corresponding to у = 1.209 is 1.540. The characteristic velocity, c{, h then cf = 1.540 V 32.2 x 1543 x 5738 x 0.03634 = 4950 ft/eec Specific impulse, l^. From Figure 1, the reduced specific impulse corresponding to у = 1.209 and & = 0.015 is 2.445. The specfflc impulse, is then = 245 Ib-sec/Ib 74. ABL start cMatfan for spedfle km* puke.91 In order to shorten the time and coni' piexity of the exact calculation for specific impulse of propellants with condensible exhaust, the ABL method makes a number of simplifying assump- tions. Chief among them are: (a) No product dissociation is considered. (b) A priority system applies to the forma- tion of the products. Thus, oxygen first oxidizes all light metal, then converts C to CO, then Hi to HiO, and any oxygen still not used up converts CO to CO,. (c) Certain latent heats are completely re- covered during nozzle expansion. The calculation can be performed with a desk calculator, but is usually done with a larger calcu- lator if available. Results of this calculation пиу differ from exact calculation results by as much as 3 percent The results do not represent either frozen flow or equilibrium flow, but agree fairly well with exact equilibrium flow calculations. The asaumption of no dissociation leads to arti- ficial. values for Tf. empirical detrnninarion of the ballistic parameters is discussed in the next fere paragraphs. fl-L MeaamoMat at beat at expiaatas. The brat of explosion of a propellant, Q, also known as the calorific value, is measured by burning in a bomb calorimeter under an inert atmosphere. Two types of calorimeters have been in common use. In the Boas calorimeter the loading density, or weight of propellant per unit volume, is Mriy high, leading to pressures of some thousands of pounds. This calorimeter need not be preprossur- ized. In a coal calorimeter, the loading density is low and an initial inert gas pressure of some 200 to 300 psi is required. Both types cf calorimeter give essentially the same values of Q. For thermochemical purposes, the observed heat must be corrected for the heat of condensation of water and for shifting gas equilibrium during the cooling of the calorimeter and its contents. This correction amounts to about 10 percent and may be so approximated." Uncorrected calorimetric values, denoted "water liquid,” are cf considerable utility as a quality assurance measure in volume production of propellants to verify that successive lots of propellant manufactured to the same for- mula actually duplicate each other within specified limits. The calorimeter test can be run with much less effort and more precision than a complete chemical analysis. The procedure for the calorim- eter test is given in a Navy Department Bureau of Ordnance report" Calorific values encountered in propellants seldom exceed 1500 cal/g and are accordingly much less than for ordinary fuels. The obvious reason for this is that ordinary fuels draw on atmospheric oxygen for their combustion re- actions, whereas propellants must carry their oxi- dants within themselves in order to function in the absence of air. 1-2. Measaronent of specific farce. Combining Equations 1 and 2 we get (25) A direct experimental measure of F should then be obtained from the pressure developed under adiabatic conditions by burning a weight, W, at propellant in a closed chamber of volume, V. Be- cause truly adiabatic conditions can only be ap- proached, a related concept, that of relative force, is used. If equal weights cf two propellants with the same burning time are fired consecutively in 10
the same doted vend at the same initial tempera- ture, W and (P — »W) m constant Then Fi, the force of the standard propellant, is arbi- trarily assigned the vdue 100 percent, and die relative force, RF, of the propellant under exami- nation becomes KF = &xl00% (26) Relative force is used in quality control of gun propellants to assure that successive kits of the same formulation duplicate each other. In develop- ing a new propellant to replace an existing one, a measurement of relative force is useful as an indication that the relationship between calculated and delivered force is or is not similar to the rela- tionship for the known standard propellant The procedure and description of apparatus for the de- termination of relative force may be found in an Army Service Forces Directive.’4 8-3. Mt assay at at of characteristic velocity. Delivered or actual characteristic velocity, c*, is defined as e*=^£/'p.dt (27) Ft J It is determined experimentally by static firing of a weight, W, of propellant in a vented vessel of known throat area, At, measuring the chamber pressure as a function of time, and integrating. The JANAF Solid Propellant Rocket Static Test Panel has published” a survey of existing static test facilities and is continuing to coordinate test procedures. Comparison of c* with cf gives a measure of the operating efficiency of the vented vessel. In similar heat engines with similar pro- pellants, should remain nearly constant. The difference between cf and c* is due largely to heat leases to the motor walls. - 8-4. MeMuranent of specific hnpcbe. Deliv- ered or actual specific impulse, is defined as This parameter is determined also by static firing a vented vessel,, but measuring thrust" Unless the operating and discharge presems are 1000 psi and 14.7 pel, respectively, the meas- ured I* must be corrected to these values. Cor- rections must be applied also for the divergence half-angle of the nozzle, since the amount of impulse delivered decreases as nozzle angle in- creases." The usual convention for half-angle is 15°. Part of the difference between IS, and is therefore due to the divergence toss. The IS* convention is unfortunately net always observed. Some measured data reported in the literature have been corrected to zero half-angle. In taring 1„ data, one must identify which half-angle cor- rection has been used. »-S. Example rairuintfan af fw fosm aremaredl l„ at nonetanJarii coadMiaaa. The following data were taken from an actual rocket firiqg: Expansion ratio, i, = = 2.779 Mean chamber pressure, Pe = 218 pda Nozzle divergence half-angle, a = 20° Specific heat ratio, у = 1.17 /„ (del) = 201.3 Ib-sec/lb The correction of I„ (del) to standard condi- tions involves the parameter thrust coefficient, C,t from interior ballistics. The thrust coefficient, de- fined as с'=га=^ m measures the contribution of the nozzle to the rocket thrust. Since c* is independent of discharge conditions, for any given rocket firing 4?- is a constant independent of nozzle and external con- ditions. The thrust coefficient has its maximum value when expansion in the nozzle is to zero pressure (vacuum) and discharge is also to zero pressure. For any other exit pressure the vacuum thrust coefficient must be corrected by a term И the ambient pressure differs from the exit pres- sure another correction involving » applied. ^tjmust be Values of Cr and «(y^are obtained from Thrust Coefficient and Expansion Ratio Tables" at which die tabulated CF is for vacuum discharge 11
and zero divergence angle. The divergence angle correction” b made by the equation A — 0.5 + 03 cos « to that the overall correction becomes actual Cr = а[с,<-ы.>-.(£)] + .(£)-.(Й) For the example at hand, using the table values: Firing ccndttions Standard conditions primary pyrolytic products are given off already premixed and in proportions such that the final re- action of die products among themselves wffl bring the gas to flame temperature and thus duplicate the hot atmosphere in temperature and composition. Although the temperature rise and ccmpotiton changes are continuous from the pro- pellant to the products at flame temperature, it is convenient for analysis to break the process down into several phases as represented by Figure 2- Region A represents the unheated interior portion 134358 021405 02699 1.75284 0.13856 0283 Inserting numrrical values, and **"**78 for standard condkioM F< s Fs C, (Brfa«)* = 02699(134358 - 021405) + 021405 - 2.779 X = 1316 Cr ДО = 0283(1.75824 - 0.13856) « 1387 Aowro 2> BwaIm cf ScU The corrected value of /„ at standard condition Пь UKfCuKCp 201.3 X = 242.8 Пмес/lb 9. Bunfag of prepelants. Heat will be trans- ferred by ratfiaticn, conduction, and/or convec- tion to the surface of a odd solid propellant impended in a tot atmosphere. If the solid is men ti ally a nonconductor-of heat, the heated sur- face wfll pyrolize, giving rise to gaseous products and exposing new surface to the hot atmosphere. The gas in immediate contact with the burning sur- face” wffl be the uncootantinated pyrolytic prod- ucts of the surface, at the temperature of pyrolysis. Moving out from the surface the gases are raised to the temperature of the hot atmosphere and undergo reactions among themselves and with the atmosphere so that the hot atmosphere continues to exist in a state of equilibrium among the sev- eral chemical species present. If the solid is a monopropdlant and the hot atmosphere comprises its combustion products at flame temperature, die •Shoe thb value b a theoretical value derived from ntW*d рШОМЙП) Й dOtf DOt MCtflNtfily aareo with a vahw of С» cakubMd by Equation 2* from m seen red /» and c*. of the solid. In region В a thin layer of the solid is bring heated to pyrolysis temperature, T«. In region C pyrolyns is taking place and gaseous products are being formed. The pyrolytic reactions may or may not involve the formation of liquid intermediates (foam zone). A layer of primary gaseous pyrolytic products at temperature Tt is regfon D. In region E (fizz zone) these gases are heated to ignition temperature. In titi' process they may undergo low temperature reactions of an exothermic character and produce some heat. The bulk of the heat is generated in the flame zone, region F, to yield finally burned gas at tempera- ture T in region G. At operating pressures in the neighborhood of several hundred pounds per square inch and higher, die thickness of the герои В through F b small, perhaps of the order of 10~* inches in total. By operating at greatly reduced pressures one can broaden these regkms. The foam rone, firn zone, and flame zone have been observed far experiments of thb type.** The linear rate of banting of the monopropel- lant depends on the rate at which the surface receives beat from the surrounding combustion products. All caponed surfaces that can “see” the 12
hot combustion products should receive heat at the seme rate and therefore bum at the same rate. The bunting surface should recede by parallel layers This coodusfoo, known as Ptobtrfr LmP1 and first announced for black powder, has been verified for monopropellants under both racket and gun conditions by examination and measure- ment of partially burned grains. It appears also to hold for composite propellants, although the ex- The rate of regression of a burning propettant surface, measured nosmal to die surface, is known aa the Harar fotrnfog rate, r. It is usually expressed in tunu of inches per second. When r is muMpiied by the area of the 1яияйщ MrfflOC, S, and by the densify we have, finally, the иеДО—or яма»— htnflio reft, expressed as pounds per second Ж = rSf (30) Several factors are reco^iiaed as affecting the burning rate. Among these are pressure at which burning is taking place, initial temperature of the ptopelam, gas velocity over the burning surface, aad composition of die propellant. •-L. Effect of prusuru Increasing the pressure at which burning takes place should increase the rale of heat transfer from the flame to the pro- pellant by increasing the density of the gas phase and thereby decreasing die thickness of regions D and E through which the heat must be trans- ferred. The influence of pressure has been stmfled in both dosed bombs and vented vessels over a period of years, and empirical equations in various form* developed by different schools of bBlKe6ciens« de Saint Robert equation” r = bP* (31a) Muraour equation** r = a + bP (31b) Summerfield equation** £=^+b^^H(31c) If the fogP —fogr relation for a propellant is plotted we get a family of curves ressmbfiag Figure 3 from propellants behaving according to Equation 31a, from which the values of b and n can be evaluated. The constant n is the dope of lhe fog rate versus log pressure line. At gun pres- sures, 10,000 to 50,000 pd, nearly all propellants follow Equation 31a, with n = approximately 0.9.“ At rocket pressures, bdod 2000 psi, n for the same propellant is generally lower than at gun ferWMchr = bT pressures. In thb region will be found propellants giving the normal straight line log rate versus fog pressure relationslap, but also many propellants deviating widely from it Two types of curves are worthy of special mention. Propellants showing a region of markedly re- duced n, as shown in Figure 4, are known as Figure 4. flute Aeriure fleletiomfop of Plateau Aepelfonti 13
“phtean** propellants.** Thb behavior is shown by certain nitrocellulose system propellants contain* tag 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, aa shown by the fept dnx with- out die lead the propellant would shw a nonaal cur< coinckfing with the high psr-jaue trench of the plateau propellant’s carve and continuing ыж- malty huo the lower pressure region hne, Figure 4). The mechanism of pialauj 1’Lnnation has not been fully eh tidated. From Equation 31a the pressure in a vented vessel is of the form** P = co«t.x(^y_’ До) from which it is apparent that a low value cf n is desirable in rocket propellants to decrease the sensitivity of die operating pressure to small changes in b (a function of propellant ambient temperature); 5, the burning area; and At, the throat area. In practical terms, a low value of я permits design of tighter weight rocket motor chambers by decreasing die requirement for high safety factors to take care of deviations o' b, S, or A, from design values. As a low value of л is desirable, a negative value is even more desirable. Propellants are known which show negative values of n wet short pres- sure ranges, as shown in Figure 5.” They are known, from the shape of the curves, as “mesa” propellants. In the region of negative slope, should the pressure increase as a result of sudden expo- sure of additional burning surface or by partial constriction of the throat the rate would drop immediately to restore the balance. The close ap- proach of the isotherms also contributes to a low temperature coefficient of performance for vented vessels designed to operate in this region. Cross- ing of isotherms indicates a region of negative temperature coefficient. 9-2, Effect of temperate*. As can be seen from the isotherms cf Figures 3, 4, and 5, the initial temperature of the propellant has a significant effect on the linear bunting rate. If all of the heat transferred to the propellant surface from the com- bustion products were used to raise that surface to a tefl^perature Г, at which vaporization or Figure 5. Me-Fnmure Itekrtioruhip cf Mete Aropelfants reaction becomes appreciable, one would expect die temperature-rate relationship to assume the form r'~ (.Г-Тд (33) where V is a constan t and T< is any initial tem- perature. By measuring the linear burning rates at the same pressure for the same propellant at two initial temperatures one could calculate T. Another frequently used relationship is r = b"P4\T, - Tu) (34) where b" and и are constants and T, is a refer- ence initial temperature. A linear relationship has also been noted.** The existence of regions of nega- tive temperature coefficient described above is not consistent with either of these relationships, so the effect of propellant temperature on linear burn- ing rate remains largely an empirical relationship. In the SPIA/M2 data sheets four temperature coefficients may be found. Of these ths tempera- ture coefficient of burning rate at constant pressure, v, = 0^^» 1» estimated from the rate-pressure curves (Figures 3, 4 or 3) using the inters ?tions of the curves for the different temperatures with a vertical line at the constant pressure of interest. 14
Япсе for a real rocket motor the working ргаяпе b not the same at different grain temperatures, thb parameter does not haw real ognificance. The tcoq*eramre coefficient of burning rate at coa- rtant К value, b determined em- pirically by static-firing rocket motors at dhferent grain, temperatures and dividing the known web dbnensions by the burning timer to get the rates Since neither the boning turface nor the nozzle throat area rhsngri appreciably with ambient temperature^ the assumption of constant К wine between rocket motors of the same design at «ef- ferent temperatures b good. The temperature co- eiBcbnt « premnre at coratant * wine. <2 = b determined from the rate-pressure curves, using the intersections of the carves for «по шпеган шфсвпшпо wim о шкв wncn J> are Horn of constant In real rocket motors the p assumption of constant ~ with changing tempera- tare b better than the assumption of constant pres- sure, but thb parameter still has only qualitative wine. The more significant temperature coefficient of pressure at constant К value, »< s0£f)x’ again determined empirically by static firing at dif- ferent ten^eratures. AH Tbur of there parameters are expressed in units of percent per degree, usually Fahrenheit. Low values of there coefficients are desirable. M. Cffisct st рв vsfiadty. Krnrive hurah* When burning occurs inside tubes of propellant such m the perforations of gun propellant and the interior suttees of rocket propellant, it b found that the Haear burning rate at and near the exit of the tube exceeds the normal rate. The shape of the “eroded” region suggests a velocity effect, and indeed the erosion law may be written г = ЫЧ1 +«x£) (35) whore V is the local gas velocity in the tube and C b the velocity of sound fas the combustion prod- ucts. In the care of a stagje mternal-buniing rocket grata ta a rocket*' motor, VA, = CA> where A, b the “port area” or the exit area of the tube and At b the nozzle throat area, so Equation 35 ticcoows r=W41 + Xi;£) (35a) which b in a more convenient form foe use by rocket designers. The constant Kj b called the “erosivtty constant and b a measure of the sus- ceptibility of a propellant to erosion. Itr value b of the order of 0.5 to 1.0. Equation 35 wfl! be recognized ss a linear TT""1*"”**"". applicable over the range of gas velocities for which the con- stant St has been developed. A theoretical treat- ment of erosion** has been breed cat the transition front laminar flow to turbulent flow of the com- bustion products within the perforation. An erosive bunting law ^ = *'* + ^£в (ЭД has been developed*1 from ecnsideratioc of heat transfer to the propellant walls from rite hot gas passing down the perforation. In thb equation, a and 3 are constants characteristic to the propd- tante binned, G is the mass velocity of the gases in the port, and L b the distance downstream from the stagnation point 9-4. Effect of cocsposiflaa. As the driving force for the burning of propellant is the temperature of the combustion products, all theories agree that hot propellants should have a higher linear burn- ing rate than cool ones. This b found quite gen- erally true at gun pressures and also at rocket pressures where the rate-pressure relationship b “normal.” Thb b a matter of no more than aca- demic interest to the users of gun propellants who do not have the problem of reconciling grain geometry to charge envelope requirements. In rocket design on the other hand, where, in gen- eral, single grains are used, it b necessary to be able to control burning tenqteratnres and rates independently in order to meet simultaneously per- formance and envelope requirements. To thb and rocket compositions quite commonly contain addi- tives known as burntag rate catalysts which gen- erally increase or decrease the normal burning rate of the propellant. The choice of catalysts and their proportions in the composition are deter- 15
mined by experiment. Temperature coefficients and erodvity constants are also properties of the compositions. M. Bendtsg rate of composite prupeBsate. A composite propellant has been defined as a solid propellant system comprising two or more solid phases intimately mixed. In all important cases, with the possible exception cf black powder, one of these phases is continuous and foams the matrix or binder in which the other phase or phases is dispersed. When a composite propellant burns, the burning surface comprises a web of binder filled with exposed surfaces of filler material Each ex* posed material burns at its own linear rate at any given pressure and starting temperature and has its own pressure index and temperature coefficient. A perfect match between die burning rates of binder and filler would be a coincidence, and easily disturbed by a c’tange in burning pressure. In gen- eral die filler surface wffl recede faster or slower than the binder, giving rise to an irregular and time-dependent boundary between regions C and D. Figure 6 shows die case of filler burning more rapidly than binder. Area I shows a filler particle not yet exposed. Area П shows a filler particle par- tially burned, while at Area HI is a pocket left by a filler partide completely consumed. The net effect cf the foster-burning filler is to increase die instantaneous burning surface of the binder. We can no longer measure the burning area, only its projection on a plane parallel to die original burn- ing surface. By increasing the actual burning area, we attain a greater apparent linear rate, referred to the projected area. In spite of the lower apparent burning rate of the binder, the burning rate of the composite propellant approaches the linear rate of the fest-burning filler. The case of filler burning more slowly than binder is shown in Figure 7. In Area I we have again a filler psrtkle not yet uncovered, in Area U a filler particle bunting at a slower rate than the surrounding binder, and in Area III an incom- pletely burned filler particle completing its com- bustion in the gas phase outside the piece of propellant. In thia instance the linear bunting rate of the composite should approximate that of pure binder. As the linear bunting rate of the composite tends to follow the burning rate of the faster-bunting phase, it is to be expected that the temperature eiMoea Qgg eiixea EWSI Figure 6. Burning of CoapatHt Propellant— Filer FalrFmtrt Thon Binder Figure 7. Burning of Composite Propellant- Filler Rote Slower Than Binder coefficient and pressure index should also tend to follow the corresponding figures for the faster- burning phase. L. a two-phase filler-binder composite various combinations of monopropellants, fuels, and oxi- dizers are possible. If both binder and filler are monopropellants, region D is all combustible mix- ture, although of a mixture of compositions. If the binder is a monopropellant and the filler is either oxidant or fuel, region D is a continuum of com- bustible mixture containing pockets of fuel gas or oxidizer gas, and a diffusion, process as well as heating must occur in region E before the com- bustion reactions can be completed. If the binder is fuel or oxidant and the filler is monopropellant, region D becomes a continuum of fuel gas or oxi- dizer gas containing pockets of combustible mix- ture. If the binder is fuel and the filler oxidant or vice versa, region D contains no combustible mixture. A diffusion step is required to mix the fuel-rich 16
gat with oxidizer-rich gat before the reactions to produce the flame temperature can be completed. With larger filler particle size the distance either gas must move to accomplish diffusion is longer and, therefore, the distance between region D and region F should be greater than with smaller filler particle size. This may explain qualitatively the observed slower burning rates of fuel binder com- posites with large filler particle size. The requirement at a diffusion step before a combustible continuum is achieved is no essential handicap in a burning regime. It is interesting to note, however, that propellants with this require- ment propagate detonation in the solid less readily than do monoprcpellants. The preceding discussion of the burning rela- tionships applies to steady state burning and assumes no pores, cracks, or fissures with com- ponents perpendicular to die burning surface. Two important problems are recognized in connection with burning. 94. Problem of Mutable bontng. For as long as modem rockets have been under investigation in the United States and undoubtedly earlier else- where, some rockets have exhibited a tendency to develop irregular pressure peaks at some time during their burning cycles. In severe cases this has led to rupture of the motor chamber. With pressure-time instrumentation of suffidently low time constants these pressure irregularities have been shown to exhibit frequencies identified with axial, radial, and/or tangential vibration modes of the burning cavity. In separate instances the phenomenon has been overcome by “resonance rods”4* placed inride the grain perforation, radial holes4' through the web, slots4' or baffles4’-44 within the grain, and most recently by adding small quantities of finely-divided aluminum41 to the composition. In each case a “quick-fix” has been accomplished but no real explanation has been given for the phenomenon. Considerable light has been shed very recently on this question by the appreciation that the propellant grain does not behave as a rigid body but has acoustic properties similar to those of the gas in the burning cavity.” 9-7. ТишаШоп from deflagration to detonation. With the advent of very large, high performance rocket engines the question has been raised whether and under what circumstances a rocket motor can proceed spontaneously from a burning regime to detonation. This question has been and is being investigated intensively. It is presumed that burning can give rise to shock and that the shock thus produced can occa- sion detonation in the propellant. That continuous monopropellants can be detonated by shock has been well documented.4'-4T The necessary condi- tions are that the shock intensity be sufficiently great and that the propellant be present in cross section greater than its critical diameter. That burning of a properly consolidated rocket grain can give rise to shock has not been demonstrated. A theoretical study4' indicates that only when die pressure rises exponentially in a few microseconds to several thousand atmospheres can coalescence of pressure waves give rise to shock as a result of burning. In an improperly consolidated propel- lant, on the other hand, with regions of inter- connected porosity it is comparatively easy to attain a condition of shock which win result in detonation. Unfortunately much of the literature which purports to study die transition from def- lagration to detonation actually reports studies of the transition from shock to detonation.41 19. Prop i flant grain- A single piece of propel- lant is known as a grain. The exposed portion of the grain surface at any time during burning is the burning surface, floaty portion of the surface which is covered by adhered nonbuming material is in- hibited. The shortest distance, normal to a burn- ing surface, that the grain bums until it loses its structural integrity is the burning distance. The thickness of the propellant wall so consumed is the web. If a grain burns on only one side, as is the case with case-bonded or otherwise inhibited grains, the web is equal to the burning distance. If two parallel surfaces burn toward each other, as in uninhibited single- at multiple-perforated grains, the web is twice the burning distance. The relationship between web and burning distance is thus not single valued. The dimensions of the grain taken collectively are known as the granulation when referred to multiple-grain or bulk charges, or as configuration when referred to a single grain. A grain that maintains its burning surface con- stant, or approximately constant, during burning has neutral geometry. Simple neutral geometries include sheets, squares, or disks with webs small compared with surface dimensions or with edges 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 burning surface is {dotted against fraction of web burned for several geometries in Figures 8-14. The portions of the grain remaining at burn-through, shown shaded in § e 8 8 S 8 2 FRACTION OF WEO BURNED A, LORO TORE, ENO-INNIOITEO TORE, RMEET. CNO-OURNCR A. IMORT TUOC. WEO 0.1 LENRTN. ITR1F VII • 0.1 WIDTH C. 01 OR, WEO* 0.00 DIAMETER lUCIRVNRNMR IRNIt Figaro 11. Slotted-Tube Grain FRACTION OF DISTANCE OURNCD A. INTERNAL OURNlNO TUBE, PERFORATION o>AM Figure 12. Progrnuhf* Gaomatry Figure 9. Natural Geometry Figure 9. Pad and SMI Grain 18
• 1.1 НКПМ «MttMt Ht*i Figun 13. Muliipli/trftrattd Cylinder Figures 10 and 13 are known as slivers. The terms neutrality, progressivity, and degres- sivity are also applied to the weight burning rate, W. Since W is proportional to both linear rate and burning surface, factors affecting the rate can affect the progressivity just as well as can geo- metric factors. In this sense a dual-composition grain in which the first composition exposed bums more slowly than the second can be progressive in spite of a degressive, geometry. Such grains are used for small arms charges. The slow-burning outer composition is created by coating or apply- ing a plasticizer to the outside of the grain and causing it to penetrate only part way through the web, leaving the interior of the web unchanged. Dual-composition grains may also be used in rockets to create a boost-sustain situation. In this case the fast-burning composition is first exposed and the slow-burning one later. Erosive burning is sometimes used to speed up the early burning of a normally progressive geometry and attain essen- tially neutral burning. Finally, pressure changes that affect the rate contribute to progressivity. In this sense all closed bomb burning is at least initially progressive, regardless erf geometry, and burning of a progressive or degressive geometry in a vented vessel is more progressive or degressive than is indicated by the geometry. IL SchedaBug of mans sate. Let us now con- sider some of the operating cycles for engines in which propellants are used. 11-1. Gu. The pressure-time relationship in a gun it 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 erf the projectile travel the quasi- constant volume of the burning chamber permits 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 addition of volume has caught up with the rate of generation of gas, and the pressure has attained its maximum value. The remaining portion of the propellant is consumed at decreasing pressure, after which the gases expand adiabatically until the projectile leaves the muzzle. The entire cycle is accomplished in a matter of milliseconds. The gun cycle can be fairly precisely analyzed, but the analysis is complicated and requires ma- chine calculation. It is obvious that the mass rate of burning is very high and that the propellant must have either a very high linear burning rate or a very large burning surface (Equation 30). Be- * ceso В STHSM, CUM Flgvru 1-4. Deprauhra Geometry 19
MCMVM FISSURE -TMVKL RSLATIOHSHIP HI • UN MtCSaUM- TIME Ktl*riMSHI> • •UH Ндип 15. Gun Cycfo burning rates, even at gun pressures, we are left with the requirement of a very large surface. The geometric problem of accommodating a charge of very lar je surface in the gun chamber or cartridge case is very much easier t^ solve by breaking up the charge into a number ot grains than by beep- ing it in one piece, and we find gun propellant charges are indeed multipte-trrain charges. In Europe where charges are hau> loaded, gun pro- pellant charges are often made up of long strips or cords approaching the full length of the car- tridge case. In the United Stater where charges are machine-loaded, the shorter single- and multiple- perforated cylinder form is preferred. Geometric progressivity is not vital; guns have been quite successfully fired using degressive cord charges. There are, however, marginal advantages to pro- gressive or neutral burning geometries which tend to shift the position of the peak pressure to a later time and, therefore, to a larger burning volume than when a cord-form charge i used.. The practice in the United States in designing a propellant charge for a new gun or in designing a new propellant charge tor an existing gun is to select a propellant composition on the basis of its force, F, and flame temperature, T„ and estab- lish the optimum granulation empirically. Having established a given lot of profellant as the stand- ard, additional lots that are manufactured must match the standard by actual comparison firing in the gun. For quality control purposes, firing in the closed bomb (Figures 16 and 17) can yield a rela- tive quickness, RQ, along with the relative force RF (see Paragraph Я-2). In this determination jp the bomb is instrumented to record directly versus pressure. The test propellant is fired in comparison with the standard propellant, and RQ is determined" as the ratio of for the test 4м propellant to for the standard at one or more pressure levels. 11-2. Catapult, The function of the catapult is to accelerate a load attached to a piston to a final velocity without exceeding a maximum accelera- tion. The ideal catapult should operate at constant pressure to afford constant acceleration. 1Ъе ideal travel-time curve for the catapult is shown in Figure 18. The same curve may be.used to show the volume of the burning cavity and the required progressivity of the charge. It may be observed not only that an extremely high progressivity is required, but that die required progressivity is not linear. For personnel catapults there is an added requirement that the rate of acceleration, d, (jerk) not exceed a specified value. This sets an upper limit on the slope of die rising portion of the pressure-time curve, Figure 18. Catapult grains may be designed in the form of multiple-perforated 20
Figurt 1& Closed loflb Assembly |M«M И|ЖМН«1 ДТ FM« MClMtKt MB yolii *bc«iu*c FlgvM 17. CImm/ tomb Record 21
cylinder! inhibited externally, or rhomboid prism burning from the corner edges, A fuller treatment of the baDiirtics of the catapult is given in reports by the Atlantic Research Corporation.’1 11-3. Rocket motor. The design requirements for a rocket motor propellant charge usually call for burning at a constant mass rate equal to ibe 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. 11-4. Cakuiattoa of a socket peepsBant charge- A rocket motor is required to maintain an average sea level thrust of 2C00 lb for 20 sec at a design operating temperature of 70°F. The total impulse, I, required is 20 x 2000 or 40000 Ib-sec. At thia point in the design a propellant must be selected. For this etrngk, OIO propellant (see SPIA/M2) which has the following characteristics is chotcn* — 212 ib-sec/Ib at 1000 peia and optimum otpanaiM CD = 0.00741 у = 1.25 r = 0.27 at 1000 peia and 70®F , = 0.0557 Ш/in» A chamber pressure is now chosen in the re- gion of plateau burning of the propellant, ao that changes in the burning surface of the propellant win саше only minimum variations in pressure and thrust The pressure selected is 1000 pshu Because of best loss to the rocket urntor and other inefficiencies, a delivered specific fanpulse with optimum expansion of 95 percent of the theoretical specific impulse is assumed. The weight of propellant required is W ~ = 212(095) = 198,5 ,b The weight flow rate is = ~ = =9.93 Ib/sec At a chamber pressure of 1000 peia Al Ct?' ” (0,00741X1000) ~ 1,40 in or D, — 1.34 in Ting Figun 19. flecket Meter Cycle 22
The optimum eiptmnwi ratio of obtained own the Thrust Coeffidont and Expansion Ratio Tobits" is found to be 8.4:1. Therefore Л. = 8.4(1.40) = 11.75 in1 , D, - 3.87 in The average propellant surface during burning is ^ = ^’^fe?)=659inl If a nearly neutral thrust is desired, then the sur- face during burning should be as constant as pos- sible, Lt., S< = Sf = The propellant burning distance is equal to rt, = (017X20) = 5.4 in At this point some type of grata design, such as a star-type, slotted cylinder, cruciform, rod and tube, etc., should be initially chosen. The design requirements can be met with a slotted cylinder. An important parameter in grata design is the ratio of the port area in an internal burning grain to the nozzle throat area. For this illustration the port-to-throat ratio is set at the minimum of 1.5:1 to prevent erosive burning of the grata.* Therefore the port area Л,^ = 1.5Л, = 15(1.40) = 2.10 in» The use of a minimum port area will result in the smallest possible space envelope for the rocket motor. With a port diameter of 1.64 in and a burning distance of 5.40 in, the outer diameter of the propellant is 12.44 in. The volume of propel- lant required is .. IT 198.5 ,<xn. . V* = f “ 0.0557 ~ 3560 Ш The required grata length is approximately r 3560____________«o . . (0,7ЙХТ144* - 1.64») ~ “ •la mors KpbhticaMI d«si|a work tbs potHMhroat ratio fraqtwally is cbossa м low м 1:1, accepting srosivs bwatas. la the early WagM of burning (until the port-to- throat ratio squab 1.9), a portion of the propaUaat will buns at a bipksr rata than normal for the «tasting pres- euro, and the grata geometry must compensate for this. The dsdgn grobteaa beseem thus more dffleult, but by п» пивав iingoMlbto. Continuing with this design, the surface area with- out slots and with the ends of the grain uninhibited, is S = 2 (~ )(OD» - ID*) + «(WML) = 2(0.785X12.44» - 1.64») + 3.14(1.64X29.8) = 393 in» The surface of die slots is therefore S^. = 659 - 393 = 266 in» Using four slots at 90°, 5.40 in high, and 0.10 in wide, the slot length becomes “ 8(5.40) ~ 615 m Disregarding the void volume of the dots for the moment S, = 3.14(12.44X29.8 - 6.15 - 5.4) = 714 in» Within die accuracy of the calculations this design appears slightly progressive. The volume of the skits is Kw, = 6.15(5.40X0.1X4) - 13.3 in» and the actual propellant length is 13 3 L = 29 8 * (0.785X1^-154») = 29 9 " In an actual problem the design should be cheeked for undesirable variations of burning sur- face by plotting the calculated burning surface as a function of burning time. Final verification ct die design would be accomplished by fabrication and static test of the grain. While it is comparatively easy to design a rocket grain to fit the performance requirements of a design problem, it is often quite another thing to fit the grain into the required envelope. Where a gun charge designer can select a propellant com- position and determine the proper granulation, a rocket charge designer is often forced by envelope requirements to start with a grain geometry and develop a propellant composition to give the re- quired burning rate. For this reason there are nearly as many active rocket propellant composi- tions as there are rockets. The propellant geom- etries and significant performance parameters of 23
most solid propellant rocket mcton used by the United State» military services are summarized in the SPIA Jato Manual." 11-5. Gm isMatar. Gas generators arc re- quired to provide for a certain duration (a) a spe- cific volumetric flow rate, or (b) a specific mass flow rate, or (c) a specific gas horsepower. In addi- tion, a maximum gas temperature is usually speci- fied, and the exhaust gases from the propellant must be dean । 11-4. CaicnWMGtagMgsneratar propafimtt charge. Assume a gas generator must be designed to provide 20 gas horsepower for 30 seconds. The maximum allowable flame temperature, T„ is 1900°K. OGK propellant (see SPIA/M2), which meets the temperature requirement, has the fol- lowing characteristics: у = 1.25 T,= 1888’K = 3398°R = 0.04576 moles r = 0.28 in/sec at 1000 pda p = 0.055 Ib/in* If the nozzle exit pressure is 50 pels, substituting in Equation 5 20 =~ x X 1543 X 3388 x [JLU*] / 50 \i a» I !-(w J W = 0.0254 Ib/scc Using a singie-cnd burning grain design s = ~ = /n&Vnnw = 1,63 гр (и.2вди.0ээ) The propellant diameter is 1.45 in. The propellant length is L = rh = (0.28 x 30) = 8.4 in If a certain mass rate at flow is required, the design proceeds as above. If a volumetric flow rate is defined, this can be converted to a mass flow rate by using a variation of the perfect gas law H = 07) MHRBKK 1. J. Comer, Theory of the Interior Ballittiei of Guru, p. 101, John WBey t Soa, Inc., New Yet*. New York, 1954 2. Allegany Ballistics Laboratory, George Washington University, Jtodter ГмАммамЬ; ABL-SB4, OSBD 3992, 1944 (SPIA Abstract No. 0574B). 3. M. Barrens, A. Laumotte, B. F. DeVeubeke and J. Vandeakerckbove, Hocket РгораЫоп, Elsevier Pub- lishing Company, In&, New Yost, New York. i960. 4. J. Cotner, toe. eb. 5. C. Cram, Innere Mfadi (JLehrbuch der BaHUtik, Bd. 2), Jahns Springer. Berlin. Germany, 1924. 6. F. B. W. Hunt, Editor, Internal BalUtfice. Phfloeophi- c»J Library, Inc„ New York, New York, 1931. 7. G. P. Sutton, Docket Propuldon Clemente. An Intro- duction io ike Entineerinp of Hockett, 2nd edition, John WBey A Sons, Inc., New York. New York, 1956. a. R. N. Wimprees, internal Balliatia of Solid-Fuel Hockett,. ЛИШагу Hockett Udng Drf-hxuml ОшМе-Ввев Propellant at FmL McGraw-Hill Book Company, InCn New York, New York, 1950. 9. M.Bamre,eroL,foc.cir.,p.9S. 10. Allegany Ballistics Laboratory, Georgs Washington Univcrmy, loc. cit., p. 24. 11. F. D. Bosdni, D. D. Wagman, W. К Evans, S. Levine and L Jaffa, Selected Faber of Chemical Thermo- dynamic Propertiee, Circular of the National Bureau of Standards 500, U. S. Government Printing Овсе, Washington, D. С, 195X IT S. L. Levy and O. A Reynolds, Hocket Propellent Performance Computations Program for the IBM 620 Computer, Allied OSvnical Corporation, Gen- eral Chemical Division, 16 May I960, Contract DA-300690ED-263S. 13. T. O. Dobbins, Thermodynamic! of Hocket Proptd- rion and Theoretical Evaluation of Some Prototype Propellant CompotUone, WADC ТЖ-59-757 (Proj- ect 314SX Wright Air Development Comer, Dayton, Ohio, December 1959. 14. Joint Army-Navy-Air Force Л4 Hoc Panel on Per- formance Cakufartioa Мейк.ч* > and Thermodynamic Data, Bulletin of the Second Meeting, 27-19 April 19S9, PCMTD2, Solid Propefiaat ^formation Agency, Applied Physics Laboratory, The Johns Mcpkins University, Silver Spring, Maryland, CON- FIDENTIAL. 15. 7. O. Hirschfclder and J. Sherman, Simple Calcula- tion of Thermochemical Properttee for Ute in Bal- Uuict, NDBC A-101, OSBD 935, October 1942, CONFIDENTIAL (SPIA Abstract No. O3O3A); Ibid., NDBC A-101 (addenda), OSBD 935 (addenda) (OSRD-1300, A-67M-A-70M), Match 1943, CON- FIDENTIAL (SPIA Abstract No. O3O3B). 16. p. de Pauw, ‘Die Verbraanungswinne des rauchlosen Pulvers," 2. gee, Schlett- a, Spratpemgu., 32,10,36, 60(1937). 17. A. O. Dekker, "Bapid Estimation of SpocMc Imputes of Solid Propellants," Jet Propuldaa, M, 572 (1954). IS. Allegany BaBistics Laboratory, George Waabingtaa University, loc. cit„ p. 274. 19. Allegany Ballistics Laboratory, Georgs WashtaWoa Uoivenity, foe. efr^ p. 275. 24
20. Allegany Ballistic* Laboratory, Hercules Powder Смвриу» uepubUAcd d*tia 21. C A. Oriick and A. M. Jacobs, The ABL Procedure jet Calculation of the /.» of Propelianti Which Yield о CondeiuMe Exhatut Product, Allegany Ballistics Laboratory, Hercules Powder Сопфапу, ABL/X-34, March 1959, Contract NOrd 16640, CONFIDEN- TIAL (SPIA Abstract No. 19064). 22 J. Сопит, toe. ch., p. 12». 23. Vtmtotorf UuMi and Procedure» for the Determi- nation of Real of Expiation of Rocket Propellant Powder», Navy Department, Bureau of Ordnance, NAVORD OD 9375, 8 June 1953 (SPIA Abstract No. 13,318). 24. Amy Service Forces, Proof Directive 12, 3rd revl- atoii, 12 February 1946. 23. Joint Anny-Navy-AIr Force Solid PropeDant Rocket Static Tact Panel, Description of Static Тем Facilitiet at РоМреЛч OrganitatioM, CONFIDENTIAL, Solid Propellant Information Agency, Applied Physic» Laboratory, The Johns Hofkim University, Silver Spring, Maryland. 26. F. A. Warren, E. L, Anderson and F. M. Ku, Evnte- atton of Solid Propellant Propertie». Part I—4 Survey of Current Method», Southwest Research Institute, Report RS 217, 31 January 1959, CONFIDENTIAL (SPIA Abatract No. 19191k 27. F. J. Malina, "Characteristics of the Rocket Motor Unit Baaed on the Theory of Perfect Gases," J. Frank- lin In*.. 23B, 433 (1940). 2». H. S. Seifert and J. Crum, Thnut Coefficient and Ex- pansion Ratio Tablet, Remo Wooldridge Corpora- tion, Guided Missile Research Division, 29 February 1936 (SPIA Abatract No. 17368). 29. H. Muraour, "Sur lea Iota de combustion des poudrea colloldaiea. 3* note," Bull. toe. chim. France, 41, 1431 (1927); ibid., "Sur les toh de combustion det poudrea coUoIdaies. 4* note,” Butt. toe. chim, France, 47, 261 (1930); ibid., "Sur une thforie de la com- btttttos, ea vase ctoa, des poudrea coUddaW,” Compt, rend., 192, 227 (1931); H. Muraour and W. Schu- macher, "La vitesse de combustion des poudrea col- toldales sous la pressioo atraospMrique,” Шт. poudret, 21, 87 (1937). (Summarized in J. Corner, toe. elt., pp. 43-3.) 30. B. L Crawford, Jr., C. Huggett and J. J. McBrady, "The Mechanism of the Burning of Double-Base Pro- pellants," J. Phyt. Chem., M, 134 (1930). 31. Piobert, ТгаЫ JAriUlerie. 1839 as cited in J. Taylor, Solid Propellant and Exothermic CompoMoru, p. 56, latersdence РиЫШт, Inc., New York, New York, 1939. Г 32. I. Taylor, Solid Propellent and Exoihcrmlc Compotl- tiotu, p. 36, Intersctonce Publisher», Inc, New York, New York, 1939. T 33. M. Summerfield, Burning Maehanltm of Ammonium Perchlorate Propellant». Part ll. Theory of Burning of a Composite Solid Propellant, paper presented at American Rocket Society 13th Annual Moating, 17-21 November 1^5», New York, New York. 34. J. Corner, toe. elt., 9.71. 1 I / 25 35. W. H. Avery, R. E. Hunt and M. N. Donis, Burning- Rate Studiet of Double-Bate Powder, АПецшу Bal- lisucs Laboratory, George Washington University, ABL/P-1, OSRD 3827, January 1946. CONFIDEN- TIAL (SPIA Abstract Na 0314); S. Zmachhuki and IL F. Preckel, Strand-Rale Ballistic Studiee of Pla- teau-Type Propellant!, Hercules Powder Company., ABL/P-13, December 1948, Contract NOrd 9709, CONFIDENTIAL. 36. Allegany Ballistics Laboratory, George Washington University, toe. elt., p. 43. 37. J. H. Godsey and R. F. Preckel, Strand Rate Ballistic Studiet of Plateau-Type Propellant*. Part IV. Char- actertttiet of Vartout Battiitie Modifier», Allegany Ballistics Laboratory, Hercules Powder Company, ABL/P-25, April 1933, Contract NOrd 10431, CON- FIDENTIAL (SPIA Abstract No. 15409). 38. J. Canter, toe. elt., p. 73. 39. F. T. McClure, R. W. Hart and J. F. Bird, Solid Propellant Rocket Moton at Acouttk Otciilctori, Applied Physics Laboratory, The Johns Hopkins Uni- versity, Report TG 335-3, 5 October 1959, Contract NOrd 7386. 40. J. Corner, “The Effect of Turbulence on Heterogene- ous Reaction Rates," Trant. Faraday Soc., 43, 635 (1947). (Summarized in J. Comer, Theory of the In- terior Ballittict of Gum, p. 74, John Wiley A Sons, Inc., New York, New York, 1950.) 41. Rohm A Haas Company, Redstone Arsenal Research Division, Quarterly Progrett Report on Interior Bal- ilttict, Report No. P-54-9, 15 April-15 July, 1954, Contract W-01-021-ORD-334, CONFIDENTIAL (SPIA Abstract No. 14391); G. Robillard and J. M. Lenoir, The Development of a New EroAve Bunting Law, Jet Propulsion Laboratory, California Institute of Technology, Bulletin of the Thirteenth Meeting of the Joint Army-Navy-Air Force Solid Propellant Group, Vol IL p. 441. CONFIDENTIAL, Solid Pro- pellant Information Agency, Apr ’led Physics Labora- tory, The Johns Hopkin» Univ, rity Silver Sprfag. Maryland. 42. A. L Antonia Development of Intermd-Bumlng Solid Propellant Rockett, Aerojet-General Corporation, Aerojet Report L3O32/35-2, 16 November 1930. CONFIDENTIAL (SPIA Abatract No. 10731). 43. Я. P. Smith and D. F, Spreagsr, Development of tniemal-Buming Solid-Propellant Racket», Funda- mental Studiet of Umaable Burning of Aeroplox Pro- pellanit, Aerojet-General Corporation, Aerojet Report 606 (Final). 4 Jnne 1952, CONFIDENTIAL (SPIA Abstract No. 12189). 44. и. E. Mitas, Jnvesrfparton of Vtutable Вахонине» Burning, Allegany Ballistics Laboratory, Htrcutos Powder Company, ABL/MPR 46 (p. 7 of Monthly Progress Report 46), I August 1953, Contract NOrd 10431, CONFIDENTIAL (SPIA Abstract No. 13532). 45. R. L. Lou end R. C. Kriger, Effect of Chemical Addi- tive» on Uнмable Burning, Aerajst-General Corpora- tion, Aerojet Report L27M-18, -19 (16 October-15 December 1937), 10 January 1937, Contract NOrd 16979, CONFIDENTIAL (SPIA Abstract No. 18.003).
44. V. РкШрскак, DwMoRnar Cwt Ptopdtaat, Аяте» meat of Fire «nd КярЫоо КвяягА йяНЧ Шяя/чс- Un, Naval Previa* Gnoond, Report IM, 11 Ancuat 1951, CONFIDENTIAL (SPIA Abetmet No. 11162X 47. Rohm A Hau Company, RodNoae Araenal Reaoarch Diviaion, Qearterip Ргв/чн Report oo hutrior ЛА- Hrike (April IS, 19S6 to HAp IS, I9S9-, Report No. P-56-14, io Aucuat 1154, Contract W41-42I-ORD 314, CONFIDENTIAL (SPIA Abairact No. №32); Ibid., J. R. Hyndman, W. W. Brandon, H. M, Shuey, IMfafraflon-DraoMNiM ЗиЛяя of Solid РгореЛмАя, Bulletin of the Т»еЖк Moatia* of the Joint Army- Navy-Air Force Solid Propellant Group, VoL Ц. p. *9, CONFIDENTIAL, Solid PrapoihM Infocmatioo Apency, Applied Phyaica Laboratory, The Jobae Hop- kiw Unhweity, Saver Spriae. MaryiaanL 43. л. Масок, "ТгаоаШоа from DoSamattoa to Detona- Пов in Chat ЕцрШма,” J. Chtm. Ркря^ 31, i<2 (1959). 49. S. J. Jacobo, "Reccat Advaacm in Ooodeawd Medfa Dotomttoaa,” XJU ЗоалмГ, 3% 131 (1Мф. SR L. E. Smith. Ju C, S. hemm and T. WMah, Rd- Kt*> Teri МяИ»Ля-С1ояяЛ ЯвяЛ Teri VeriMee. A Iririe» of Proof Directive 13, Srri lUririoo, Petr» orp 13, №ff, SmaSownr Ordnance Worka, Horadoe Powder Company, • July 1939. 31. M. L. Rioe, I. HnB, B. Watea and A. C. Scarlock. A Stirip of РгореВвм Chorpe Raialwmtnw foe the С-10 СвяяреЛ, Atlantic Raoearch Corporation, No- wtobor 1932, Contract NOrd 10721, CONFIDEN- TIAL (SPIA Abatract No 13Д37); M. L. Rica, T. Dnvie aad A. C Scutfock, A Cotoporieoo of Rtaam unit PooAer СеяеоиЬя. Inly 1934, Contract NOrd 10721, CON 1*'»N 1AL CSPU Abetract No. IA4Q3). 32. hrio Maud Vohutte 1. Berfy Eeperiottofol leto Volte, Solid Propellant Information Apeacy, SPU/M1. CONFIDENTIAL; Roefat Motor MmmwL Fofaaie 11 (of Joto МапмО. Vrite of Correiri liter- ett, SPIA/M1, CONFIDENTIAL, SaUd PrapdBant Inform otinu Араму, Applied Phyaka Laboratory, The Мив ЯорЫм UMwn^SRavr Sprinp, Merytaad. 26
СНАРПЯ 3 PHYSICAL PROKitTIRS HQUIRUMMTS 12. Gtuml. Jut as propellants have different ballistic requirements depending on the uses to which they are put, the physical properties re- quirements of propellants will be different depend- ing on use. 13. Density. Since in a solid propellant heat engine the propellant is always contained within the engine, the propellant must have a density high enough that the charge can be so contained. Two factors enter into the determination that the charge will fit into the chamber: the density of the pro- pellant itself, and the volumetric efficiency of the charge geometry or the fraction of the propellant envelope occupied by propellant. The density of a propellant is calculated .from the densities of its ingredients, assuming.no volume change 11 a result of mixing. <’«> In the case of я propellant undergoing chemical reaction during the mixing operation, as is the case of many fuel Under composites, the ingredients indude the reaction products (e.g., polymen) and not the reagents actually charged (monomer). In the case of a propellant manufactured with in- clusion of a volatile solvent later substantially removed, that portion (residual solvent) of the advent remaining in the finished propellant must be considered an ingredient. Density can be measured with a mercury dis- placement volumeter* or with a pycnometer* or, more roughly, from the weight and dimensions of the grain. Comparison of the measured density with the calculated value gives a measure of poros- ity, cracks, and fissures in the propellant Micro- scopic individual pores, as around crystals in composite structures, have no apparent effect on the burning of the propellant, but cracks and fis- sures constitute undesirable burning surface that cause excess pressure and interfere with the sur- uled maxi burning rate, and interconnected gentry porosity can lead to detonation. In monopropei- laats measured density is usually very dose to calculated density. In composites a difference of more than 2 percent indicates trouble. 14. Cravlmefrit dsarity. Gravimetric density ф measured on bulk gun propellants as the weight of propellant required to fill a specified con- tainer when charged at a specific rate from a hopper at a specified height.* (The density of pro- pellant as loaded into cartridge cases can also be determined.*) This datum is influenced not only by density and dimensions but by the smoothness of tire sur- face and the presence сиг absence of tailings from die cutting operation. It is used as an indication 'that the required charge weight can be contained in die cartridge case. Iff. Hygroscopicity. Most propellants contain constituents that are hygroscopic and this property is passed along in some degree to the propellants. The mechanism of sorption and desorption of hygroscopic moisture probably involves a rapid attainment of the equilibrium, dependent on rela- tive humidity, at the surface of the grain, followed by slow diffusion within the grain. The effect of hygroscopic moisture is the same as if die formula contained the same fraction cl water. Hygroscopicity of propellants for cannon is de- fined as the equilibrium moistuu content at 90 percent relative humidity and 30°C temperature. For small arms propellants hygroscopicity is de- fined as the difference between the equilibrium moisture contents at 90 percent relative humidity, 30 °C temperature and at 20 percent relative hu- midity, 3O°C temperature. The procedure for small arms propellants* involves successive exposure of the same sample to controlled humidity atmos- pheres, whereas for cannon propellants* a single exposure and a chemical analysis for moisture are required. Hygroscopicity of propellant charges loaded in engines has been controlled by hermetic sealing of the engine or its shipping and storage container, or by loading a desiccant either into die engine or the shipping container. Hygroscopicity of indi- vidual grains has been minimized by formulating to a minimum content of hygroscopic material and in the case of coated grains by building a layer of material of low permeability into the surface of the grain. 27
xti. Ceefoefauf ef thuaai еарммйп. At the level of about 10~4 per degree C, the thermal ex- pansteu coeflldcot is of Httie moment to multiple- grain charge*. Fur single-grain charge* loaded into chamber* at small clearance*, care Bnul be taken to verify that the clearance* between grain and waQ do not disappear in th* upper range of stor- age or firing temperature* became of die different expansion coefficient! of propellant and chamber material. In tiris event the chamber wall would exert stress on the grain earning it to deform or even fracture. If the grain is enclosed in a rigid inhibitor, the coefficients of the-grain and inhibitor should match as closely as possible for the same reason. If the grata is to be case-bonded to the chamber, it is not ordinarily feasible to match the expansion coefficients and the grata must be formulated to accept the stresses due to differen- tial expansion. 17. Thermal eearitactivity. Propellant* are in general very poor conductor* of heat This prop- erty is a useful ccr for ballistic design, as it can be safely assumed that the unburned portion of a grata will remain at it* initial temperature through- out the combustion process. On the other hand, in a large grata the time required to bring dm propellant to a uniform temperature following a change of environment may be several hours or «ven day* depending on temperature differential, air circulation, and grata she. If the grata is fired while it contains a temperature gradient, the rate of gas production will reflect the temperature gm- dient Thermal stack from too rapid change from very cold to very warm or vice versa may lead to cracking of the grain. The interior of grain* stored in munitions in hot climates foils by a wide margin to attain the maximum diurnal temperature».’ 1*. Mechanical prepertiv. Ths mechanical properties of propellants must be such as to enable them to withstand the mechanical loads imposed during shipping, ieandHng, and firing. These re- quirements differ widely from one engine to an- other. Method* for measuiug physical strength and deformation ate reviewed by the JANAF Pond on Physical Properties of Sofid Propellant* and reported in the pubHcations of that pend. Numerical values below are as measured by stand- ard JANAF taste.' Results in such tests are strong fractions of the rates of tending, propellants gen- erally appearing stronger with higher rates of teed* ing. The rate* of loading in actual rocket motors vary from low rates during storage due to tem- perature changes to very high rates during firing. JANAF mechanical properties test data are sig- nificant to the extent that they compere proptiiants under test cooditioeut and imply that the tame com- parison will be valid under operating conditions. 18-1. Ultimate tensile straegA. Tensile strength is important for rocket grata* supported at the head end during acceleration. For other applica- tions it is of academic interest, or perhaps useful as a quality control measure to assure that succes- sive lots of a given propellant resemble eroh other. Tensile strength ranges from about 10,000 pounds per square inch for straight polymer mooopropel- lants to below 50 pound* per square inch for some case-bonded propellants. IM. Eloagatien in tendon. Caso-bonded grains must deform to accommodate changes in dimensions of their containing cases with change* in temperature. Although requirements very from rocket motor to rocket motor, a minimum of 15 percent elongation at rupture at the lowest storage or operating temperature is a typical requirement for a case-bonded propellant in a large rocket Many such propellant* have reported values of 50 to 100 percent elongation at normal ambient temperature. IM. Modules in tension. Alow vahie of modu- lus is required of case-bonded grata* <n order to avoid dittortion of the case or rupture of the adhesive bond when the motor is tooted. A typical value for modulus of a case-bonded propellant is 300 to 600 pounds per square tach per inch per inch, cr dtatenstonally pound* per rquare inch. Ultimate tensile strength, elongation, and modu- lus are all determined ta the same test* A test tootalladoo is shown in Figure 20 and a test record indicating the derivation of data in Figure 21. 18-4. Stress retantian. It is advantageous ta a case-bonded propellant for the stresses produced by distortion to be relaxed as the grata become* accommodated to its new environment so that residual stresses will not lead to cracking ta areas of stress concentration. The property of relaxation under tension may be measured by measuring the tensile stress at fixed etengatten as a function of time.1 28
Q PROPELLANT SAMPLE © SAMPLE GRIPS ©MOVABLE CROSSHEAD ©FIXED CROSSHEAD © LOAD CELL © STRESS-STRAIN RECORDER ©RECORDER CONTROLS ©CROSSHEAD CONTROLS Flgun 20. Tuntilt Tert Setup 29
Figure 21. lentil» Tul Record Showing Derivation of Ultimate Strength, Elongation, anti Mulut (Road curve from right to left) 30
18-3. Creep. A lower limit on tensile modulus of case-bonded propellants is set by the require- ment that under its own weight the propellant not deform so as to decrease port areas or substan- tially change shape and dimensions. Whether such deformation is elastic due to too low modulus or inelastic due to cold riow it is known as creep. Creep has been responsible also for departures from design ballistics of cartridge-loaded rocket grains. The best criterion for assessing the tend- ency to creep still appears to be experience. 18-6. Compressive strength. Cartridge-type rocket grains supported on traps or otherwise at the nozzle end are subjected to compressive stresses during firing. The magnitude of such stresses and, therefore, the compressive strength to withstand them can be computed for any instance from the designed acceleration of the rocket. Compressive strengths of propellants are usually of the same order of magnitude as ultimate tensile strength, and for design purposes the tensile strength of the propellant is frequently used with suitable safety factors. Compressive strength can be readily meas- ured on equipment shown in Figure 20. 18-7. Deformation at rapture in compression. The most severe stresses on a gun propellant occur during ignition when the grains impact on the cartridge case or chamber wall and on the base of die projectile as a result of having been accel- erated by the igniter gases. If the grains shatter in such impact, the added burning surface leads to excess pressures in the gun. Redesign of the igniter is the usual remedy, but the propellant is required not to be brittle. The test specified for brittleness is deformation in compression at rupture. Unless otherwise specified the required minimum value is 30 percent. *• 18-8. Modulus in compression. For cartridge- loaded rocket grains the deformation due to com- pression during acceleration must not be great enough to cause significant departures from design geometry. This fixes a lower limit on the permis- sible value of compressive modulus. The value of this limit has not been precisely evaluated as high values of compressive modulus usually accompany the required compressive strength. 18-9. Shear properties. Case-bonded grains are stressed in shear during acceleration. The weight of the propellant must be supported by the shear strength at the bond between the propellant and the case. Per unit of propellant lengt', neglect- ing the perforation, the weight cl the propellant under acceleration and therefore the total shear force is ^d2pa where d is the grain diameter in inches, p the propellant density in pounds per cubic inch, and a is the acceleration in g’s. The total shear force is applied over an area of ird. The required minimum shear strength, in pounds per square inch, is itd^pa _ dpa 4*d ~ 4 Procedures for measuring shear have been re- ported.11 18-10. Brittle temperature. For many plastics the second-order transition temperature1* sig- nals the onset of brittleness. This appears to be the case with casc bonded propellants. It hes not been established that the same significance of the second-order transition temperature holds for car- tridge-loaded propellants which perform well at temperatures considerably below that of a second- order transition. The second-order transition temperature may be measured" by noting a break in the curve of specific volume versus temperature or an abrupt decrease in mechanical properties such as impact strength at that temperature. REFERENCES 1. C. G. Jackson, “A Mercury Displacement Volumeter," J. Sci. Instr., 6,261 (1929). 2. MIL-STD-286, Propellants: Sampling, Inspection and Testing, Method 310.1.1—Specific Gravity (Pycncm- eter Method), 28 June 1936. 3, MIL-STD-286, Propellants; Sampling, Inspection and Testing, Method 502.1—Bulk Density, 28 June 1956. 4. MIL-STD-286, Propellants: Sampling, Inspection and Testing, Method 507.1—Density of Loading, 28 June 1956. 5. MIL-STD-286, Propellants: Sampling, Inspection and Testing, Method 503.1.2—Hygroscopicity, Small Arms Propellants (Equilibrium Method), 28 June 1956. 6. MIL-STD-216, Propellants: Sampling, Inspection and Testing, Method 503.2.1—Hygroscopicity, Cannon Propellants (Equilibrium Method), 28 June 1956. 7. J. N. Sherman and H. M. Burns, Temperatures Pro- duced in Solid Propellant Rockets by Exposure to Climatic Extremes, Allegany Ballistics Laboratory, Hercules Powder Company, ABL/X-37, June 1959, Contract NOrd 16640, CONFIDENTIAL (SPIA Ab- stract No. 19341). 31
S. Joint Artny-Navy-air Force Panel on Physical Prop- erties of Solid Propellant», Methode for Determining the Tensile Propertier of Solid Rocket PropelianK. Part 1. Nitrocellulose Bate Propeliantr, SPIA/PP8, March 1956; Port II. Composite, SPIA/PPS, Feb- ruary 1957, Solid Propellant Information Agency, Applied Phyaica Laboratory, The John, Hopkina Uni- versity, Silver Spring, Maryland. 9. К, H, Sweeny and K. W. Bill*, Jr., Appanttiu for the Measurement of Street Relaxation Behc lor, Aerojet- General Corporation, Bulletin of the Seventeenth Meeting of the John Army-Navy-Air Force Panel oa Phyaica) Properties of Propellants, SPIA/PP11, p. 91, May 195», CONFIDENTIAL, Solid Propellant In- formation Agency, Applied Phyaica Laboratory, The Johns Hopkina University, Silver Spring, Maryland. 10. MIL-P-270,4, Propellant, Artillery, 5 March 1959. 11, F. A. Warren, E. L. Anderson and P. M. Xu, Evalua- tion of Solid Propellant Propertlee. Part I—A Survey of Current Methods, Southwest Research Institute, Report RS2S7, 31 January 1959, CONFIDENTIAL (SPIA Abatract No. 19191). 12. F, W. Billmsyer, Jr., Textbook of Polymer Civmitiry, p. 40, Intendence Publiaben, Inc., New York, Naw York, 1957. 32
СНАРТМ 4 BLACK POWDIR 19. CumiL Black powder is our oldest pro* pritasL It is older than any at the heat engines (guns, rockets) in which propellants are used, and has been used as a pyrotechnic and as a bunting charge for centuries. It is an intimate mixture of saltpeter, charcoal, and sulfur. There are two types of black powder, one made with potassium nitrate and the other with sodium nitrate. The potassium nitrate type is the older, and for ordnance uses is still the more commonly used. In ordnance circles black powder it the potas- sium nitrate type unless otherwise designated. The name black powder is a translation of the German “Schwarzpulver," named after Berthold, Schwarz who experimented with it in the fourteenth cen- tury.1 In the English language the material was known as “gunpowder” until the use of smokeless powder in guns made it necessary to differentiate between the black and th smokeless varieties of gun propellant. GunporAk. ..xluded Musket Pow- der and Cannon Powder, later Rifle Powder and Sexting Gunpowder. When used for blasting, gun- powder was called Blasting Powder. The present United States terminology is “A" Blasting Powder.' The sodium nitrate type of black powder was developed in the United States in the middle of the nineteenth century9 an^. is known commercially as “B” Blasting Powder. When used for ordnance it is called sodium nitrate black powder. 20. Appearance. The appearance of black pow- der is shown in Figure 22. The grains are irregu- larly shaped solids, resulting from the fracture of larger pieces on the rolls of the corning mill, of roughly uniform size as a result of screening. Black powder may alternatively be pelleted into grains of uniform tiize and shape. 21. СсшрваШоо. The nominal composition of black powder as available in the United States is shown in Table 3. The same compositions are used for both military and commercial grades. Selection of the charcoal has an important bearing on the quality and performance of black powder. The charcoal is not pure carbon, but contains 13 to 20 percent volatile matter and 2 to 5 percent moisture. 22. Ciwslaiion. The standard granulations of potassium nitrate and sodium nitrate powders are shown in Tables 4 and 3, respectively... 23. Thrrntochtibtry. Lacking knowledge of the nature of die volatile matter in the charcoal, and considering that manufacturing tolerances per- mit 1 percent variation in the fraction cf each TABLE 3. NOMINAL COMPOSITIONS OF BLACK POWDER AVAILABLE IN THE UNITED STATES UNO,type 4 NaNOitype* KNO>, % 74.0 — NaNO„% — 710 ~ 2 Sulfur, % 10.4 12.0 * 2 Charcoal, % 13.6 16.0 «2 Ash, muimiMi, % 0.80 1.3 Moisture, maximum, % 0.30 0.70 Specific gravity 1,72-1.77 1.74-1.S2 ingredient, it is practically impossible to calculate the gas composition or volume of black powder, A rough approximation may be got by assum- ing that the volatile matter is largely carbon, that the potaasium appears in the product as K2CO8, the nitrogen as the carbon as CO + COa, and that the sulfur and such hydrogen as is in the vola- tile matter do not make an important contribution to the gas volume. Under these assumptions the gas volume would be given by [C] + W[N] - M[KJ. Since the IN} and IK] are present in equal num- bers, the gas volume of black powder is deter- mined roughly by the fr.Mion of charcoal in the formula, In the United States grade of potassium nitrate type of black powder, one gram contains 0.0130 gram atoms of carbon which when burned should give 0.0130 moles or 290 cc (STP) cd gas. An experimental value of the gas volume from three samples of British black powder recently examined in the Imperial Chemical Industries laboratories has been reported at 280 cc (STP).* The same author reports a beat of explosion, Q, of 720 cal/g and a kulated flame temperature, 33
figwt 22. Block Powder, Grade ffffG, BX Magnification 34
TASLE 4. GRANULATIONS OF POTASSIUM NITRATE «LACK POWDKBS Sieve ita Retained (maximum percent) Sieve ate Military grade ‘ A-l • 4 3.0 s 3.0 A-2 4 3.0 12 ЗЛ Cannon 6 3.0 12 5.0 A-3 12 3.0 16 3.0 A-3a 12 3.0 20 ЗЛ Muaket 14 3.0 23 3.0 FFG 16 3.0 30 5.0 A-4 16 3.0 40 5.0 Shell 16 3.0 30 3.0 FFFG 20 3.0 30 ЗА A-5, Fuse 40 3.0 100 5Л FFFFO 43 3.0 140 SA A-6 100 5Л 140 13.0 A-7 100 3.0 140 ЗОЛ» Mad 100 3.0 200 50.0 Sphero-texagonal: 123 «> 2 grain* per pound, 0.6-jneb grain diameter Commercial grade Sporting Whaling 32/64* 3 4 12 Life Saving Service 6 3 12 12 Cannon c> 3 / 12 Saluting 10 3 4o 12 Fg 12 3 16 12 FFg 16 3 30 12 FFFg 20 3 30 12 FFFFg 40 3 100 12 "A** Stating FA 20/64» 3 3 12 2FA 4 3 12 12 3FA 10 3 16 12 4FA 12 3 20 12 3FA 20 3 30 12 6FA 30 3 30 12 7FA 40 3 100 12 MmID 40 3 — — Meal F 100 3 — MetlXF 140 3 — — * Diaawtar of circular pwfenitjonr in pitta. 35
TABLE 5. GKANULAHONS » SODIUM NTISATB BLACK POW9BBS Store lias ММагуОемй • JANC 9/14 iacb JAMB 4 JANA 12 СвммШ Gtada > ТИмйч ccc cc c F FF FFF FFFF MrelBB 40/44* 34/44 27/64 20/44 4 6 12 14 MM1BD Busis sit (axtonm psmat) 0 iii Sato 0 3 16 s 3 40 3 75 32/44* 75 75 24/64 75 75 11/64 75 75 5 75 75 a 75 75 14 75 75 40 75 75 — — 75 'DiMMtar ft circular parforMk*» ta pteta. Г„ of 280C°C. Products identified in the ca<n- bustioc products include mainly K3CO«. Kj3O«t KfSg, CO3, N1( some H3, H3S, CH«, NH-, H,O, XCNS, and some unreacted KNO3, C, and S.’ As the fraction of charcoal increases and the frac- tion of saltpeter decreases, the gas volume should increase and T, should decrease. The force, F, calculated from the Imperial Chemical Industries data, is 110,000 ft-Ib/lb. The initial condensed phase reaction in the burning of black powder has been identified as the reaction of molten sulfur with occluded hydro- gen* or oxy hydrocarbons in the charcoal,' or with the potassium nitrate.1 A sutturiess grade of black powder is manufactured in Great Britain. Uris has a considerably higher ignition temperature than normal black powder because molten saltpeter is required to initiate its combustion.1* The concept of linear burning rate as presented in Paragraph 9 has little significance when applied to the irregular shapes of black powder. The term linear burning rate, when speaking of black pow- der, is applied to the rate of propagation along a column of the granular material, /л., a fuse. 24. 3ypwcopictfy. The hygroscopic nature of black powder has long been known and is recog- nized in the familiar slogan “Keep your powder dry.” Uris hygroscopicity is primarily due to the saltpeter. It may be explained on the basis of moisture pickup at any time that die atmospheric humidity exceeds the partial pressure of water over a saturated solution of die saltpeter. Humidity cycling results in a clow deterioration due to crystal growth of У*е nitrates. Submergence of black powder under water causes the saltpeter to leach out 25. Shelf fife. At elevated temperatures, physi- cal chauges in the sulfur can occur. The hygro- scopic effects are also deleterious to shelf life. Apart from these influences, black powder is very stable thermally uui under optimum conditions black powder can be stored for many yean with- out serious deterioration. 26. Manufacturing precam. Both types of black powder are manufactured by the process shown schematically in the flowsheet, Figure 23. The charcoal and sulfur are ground together in the pul- verizer, which is essentially a ball mill using short steel cylinders for balls. The “composition dust” is discharged from the pulverizer through a “reel” or screen which rejects the coarse material. The saltpeter is added to the composition dust and 36
rework in the whed mill, shown in Figure 24, along with a small quantity of water. The indi- vidual wheels of the wheel mil' may weigh 10 tons and stand 7 feet high. The functions of the wheel mill indude in addition to grinding and mixing the achievement of a state of “incorporation.” Although incorporation is little understood, it is believed to be a state of very dose contact among ingredients, perhaps without intervening films of air on partides, and accomplished by very con- siderable mechanical effort in the form of shearing pressure.1 When the wheel mill cycle is complete, the whed cake is shoveled out and transported to the press house where it is first broken down by passing through rolls, then pressed into cakes using a horizontal press shown in Figure 25. The press cakes are broken into pieces of about M -inch size on the cutting rolls shown in the back- ground of Figure 25. The sire is reduced further on the corning rolls. The product from the coming mill is screened on a reel, the dust being sent back to the press. The product size and shape do not change essentially after the corning operation. The remaining operations are glazing and screening to separate the various grades produced. The glazing operation is carried out at elevated temperature in order, simultaneously, to evaporate water down to the specified level. If fuse powder is being made, two or more grades of different burning rate are produced by varying the ratio of sulfur to char- coal in the formula and these are blended to meet burning rate specifications. 27. Uses. With a force, F, at 110,000 ft-lb/lb, black powder was an effective gun propellant. The presence of solid reaction products led to large volumes of smoke and to a corrosive barrel trffce requiring thorough cleaning of Ле gun dt^gw after each use. When propellants known as sdttjie- less powders with higher force and аиЬМаашйу without solid products became available, qfock powder became obsolete for gun use. The chjjpige was not made overnight because a gun designed for blade powder was not ideal for use with srdcke- less powder and vice versa. There are still a few antique sporting pieces in the hands of hobbyists who fire them, but the use of black powder as the propelling charge for guns no longer is significant. During World War II a need arose for a flash suppressant for use with certain guns, particularly the 155-mm gun. It was known that potassium salts are effective in suppression of flash. As black powder is roughly three-quarters potassium nitrate and a propellant in its own right, the use at night of an auxiliary charge of black powder was under- taken with considerable success. This use of black powder is not expected to outlive the present in- ventories of smokeless powder, however, since new propellants containing largely nitroguanidine have been developed which have at the same level of force lower burning temperature than those of the World War II smokeless powders. These nitro- guanidine propellants exhibit much less tendency to flash, and the incorporation of small fractions of potassium salts in them generally inhibits flash completely. Black powder was also the original rocket pro- pellant. In the decades before World War II, ex- cept for Goddard’s experiments, rocketry in the United States was confined to fireworks and 'mall signal rockets of modest range and velocity h<id small payloads. For such rockets, black powder 37
Cewtt»)/ с/ Ж. t. 4мЛм1 <й AFemow* Л Co., /яс. figure 24. Week fowdar Wheel MH 38
Courtly ct 8.1. duFort tic Ntmoun • Со.» Зле» Figure 25. Ы<кк Powder Prow 39
has been quite satisfactory. The smoke and sparks of die exhaust were desirable and there was no disadvantage connected with residue in the spent motor chamber. When military rockets were de- veloped during World War II, first abroad and later in the United States, it was recognized that the low calorific value of black powder took it out of competition with the more energetic propel- lants that were available. Manufacturing processes moreover were not available to form black powder into the grain geometries required for these higher performance rockets., and it is doubtful that the physical properties of black powder would be com- patible with the thermal and acceleration forces of such rockets. As a bursting charge, black powder has been supplanted largely by more potent high explosives except for some practice bombs and projectiles where the smoke puff helps locate the impact point In primers for gun charges and igniters for rocket charges the easy ignitibility of black pow- der has made it a preferred ingredient The high content of potassium nitrate has abo been recog- nized as favorable for such use, because potassium salts are good emitters of radiation and radiation may be an important means of transfer of heat from the primer or the igniter to the surface of the main propellant charge. As the first civil as well as military explosive, and for a long time the only available explo- sive, Hack powder has been extensively used for Wasting. For this use the sodium nitrate Wack powder has been preferred ever since its introduc- tion, in spite of somewhat greater hygroscopicity and slower burning rate, because of its lower price. Black powder does not detonate, even when ini- tiated with a Wasting cap. The observed propaga- tion rates of 100 to 600 m/sec’-11 when confined in steel pipes and initiated with a detonator are accounted for by shattering of the black powder by the initiator and burning at the attained pres- sure. Black Wasting powder was first supplanted by commercial high explosives for blasting in rock because the detonation cf the high explosives was very much more effective than the burning of black powder. For Wasting in earth, Wack powder with- stood the competition of high explosives tor a longer time because the shock of detonation of high explosives wu rapidly dissipated in earth TABLE 6. CONSUMPTION OF BLACK BLASTING POWDER (ALL TYPES) IN THE UNITED STATES1* Year Founds (thousands) 1915 197,722 19» 254,140 1925 156,964 19» 99,473 1935 64,441 1940 59,754 1945 36344 19» 20,653 1955 6,624 1954 5,594 1957 3,644 1934 2,492 whereas the slower burning black powder main- tained pressure longer and gave more “heaving” of the burden. Coal miners like black powder be- cause it breaks the coal into higher priced lump coal and produces less fines than even the low rate permissible high explosives. Unfortunately the reaction time of Wack powder lasts longer than the initial fracture of the coal, resulting in occa- sional ignition of methane (fire damp) and dust in the atmosphere of gassy mines and even of the coal itself. Use of black powder tor blasting in coal mines engaged in interstate commerce is now for- bidden by federal law. The largest current use of Wack powder is for safety fuse. This b a column of Wack powder en- closed in a fabric tube. The rate cf burning is carefully standardized so that the shooter can pre- dict the length of time between lighting hb fuse and the shot. Black powder has also been used as the timing element in some military fuzes. It has the disadvantage of producing a considerable volume of gas which either must be vented or it increases the pressure on the powder train and hence its bunting rate. It has the further disadvan- tage that it b difficult to ignite at reduced pres- sures and impossible to ignite ей pressures below 100 mm. For use at high altitudes it b necessary to assure that any device relying on the burning of black powder be pressurized. The decline of the Wack powder industry in the United States i’ shown in Table 6. Recognizing the obsolescence of Wack powder, the military forces have sponsored research on substitutes tor Wack powder in all applications. 40
KfUAiMU RCnKBPIvv* I. A. P. VanGeider and H. Schlatter, History of the Ex- plosives industry bi America, p. 10, Columbia Uni- versity Pima, New York, New York, 1927. 2. C. W. Brooks (E. L duPont de Nemours A Co., Inc.), private communication. 3. L. duPont (to E. I. duPont de Nemours A Co., Inc.), U. S. Patent 17,321 (1837). 4. JAN-P-223A, National Military Eaabllthment Speci- fication Powder, Slack (12 January 1949) with SCN No. / (23 March 1939). 5. JAN-P-362, Joint Army-Navy Specification. Powder, Black, Sodlam-Nitrate (28 June 1946) with Amend- ment-1 (23 December 1946). 6. J. Taylor, Solid Propellent and Exothermic Compo- sitions, p. 19, Intendcncc Publishers, Inc., New York. New York, 1959. 7. H. Debus, “Chemische Theorie dee Schiesspulver*," Ann., Hi, 257 (1882); 213, IS (1882). (Smnmsrtied in J. Taylor, loc. clt., p. 20). 8. J. D. Blackwood and F. P. Bowden, "The Initiation. Burning and Thermal Decomposition of Gunpowder," Pmc. Bay. Soc. (London), A213, 285 (1952). 9. C. Campbell and G. Weingarten, "A Tbenaoanalyti- cal Study of the Ignition and Combustion Reactions of Black Powder," Tran*. Paraday Soc.. 99, 2221 (1939). 10. J. Taylor, loc. tit., p. 21. 11. Hercules Powder Company, unpublished data. 12. U. S. Bureau of the Census, Statlttical Abstract of the United State*: 1940, 62nd edition, p. 860, Wash- ington, D. C., 1940; ibid., Statistical Abstract of the United State*: 1939, 80tb edition, p. 813, Washing- ton, D. C., 1939; U. Я Bureau of Mines, Mineral Market Export No. MMS 3973, Washington, D. C., 1959. 41
СНАРГМ f CRYSTAI'.iNE MONOPROPELLANTS 28. General. The shape of black powder grains suggests crystalline material. A crystalline chemi- cal with better thermodynamic properties than black powder should have advantages over black powder not only in ballistics but also in uniformity of composition and ease of manufacture. Such chemicals exist. They have not been exploited as propellants because they became available at a later date than nitrocellulose and smokeless pow- der, and the background knowledge that would have led them to be appreciated is of still more recent origin. The list of possible monopropeUants includes many chemicals used as miKtaiy high explosives, as the thennochemistiy of propellants is essentially the same as that for high explosives. The difference between combustion and detonation of a crystal- line monopropellant is merely a difference in re- action rate.' Except for primary explosives, which can detonate from burning and are therefore ex- cluded by definition from possible monopropel- lants, these chemicals will burn quietly when ignited. They will detonate only under the influ- ence of a mechanical shock of severity far greater than can be found in a gun or rocket chamber. The thermal stability as well as the sensitivity of these materials have been extensively investigated in connection with their use as high explosives. In general, they exhibit long shelf life and are very stable at temperatures up to nearly their melting points. In common with black powder grains, single crystals of monopropellants are not' subject to being shaped to accurately controlled dimensions and large sizes. Again like black powder, however, they can sometimes be pelleted under sufficiently high pressure to moderately well consolidated large grains of controlled dimensions. The densities, melting points, and ballistic pa- rameters of several possible crystalline monopro- pellants are tabulated in Table 7. 29. Nitrogaaaldine. Nitroguanidine may, as an approximation, be considered 'to react according to the equation CH4O,N4 = CO + H, + H2O + 2N, (39) The gas -volume, of nitroguanidine it quite hi^h, and the fraction ot nitrogen in the gas is un- usually high for propellant gas. The burning tem- perature of nitroguanidine is some 150°K lower than that of a smokeless powder of the same force level (see Ml in SPIA/M2), indicating that nitro- TABLE 7. PHYSICAL AND BALLISTIC PARAMETERS OF CRYSTALLINE MONOPROPELLANTS Density (g/ec) Mdtinr point Ct) 1/M (moiea/lb) T. СЮ cfo Fcrct (ft-Ib/W) (ibeec/ib) Nitroguaaidine* 721 0.0481 226> 303,000 Nitroguaaidmcf 4.715 246 2405 1819 321,000 199 RDX, eycJotrimethylene- triaitretninc* 1.(2 202 1360 0.0405 4020 3250 452,000 255 HMX, cydotctramethylene- tetranitnunine* 1.92 276 1321 0.0403 3940 31(0 430,000 253 PETN, pentaaythritol Mranlnatt* 1.77 140 1531 0.034S 4220 3510 40,900 250 АлшюЫшп nitntef 1.72 170 334 0.0437 1622 1245 197,000 159 Ammonium perchloratef 1.9: Decomposes 335 0.0362 184» 1408 1(6,000 153 *Н1гмЬШ4аг-&мпаш cslcuistioo (see Pananwb 74). t Exact cskulstion (ме Fuajtepb 7-5) 42
guanidine should cause less gun barrel erosion than a comparable service gun propellant The higher content of nitrogen in the gas should result in less tendency to flash than a service gun propel- lant at the same flame temperature and an even more pronounced advantage at the same level of force. The usual crystal form of nitroguanidine is needles, resulting in quite low gravimetric density and small web. No successful work has been re- ported on growing crystals of size and shape that would permit using nitroguanidine as a gun pro- pellant. The linear burning rate has apparently not been measured. Although uitroguanidine has not found use as a monopropellant, the disadvantages of its crystal form have been overcome at the cost of some compromise of ballistic parameters by formulating nitroguanidine as filler with plastic monopropeliant binders into composite propellants. Development of such composites has also permitted a continu- ous spectrum of force and flame temperatures in the triple-base system described in Chapter 7. Nitroguanidine is synthesized by the fusion of calcium cyanamide or dicyandiamide with ammo- nium nitrate under high pressure and temperature to yield guanidine nitrate, followed by dehydration with mixed sulfuric and nitric acids* CaNCN + NH4NO8 + 2H2O - Ca(OH)2 + NH: C(NH2)NH2 • HNO8 (40a) NH: C(NH2)NHCN + 2NH4NO, = 2NH: C(NH2)NH2 • HNO, (40b) NH: C(NH2)NH2- HNO, - H2O ~ NH: C(NHj)NHNOa (40c) Other syntheses are known. The thiocyanate process* depends on the series of reactions 2NH4CNS = NH: C(NH,)NH,CNS +,H2S (41a) NH: C(NHi)NHaCNS + NH4NO, = NH: C(NH2)NH, • HNO, + NH4CNS (41b) The Roberts process* proceeds through ethyl pseudourea and guanidine sulfate CCXNH,), + (C,He)2SO4 = NH: C(NH,)OCaHg + C,HBHSOg (42a) H2SO4 + NH: C(NH2)OC2Hj + NH, = NH: C(NH,)a • H2SO< + C2HBOH (42b) NH: C(NH,)a • H,SO4 + HNO, - H2O = NHC(NH,)NHNOa + H,SO4 (42c) 30. RDX. RDX (cyctotrimethylenetrinitramtae, cyclonite, hexogen) may be considered to tract according to Equation 43 (CH,N,OX)S = 3CO + 3HaO + 3N, (43) The force and specific impulse, from Table 7, are quite attractive, although the flame temperature* are higher than desirable for gun applications. RDX has been fired in sporting and small arms successfully* with ballistics comparing favorably with those of smokeless powder. As expected, the quickness was found to depend on the crystal size, finer crystals being quicker than coarser. The high burning temperatures may be tempered by formu- lating to a composite with a binder of lower burn- ing temperature. RDX is manufactured by the Woolwich proc- ess' by the nitration of hexamethylenetetramine (CH2)eN4 + HNO, = (CH2N2O2), + gaseous products (44) or by the Bachmann process' by reacting ammo- nium nitrate and nitric add with hexamethylene- tetramine under dehydrating conditions (CH2),N4 + 4HNOa + 2NH4NO, -6H2O = 2(CH2N2O2), (45) 31. HMX. HMX (cyclotetramethylenetetrani- tramine) is homologous with RDX and may be assumed to react (CH2N2O2)4 = 4CO + 4H2O + 4N2 (46) The ballistic parameters are similar to those of RDX. It is somewhat more dense than RDX and has a somewhat higher melting point (Table 7). Like RDX, HMX can be compounded into composites such as PPL 949 (see SPIA/M2). HMX* appears as a by-product to the extent of about 10% in Bachmann-process RDX. No attempt is ordinarily made to separate it from the RDX, because for most uses it is the full equiva- lent of RDX. By changing the conditions of opera- tion of the Bachmann process, the fraction of HMX can be increased substantially to where iso- lation of the HMX is practical. 32, PETN. PETN (pentaerythritol tetranitrate, penthrite) may be assumed to react C(CH,NO,)4 = 2CO + 3CO, + 2N, + 4H,O (47) 43
With buming fcinpfretuit, aftij lower gas vtMj-'к, thf force and specific tmpulxe <X PLTN ass compa-able w th-ж of RDX and HM.X (Table 7), S:*л r’ETN has lower density and к>*:т melting no>j3i than R.DX »л1 НИХ, these kier material; ilrc-uld be. preiened to PETN either as monopf ope Hants or as filler for composite propellants PFTN is manufactured' by the nitration of penuerythritol стенной), * 4Hno, = CfCHjNOP, + 4H3O (48) 33. А «ни мйми вйп^е. Ammonium nitrate may be auumed to react NH.NO. - N, 4 SrijO 4 ИО, (49) As ». tnonopropellant, ammonium nitrate produces a working g« contaiainr free oxygen For this reason, although rtt foe atsd apecific impulse art •omewbat modest, when cotapectnded into com pochn with my incompletely oxidized binder» аишюсгсш, nitrate befrsves in par, as an oxi dam Such composites tire diacuwed further in Chapter 9 Anunonlum nitrate is hygroscopic a. relative mmudities above 40 percent Any propellant charges comprising ammonium nitrate murt be protected from hunridity Ammonium nitrate also undergoes a series of phase changes a: different temperature’, including one at 32.2‘C,' all of which are accompanied by changes iu de Bitty. This и destructive to the integrity of single crys- tai* Whrs’ into * ccs2pO2ti «^.th hydrophobic or oonhygroscopic binder, »£ of tfr ammonium nitrate crystals within the binder rt protected from moisture pickup The ph ase changes can also be contained, as the crystal sue of the «nmoniun nitrate is preferably very «nail and the stresses produced by the volume change of the individual partides can be absorbed by the binder. When forated into large grains by romp-ession molding, hygroscopic effects are likewise confined io ibr material near toe surface Phase changes in such propellants cause them to swell somewhat on aging, bi t do not appear to interfere with then normal burning processes. Such grain' have been studied * but 1 ave not fe-itd service use Ammonium nitia'; ci an article of -ommerce, being widely used as t> fertiluri ingredient and as i constituenl of cocamercial high explosive*. 34. АпыьоаМк^ регсКотме Ammonium per- chlnratc may be asspnwd tc react NH,ao4 = kN, -s- ИСТ -r- %H,O < »«O, (50) As t mocipropieUani, animon.um perchlorate is even more oxidmng than ammoniurr nitrate Like ammonium nitrate, ammonium perchlorate is hy- jroscopk The presence of hydrogen chloride in the products of «за. nation тьке« asworiuin per- chlorate unaXiracUvt !c use in engines used repeti tiv.ly, such as guns For these reason з imnwit m perchlorate has not tieen used *s a mocopropell mt charge It is wkiely used as an oxidizing fukt in composite proptliana for rockets, at discussed further in Chapter 9, and in ORDP 20 176. Ammon: um peirhlcrate is prepared by electro- lytic oxidation of sodium chloride, NaCI + 4H-O = NaCO* + 4H, (5'a) followed by metaihess with an ammonium salt NeOO, + NHr = КН4СЮЛ t Na' (51b) I L Wohler wrd F. J. RrXh. “Ucbrr die Brisaaz <w Елркоаумйгг,- Z. get Schutt- к Spreng coffn., 29, 9(1934). 2 G Б. L Sajlh, V J Sabriu sad O. F Suir.bach, Jr, “Qutaiioiivr Stud, at the Prcperaticai ol Guar.wtiw b’iljtl» s_aJ Nitroguiuudioc," iai. Eng. Client., 23, 1124(1931) 3 . The Synrlieiii алД Eioeruts e>j Sirrc^uanldine. Na'al ГCCU,',, f.Tau Afvre.is V* ». <u 15 Juw 1950, CCNI'lDtNTIAL (SPIA Abstract Ho 106401, Sfiuiufj or A'lirojf L-rudi**, ibu!. Re pert QR 12, 15 Jub 195!. CONFIDENTIAL (SPL', Abarwci No llAAi) 4 . Hcrculei Powder Ccraiwr.y unpubUsbed dsu 5 W. M Rinleebach, Extlosiies <Kifhi. in Enrfclo- feiu of Chtnitai Teth-xolory, Vol 6, p 4C. Inter science Publishers, lee. Ne* York. Ne* York, 195’.. 4- W. F Bachmann, U S Pstetii 2?9S,«10 11957j. 7. E Berio», R H Barth tod J E Seo», Tne rente enivib-Oi p 34. ».et=bcH Pubis vms Corpcrstiss. Nr* Yorl, New York, 1954 t inle,-national Critical Tablet cf H'ameiical Date Phjrict, Chemittrf and Technolorj. Vol 4, p 7, McGrtw Hiff Book Сотри:», Inc, Nr» York, New York. 1926 9 F R Groves. Jr sad L Greraer. A»"wew,«"i biiirat' SoIid-Frope'Jci; Inictiifotion Fcpenrr»e-.i Isarp rated. Technical Publktucm 144. I April i957, Cesv usev NGrd 16490, CONFIDENTIAL 44
CKAFTW * •LASHC Л5. Pias/к mono} repellents, rom- tnooly known as sraokr-less powdas,* have ч-г, iis uy for abot'l '75 yean. The firs: such propedaii’ > » made by Vieilk in France in 1884.1 Vreilk's pioduct was etsentiaily nitrrxcllulote, changed from it* originally fibrous form to a dense ptatic by coUmding with ether and alcohol, forming into g ain.,, and subsequently removing most of the solvent A few ye?,-, later Alfred Not*’ introduced a different variety of smokeless powder in which nitrogiycenn is used as a collriding plasticizer for the nitrocellulose ’ Propellants containing nitro- glycerin are клети as douNe-base because they contain two explosive ingredients it- contrast to engic-base propellants whsch coo taiu nluvcetiu- k»e as the only explosive ingredient. Addittou of fnel-type or “deterren'” plasticizers to the forma- taxon gives the necessary flexibility for calorific value and nitrocellulose content to be variec inde- pendently, an important consideration alien both ballistic qualities and physical properties may be specified. Ballistic qualities are largely determined by the calorific salue, and phyvkal properties by the polymer content A smokeless powder, looked at in this light, is a singk-phate or mooc-propellant comprising three ingredien' . a polymer, to Xly DjlroccUukxe, an oxidant ptastitizer, usually nitro- glycerin, and a fuel plasticizer, fot example, di-n-butyl phthalate. Toe terms ungte-Ьазс and double bxsc fisvc thru Mguificauce, *iiut*e- baae being just a special case in ’»hkh the oxidant plasticizer content happens to be zero 34. Forastaos. The relationship* within the family of nitrocellulose mrwopropeliants are shown qualitatively tn the triangular diagram of Figure 26. For ballistic purposes the как of Figure 26 should be considered about hneai in wei^h' frac- tions ^'or physical properties i’ is about linear <n volume fractions. Ln tbit figure the Use PH rep- resents all possible composraons with the same calorific value as pure polymer, P. Lines parallel to PH are lines of contUnt calorific vrlue. Com- positions to the lefi of PH are ‘'cooker,” пл-t lower ca.'srific value (lower dame temperature/ than that •Although the term "«токек** powdc" ч «ей! cwrwr. ataxd sad in Lniicd Suie* commerctaJ circle», th* De- pantnesi of De Itrue h»> йиняЮаик! the ussjp: ' of pure poJywxr Io the right of PH, they art “hotter.'' have higher calorific vahte (higher force or specific impute) The line BC represents com position» cf the minimum practical Yeung's tsuxfas- lus for propellant use. Below BC the politest cannot be relied on tc maintain itn geoosetry, e»ea when supported by being bonded tv the chamber wall The line А В define* thr lowest adori&c vahx thzi ait end-item designer can profitably use AU useful ruttoceUulosc одлххтгореПагШ are, there fore formulated within the polygon PABC. Since gun erosion limits ’he allowable flame temperature of a propeliaat, gun propellant for- mute* tend to fall to the left of the hr*. PH, although fot some appheafiotu they иду be well to the right High perform «лее racket propellants art fooou tc the right of the tine PH. Case-bond- able propellants fall in the neighborhood of the tine BC. Propellants to generate gas at moderate temperatures for aircraft riarier engines aad влй- Ur appiscatiocs arc fowsd tn the neighborhood of the hne AB. There exists considerable overlap between the formulaltoc areas fo< different types of end use in adiittoc to ак uirt- baste: ingre- <fi»nts a stabilizer is universally used tc mmase the storage life of the propellant, and additives may be incorporated to reduce flash, to improve ignitability, to reduce metal fouima in gun barred, to reduce the pressure etpooeat, n, to provide upiuiy. шк! tor various other reasons. M-l Fcdywer. Nitroceliukwe is the usual poly- mer in plastic morK j-TOpellanU, but other polyjten can be, and have been, used Ftgvrt 26. Nkrocahulae* M^nuprofl^ikinr SytHtn 45
34-1.1. Nltrs»ecfla»r»w. Nttf-tceihilose » the product of partial tutratwn of cellulose. which » » natursl polymer of empirical fonaula (C„HlftOs j, *nd «trur<ursi fr rymtU Of the three -OH grwpt. those at me. 2 and 3 po..tjocn are secondary, while that in the 6 posi- tion is p imary. All of the -OH groups can be nitrated, and when celb’Jose it. completely nitrated the resulting nitrocellulose has a nitrogen content of 14 15 percent. SltroceUulou as ujsd ir com roerce, and as used in propellants is lesr than eompfcteiy nitrated NttroceLukses are character- uxd by nitrogen content and viscosity as inde- pendent variable. Hygroscopicity and solubility in various solvents depend primarily on the nitrogen content. Significant commercial grades cf nitro- cellulose are those used for lacquers at 12 pt rcent nitrogen, for dynamite at 12 percent nitrogen, and for plastics at 11 percent nitrogen The grades of significance to propellants tn the United States art guncotton or high grade at 13.4 percent nitrogen, pyrocellulose at 12 6 percent nitrogen, and one as yet not officially named at 12.2 percent nitrogen ‘ Foreign propellants frequently contain uitrocellu- loae of krwer substitution than 12 percent nitrogen Ouncottr..; i. not used as iix от.1у nitrocellulose in Americas propellants, but is commonly blended with pyrocellulose to yield a "military blend" at about 13 15 percent nitrogen x a blend at 13.25 percent nitrogen. All fibrous nitrocelluloses look alike, and indeed look much tike the original oellu кие White there could be merit in aeparately for- mulating two nitrocelluloses into a propellant, the еЬтопаЬос of possible coofusjoci between ditfer- eat grades of nitroceUakwe and the oppvwrotrity of adjusting the ratio at the nitroceliuloeet whale in the fibroui state to an exact blended nitrogen coatent argue strongly for blending M-l.1.1. NNregM ceatutt- As indicated in Table 2, the contributke o' the тшхеПикие to the calorific value, flame temperature, and there- fore force, ’prcific impulse, or characteristic vt locir of the j.TCpeIIs.n! i« higher the higher the nitrogen coate*4. 34-1.1.2.. SuUMMj. Nitrocclluloae al 12 2 pc - cent от 12.6 percent nitrogen is completely edub’c i.e., miscible in all proportions, in a mixture at 2 parts by volume ether and 1 nvt alcohol, used in the required solubility determination * At 13.4 per- cent nitrogen only a small ft action of the nitro- cellulose enters the solvent phase. No attempt is made to пинигге the solvent content erf the nitro- cellulose phase Neitner the high solvent fraction nor the proportion of ether and alcohol used in this determination is representative of the system involved in the manufacture cf propellants, where the nitrocellulose imbibes all of the solvent and tw separate solvent phase is present Nevertheless, es shown in Figure 27, under the microscope mdi vjduai fibers can be seer, to have maintained their identity in uaptasticized propellant made from military blend with ethtr-tkohol solvent. Intro- duction of plasticizer into the formula usually obliterates this pi < nomenon completely. The rea- son for this is that nbibttion of solvent pi us plasti- cizer so softens the nitrocrUukae fibers that the fibrous structure is destroyed by 'he mechanical forces acting 'luring mixing and subsequent opera * 'v taHTCZv-tSHaSwSsw «й ШwA^d^CtTiD folk'»; ft ixrally the solubility in ether-alcoho’ Solvents risen used to fabricate double-base pro- pellanu usually contain acetooe, in which all of the military grades of nitrocellulose are soluble. Detenmoatioe of etixr-akohol solubility has little rea! Hgntficance c.ttier to the manufacuue от per- formance of a propellant It does sene to indicate that a given lot of nitrocellulose resembles the particular n •roceDukne used when the propellant was originally standardized Л4-1.13. tlypMcaptrify. The ию»*'ч.|'г content of nitrocellulose m equilibrium with a sars'Med atmosphere at 25 rC has been expressed1 by the eoualkm H - 405 8 ~ 28 7* i52y H ” 31.11-5 132) where h is the percent nitrogen in the nitrocel'u- кие. From tixLe equation have bee» calculated ’he values shown io Table 8 for the niirocdiua'sea used in propellants.
PjQ'jff1 27. Ccgjs SeHton or G'C*n о/ /MJ? SmoltJen PcwJe< to' Arms, Phc»fO0fCipb*d in Uh'OviQltt Uj-И. H?> Mog^jficc*K>n 4?
ORDP 20-1 25 ТАМ.* 8 HYGROSCOPICITY OF MTNOt ELL I LOSE №клфса in NwrxfUuioK Wall' ijtffrcrat) (percent) 1Э 40 I H IJ.iS i J* li.M 2 И И.20 2*1 The naruie of this relationship may be explained on the beat that it и the unni(rated —OH groups of the nitrocellulose that sorb ruou'wc М-1 1.4. Vlwroakty. Viscoairy in very dilute *o- iutKMi it a quantitative measure at tbe avetagr molecular weight of x polymer, ш *hwn by tbe equation' “"C —» 0 — 1 .-= D— (33) Gt. / 200 - where , is the measured viscoeriy of the solution, 4, й the viscosity of the solvent, C i-> the concen- tration of the тС-ч-Л^оас in the sdulM®, aad DP is the degree of polymerization The value 200 is empirical aad varie slightly with the degree of aubstitution and with me solvent used. Tue nguie shown here is used for acetone solution. The left member of Equation 53 is known ar the intrin- sic "iwoeiry The ratio - is called the relative 1* viscvsity At higher «wKwraticn secondary effects, no» completely identified, influence tbe viscosity For example, two mtrocellukжа of different origin, •bowing the same intrinsic viscosity, may have widely differing measured viscosities in more con- centrated solution. Fot propellant use viacoary is measured' by timing the fall of a %e-inch steel I all through a 10 percent solution of nitroceliujose in ккиое. Турка! values of nitrocellulose vis- cosity for propellant* are £ to 25 secor-is, but niti oceiluktses of higher and lower viscosities are sometimes used Th- conditions of the viscosity determination art not representative of ary con- ditions present during propellant manufacture The deurmination has as its principal significance the assurance that the nitrocellulose examined re aembtea that used in the standardized propellant M-1*4, Other pofyeen. Tbe polymer in the propellant deed oct be nitrocellulose Other ener- getic polymers may be used such as poly (vinyl nitrate), polyfpetrin acrylate), polyftrinitroethyl acry’atr). and even fuel-type polymers such at cellulose acetate or poly (methyl methacrylate). I* lh-.»a. cases tbe negative or deficient contribution on the part of tbe polymet tc the force of tbe prof client is oveicome by the i se of oxidant plasu- cIzcts strh as nitroglycerin and other nitrate esters. C x>l polymers if useo must be physically com- patible with the hot pla^ficixCo, This accounts fci the fact that die cool polymers cited above are JI esters Cellulose acetates, like nitrocellulose, are de- rived from cellulose, are not completely esterified, and are chai к'.trued by degree of esterification (e.-.prtssed as pet cent combined acetic acid) and by viscosity. Also like nitrocellulose, a cellulose acetet’ tn a propr’lant has its higliest degree of polymerization at the time of intr. duction into the mixer Synthetic polymers may be polymerized in ad- vance of introduction, in which case charac- ter. ration is possible. Alternatively, they can be polymerized in situ after mixing M-2 SttMKw. In couimoi) with other organic chemical*, nitrocellulose tends io deteriorate with »$e by a proceu known as thermal decomposition In the ca.sc c* nitrocellulose, thermal decomposi- tion suns with the splitting off of NO, from the nitrate groups’ This NO, reacts immediately with •сМ^ЙлТе^ ЙмшГш] Hj LlJfc prCipitliTiS \LkTVIkisliij!& "‘iuu- celiukne) and is evolved as NO. The secondary reaction of the NO, with the nitrocellulose accel- erates tbe thermal decomposition Hence thermal decomposition should be minimized by adding to the formula a chemical that will react ith the NO, to give a stable product and thus prevent secondary reaction of NO, with nitrocellulose. The other product resulting from the loss of the NO, is a bound free radical which also tends to react further to more stable product) An additive to letnove the free radical character of toe residue should also result in stabilizing the propellant Nitroglycerin behaves in a manner similar to that of nitrocellulose and can *x stabilized in the same way The stabilizers in c irrerr use in tbe United States are dipl enylamine, 2-nitrodiphenylamiLe, and ethyl centralite These are all weak bates, but they function by being nitrated lather that by fora ation of tali' Other siabiliztis that have been proposed include N-cthy'amhne, carbazoi", 48
/?-пс’оЬп, and К me thy! p r.itroar.ilinc Mineral jell». an unsaturated aliphatic, function:. as th stabd-zei in some Htitish piotellant* 3*-2.1, Diphenytawiuc, Diphenylamine., (C»Hj!sNH. is prepared by subjecting aniline V high temperature tn an autoclave 2C4H5NH, = (C4H4)aNH + NHj (54) Ju history in the aging of propellants has fven traced 1 The first reaction product is diphenyl nitrosoaminc, (CeHs)aNNO, followed by ring rutraili-c Diphenyl amine is sufficiently bask to attach nitroglycerin, so that its main use is in si gic-Ьаж propeDanu X -2 2, 2-NifiniWyhrayhihi. 2-Nitrodipben у I - amine is less basic than drpheayhanine and is inert toward nitrogiycei.n while still being a good sta- bilizer I* is preferred to dipbeoylamine as a stabi- brer frjr double-base propellants It is made by reacting l-chloro-2-citrobenzeof with aniline. (55) 34-2J. Efliyi cewtnribe. Ethyl centealite, oen tralite-1, or centralite for short, is zym-dkthykb- pbenylures, COfNCC^H*XCtH4))a It is made by reacting phosgene with N-ethyl- or N,N-diethyi- artiline Its reaction history is considerably more fC-T’plvili-'' tht'*"--' -tip"— up with nitrated anilines * The methyl analog. centrahte-2 or «.vm-dnnethy'diphenylurea, it also known and is used somewhat abroad The cen- tral? ч it considered to be asmewhat less elec- tive as stabilizers than 2-nitn<fiphenylarnjne, but they »re also quite good plasticizers. When found in propellants they are frequently used at higher fractions than the diphenylsminet to take advan- tage of their pfaslkuzing properties 34"5, OxkAaat-type pfawfirhan. The required properties of an oxidant-type plasticizer are that it contribute oxidizing as well ~s fuel elements to the competition, that it be physically compatible wit,' the polymer, and that its vapor pressure ovei the composition be low enough that the composi- tion will not change substantially over the rife of the propellant Nitroglvcerin was the original oxidant tyj-e ptas ticizer and n is still the roost used of thi,- type plasucizei in ihr Uni'td States It is usually pre- pared on the propellant plant site, by the nitration of glycerin w,J> mixtur ot nitric and sullunc acids Nitrate esters other th?_n nitroglycerin have ». so been used In many cases these plasticizers ax wokr than the ruiroceliulose, •wverthclcss, pi ope - lants in which they are contained are stil! knowr as double -base. Diethylene glycol dinitrate, DON, NOjtOCjH^jONOj, and trie thy lent glycol di- nitrate. TGN, NO;(OC'jH, jONOj, art the moat important of these nitrates The ether bonds in these esters axe considered advantageous in im- proving low temperature physical properties of the propellant. DGN his been used more abroad than in the United States Other nitrates for which feasibility is established art metric! trinitrate CHtC(CHaONOa), 1,2,3-butajwtriol trinitrate CHjONOjCHONOjCHONOaCHj l,2,4-butAnetnol trinitrate CHaONO1CHONO1CHaCHjONOa pctr,- CHsOHC(CH;ONOj)» dsethanohti'j amine duritrate (DINA) NOjNfCaH.ONOak 34*4. FaeMype pfcartirhwn. As u the case with the cxidaattype p!eit,’"izm, fuel type pUsuCuers must be physically compatible with the nitrocellu lose and should have sufficiently tow vapor pres sure to remain in the propellant during its life In contiast to the oxidant-type plasticizers, fuel- type plasticizers contribute no oxidant or only a little oxidant to the composition and thus tend to reduct th. force and flame temperature of the propellant It is difficult to draw a sharp line be- tween chemicals which are oxidant type plasu cizcrs and those which art fuel-typt plasticizers, this distinction is not reaD) very important and one is perhaps better ofl to consider both as Nas- tKizers Fuel-type plasticizers are frequently the same pl sharers that are found in commercial plastics and protective coating They are used because they are available in quantity at reason- able prie s They may be esters such as diethyl, di- methyl, di-n-butyl, or di-(2-ethylhexyl/phthalate, 49
ir.a,?! . the a,fi pates and sebavatei ntUo <•'”> “• ;«' I- зг- 'Л:. subK.tUte'j tifcA» such &s Ufa ir«(ailK4 «W CSC" miners’ leliv ».« used in ин- British curd its. I' the propcuant is made bv a p-,». ?ss involving a volatile solvent, the residusi kiieat brh*ve« v- a tuei type rlastici/e' an,. differs from the n ,t of the fuel-r-pc plash ciier.. only in that is has a hjgbwr: vap г pressure than is desirable G?a luai loss of resic iai yjheni on aging of ptopellar’-. -nil change ue ballistic characktistics. Choic- among the fuel-ivpe plasti- ciren is usually made on the basis of г variability and coat phis the contnbunon ic ’h* physical properties of the propellant. 36-5. Additives. In-- combustion proc sets of plastic monripropcUar.ts contain gases such as CO and H8 which ate combustibk in all If the tem- perature at time of discharge to the atmosphere is high enough, ignition of these exhaust products in air may take place. This phenomenon is known as flash, or more 'pec’ftcaliy secondary flash Flash is wv icurible in gunnery because it discloses the position of the piece ano tend; to interfere with the vision of the gunners, particularly during night firing In rockets flam can likewise afford data on the position of the launcher. Flash is also re span »;bk, a least in pan, for the attenuate® of radar signals to and from rocket rnissiks. interfering with guidance ano tekmetrv. Io avom or diminish flash, adds :« are frequently included in propel- lant comp ;-tiw.s to supprej this ignition These additives , v take the fnnri of poussirm salts which funcn -n аз negative catalysts for the re artions of CO and hydrogen with atmoenherw oxygen. Of the potassium salts available in ths United State;, potas, лп sulfate is the most fre- quently used, though potassium nitrate has been used in some prup*Uants Potusiurr cryolite has been used abroad in propellants mixed tr water slurry since it is insoluble in water. Potassium nitrate and barium mtra’e have been used in some prcpc 'ants to make the propellant more readily ignitible. Mete'lic tin and metallic bad “re examples o! add;t;‘-ca ;r, gun propeilartb tv reduce meta! foul'ig They function by lower- ing the melurg point ot copper which is deposited in the barrel by Urc projectile during travel through the bore Cencir lead and coppet salts have been found effective in lowering the pressure coefficient of hcimng rate in double haw tnckrt propellants Caibot biack and «thcr pvgnienis Су-г been need in son e propella-tts to provide opacity and thus Krtctt malfu'Kmm diie to !П“1йЧ! below tn? su: face at the site of mmvt imperfection:, b.trtnl wire either in chopped (опт- or strung continuously parallel i<? the vns of end-burning grains increases the -flcctiv; burning rate of grains in which they w incorporated by increasing ’he burning surface Other additives of claimed v.rtvr are found in some r>rops)la/ u. Solid products in the propellant eas resulting from th- incorporatou of additives contribute to smoke, which is objectionable fo. reasons similar to those for flash The amount of additive used for a given purpose, eg , flash suppression, must te conddered in the light of the contribution to «moke As discussed in the next section, carbon may also appear in smoke 57, BsdUrtk characteristics. Th: calorific v allies, flame temperatures, and gas volumes of plastic mcnopropeHants may be estimat’d from the dau of Table 2 fpag. 7). from which can be derived the force, characteristic velocity, and specific im- pulse as outlined in Paragraph 8 Calorific values range downward from a maxim 'tin of about 1 T calories per gram to quite ’-w or even negato* values It i. surprising perhap. that a propellam with a negative calorific value will bum to pro- duce a useful working fluid That it doe; so is due to the fact that thermodynamic equilibrium it not attained at low flame temperature and endothermic species appear in the gaseous products Fl "me tomperatures, T., constant volume may be somewhat over 700dcR for sporting or pistol propellants and may be below 20G0°R tor gat generator propellants The composition of the gaseous products may he determined as outiined in Paragraph 7. In gen- eral, only minor quantities of solid products will be found from the combustion of plastic mooo- propellano The solid product» are derived from the additives except that some cool-burning gas generator propellants tend to be smoky. The ttmoke is ca'bon derived from the propellant compos; tior; Choice of fuel-type plasticizers has a coe- siderahk effect on smok'.. It is claimed that long carbon chains and particularly benzene rings in the fuel-type plasticizers art more prone to smoke than ut sliort aliphatic chains 11 50
POLYMER CONCENTRATION. «Асе figvr* 28 ft./vent VeriLt folyrmti Cor^inirattor ЗА. Fhyssca) aroaertita. Plastic monopropellants «re thermoplastic, tTanslucent unless pigmented, and resemble generally the inert thermoplastics of cotmnenx. Many of tbe physical properties are ikttrmijed by the polymer cootenL probably best expressed in terms at ooooentratioo (weigh’ frac- tion multiplied by specific gravity) of polymer in the propellant Fipvrt 28 presents uata on the ultimate «treneth. deformation at rupture, crxi hygroscopic» ry typical of these propellants ЗА-l. lAbMie ab'uagttu Unplasticized niuo- cellulose hrs au ultimate uensile or compressive strength near 10,000 pit As plasticizers of any de senption are add d the strength decrease!, rapidly to values in th*, order У 2000 psi at a nitrocellu
to*e сспсегьи'.ог' of ° 9 g/cc and continues to decrease to SOO pai al 0.7 g/cc. 38- * MwBiiiod at naptm. L'npUstKiXffd »tmcdlulov£ 'l hww №M btltlk, Гм; — Hiring in either tension o- oarupressiou •' itu шал 10 percent deKtrnatJon. Fltsticucr» in. prove ihw provert?, to about 50 percent at a concert it *tio<i of 0.9 g cc and to 100 percent al 0.7 g cc. 34UJ. UAifcw. Ir ownnwci with c-thei thermo piu'H'e. plaitk Bjonopropellants have a tendency toward cold ftow that become* more pronounced ai the polymer concert t-atior, Is decreased. This tendency can be counteracted by сто»*-linking the polymer Bifunctional OH-reactsve chemicals such u diisocyanate* and anhydrides have been used (uccMfuOy." 33-4. Hyiywrupteifr, The bygro»cop*crty of anpititazed nitrocellulose propeBant is roughly the tame as that of the tjtrocetiukMe from which h u made Upon zddttioc d plasticizers the hygro acopidty of ргореЛапм drop* oA a little mote rapidly than can be accounted for V* simple dilu- tion of the mus-ccliukae, indicating that ы a rule piasbcioen tend to interfere somewhat with the accptioo of water by the unnjtraced OH groups of the ttitroceBuluae. M>3. Daoeky. The aasumption seems to bv gen- erally food that no volume changes occir during the mu tug of nitic-;iUulu*c propellants. Tbec- rental densities are computed according to the formula — = * — (*•; where a u the weight fraction s nd & the density of ingredient / Measured deusiro* of propellants an juit». dose to tbe values. 38-4. vapor раките. Nitrocellukxe itself u nonvolatile pituticuers in general do have twv urabl but tow vapo; prewurr*. Propellants in which tbeae plasticizer* ar» used should and acnuuiy do have vapor pressure* which arc the turn of toe partiaJ vapor prewires of tie plasti- cizes* and volatile*, including hygroscopic mots- tare and residua! advent* The vapor pressure of nitroglycerin over propellants ha* been exten arvely in vestige ted,'*11 without, however, subitan rial agreement as to its value. 38-7. f oeftrkit d tteswai сяцийьйои, Aval; frble data irxi'cstt a tbetmal ixpansitm cceflk eut for propedantj compris-r^ laigrh- nitrocellulose of about 10“’ in.-"in.'4C. This is coasi&rably prater than the expansicc cotSdai of chamber materials usually used Ccliutore acetate plastic hat about the инк exg «jecoc coefficient as nitro- cellulose propellant, sod this explains th; use of rellutote acetate ar peripheral inhibtUx for mar? large grains If the propellent is to be 'rase-bonded the exm.cnrr of a considerable dift’r-ental in rht expansion codfideuts requires that the propeuan. tx deformable, hair tow modulus and large defor- mation (e g . BUU, SP1A/M2). 34-8. Pfawteiry. Below a nitrocellutose concert- Vatiori 0* about 0.9 g '<x, propeUant* can be fanned under pressure a: temperatures considered safe for ma.nuhtotujiag operation: If the polymer woceatiatioc is much higner than this ir.Tit, vola tile aoivtnt trust be used in the maculae Luing process. When volatik aolvenls are au used, they are c. stomarily added in sufficient amount tr per- mit mixing and granulating at ambient temp<- ,a tore Thii requires adding enough solvent to tower the rvJymer coocehteatioo to about 0.6 j/tx 39. Tlwnui yrn|iMftai The thermal decora- pjwttou of mtroctUutoae propellants has been introduced in Paragraph 36-2 under the subject of atabdiner Thermal stability of plutic пккюргоре!- lanu is measured by the 134.5°C neat test” for aingie-baie propellants, by the 1204’ beat test” fos double-base propellents, and by the Tahani teat" for the larger grains used in rockets and gas generator* In addition a surveiHance trit” at iWF t65.5'C) is used to indscatc the useful life of propellants There tests are all ruu «I elevated temperature* in oroe to get an eod point, and are subject to the obyctiin th.it the icrupvi»ture co efficients of the decortijostltor. resetto?» are rot precisely known. In the 134.5 4 heat tert a life of 45 minutes is requned The 65.5eC surveillance lite ranges from about 1 year for a propellant con- taining 40 percent nitiog’yo’rin to about 3 year* f™ a plMticired «л»’t-bxse p.opeilint A sscapk of 40 percent nitroglycerin sporting propellant stored under water since 1899 i* still stable and reproduce* its original ballistics.” The devetoptnent of iuperremic aircraft carry lag munitions and propellant actuated derices has focused attention on it.* life of plastic шоаорго 52
ftfjrtr 2r Ke’et.-omn-ps .more F, F, and Q For Gun Frop^.'.Grrts pcl/anb a! elevated temper;.lure; 1 ix test io: tins, known as ilu. autoignition les'.11 is contpaiat vcl) new. arid no? many data are available Values of 2ftC‘ F for 1 hour and 25'J’F for Б hous arc typical of propellants cotiUnung 40 percent rulio- 40. Lses. Plastic nionopioptlian:= have been used in all types or eng.net, inc’uding gvn>, rovcet motors, and gas genetators 40-1, Gub prcipclUnb. V. ilh the exception of antiques, and sonic signalling ^uns as well as mo1, tog picture and television weapons where the puff is at leas’, ar imi'O-tant as any other rfi-л all guns use prop- liaots btaed or. nitroczllc- |<-s Figure 29 shows the relationships among fii'iie temperature. force. . , ana heat of ex plo-ton, (?. of selected gi r [ roptllar.ls from SI IA М2 du.ta sheets From these da’a it is ap- ftb’eni th»7 th.re i, rvr- systematic hainstn. c Fcr er-се between ’ing'c- an-. double ba;e p-opeliar,:s a' the same force level and indeed the force and flame temperature .л: be predicted reasonably from th? calon'K value ’be accuracy of such prediction approaches that of the Hirschfstder- Sherman calculation (Paragraph ?ч-;. If mor. pre- cision is needed, the exaci calcu’-adofi (Paragraph "7• J i Sin.uiu */€ рч-ifvv r»’ni-w tL • j.4.Hii’itt»ioj «доний* etrv become» unreliable ut values of (J somewhat below SO.- Cai ц. due to fa.lure to attain chemical equilibrium at the k-w resulting ‘.enqxrature in the calorirr-etric tomb Ther is a difference m physical properties h. twee., si’glt- ;md dcuh'e base propidanu at the same force level, ctoubk-base being softei because of lower polymer content in thr I nited States nilrotellulos ? concent!i-’lCHi. of uun ргч;ie ll.»l-o, have been held to a mrr.imun. of atxn.il 1 У g oc except fs. thin-webbed ignitron or trench mortar propellants This nas necessanh led to res dim1 vc’vcnt, particularly in prerellan-.v о large web That th-- high polymer content is not reai’y rf q-uirtd ‘ >r futtc'ioning Itt gons 5 Wit- :sxil by Or (act that gun propellants v- th polymer conc.ntf* S3
Fid' '* ЭС SpeclFc impuls* of DovUo-3om Fc-cl»1 Fropeftonft ai a Fiocbon о/ T, lion below 0.8 g cc have loog been used in guru abroad British Cordite S.U. and SC, и mi u ample of nuih a propellant Residual solvent can bv dutvd Cut Cn чьЬ ргОрсИлйкз with p-jj¥uiC4 conaentratioD u high ac 1.1 g/cc," and propel tanu with poSynier concentration below 0.9 g'cc car be manufactured without volatile solvent. 4b’1.1 frgf iB—ti for самим Barrel life and secondary flash are fee ton in the detection of propellant* for cannon. Probably the ьхм< widely used cannon propeUant in tbe United State* mill Ury sendee* u M6 Hotter propellant* art uaeu higher mnrHr ynprtrw к rwitritwi tK*n i* c«ebvered by Mb Cooter propellant* are used for guru in which Mb exhibit* muccte flash ur un- acceptable barrel erosioe. 44-1Л FrepeRaafe for «май araaa. For many yean 1MR prope'ar.i was tlw eandard propel- l«u for small nrro* Limited barrel life in high firing rate machine guns has now shown that tbe flame temperature, 2835‘K, of IMR is too high Cooter propeUant* such as M18, Г, = 2577’K, are do*» preferred A reefni *rvdy*' La! «hr»» о that other propellant* of tbe same T, as M18 will yield comparable barrel life 4Ф-1Л. FrapalMts tor asartars. High force has been the design goal of mortar propellant* Barrel erosion appears to be unimportant *od flash can be tolerated Flash can be eUaumued by mdng cooter propellant, but at the oost of increased charge weight *' ♦Л-Z. Rotfas aad pas gMarfoer yap Дм», FropeUanl» for rocket* and gas generator* have usually coostetereNy greater web than gun propel hum have For lfc*i reason tbe polymer oottoeob*- tx>n moat be kepr low m order to permit removsJ of voiadk soiveot or manufacture without volatile solvent. Ld Figure 50 are shown the meaMiHd ape- 54
08 BURNING RATE, r, AT lOOOpil, TO* F (in/мс) X > X 1 r ж X A : x I! — U ИИ s = 2 X-IS »; Tie T3? M ОЭК & о “ Й ©is x-e ] J₽N MT ISO 200 220 240 CALCULATED SPECIFIC IMPULSE , 1*^ fl*** fl. кпшч Mw W ftwMi law *ocfcw «mW Gm Ge«>ar«tar 35
сйк impulses of e number of double-base rocket ДофеUanti as a function of flame temperatv T,_ taken from selected SPIA/M2 data sheets. The significance of the line shown is merely that the points above the line are aU high because they were either measured at higher than standard pres- sure <x calculated, white those below the line were measured at lower than standard pressure or with inefficient expansion and should be corrected upward These data, representing for the most pari propellants in service use, were reported before the adoption of the standard practice of correcting measured specific tmpuhes to the standard condi- tions described in Paragraph 8-4. Bunting rates of douWc-bate rocket and gas generator propellants at 1000 psi, 70rF a* a func- tton of calculated specific impulse arc shown in Figure 31. 4B-2.L Prep M—li far rerkite, Design spectfi- catfons for rockets have usually required propel- lant burning rates between 0.25 and 0,5 incites per reomd is suitable geometries. For short range applications, short burning times and high accd- eratxxu may be more important than high burn- out velocity, and propettaats with higher burning rate than < .5 are used. With heavy patytoadh, specific impulse is frequently sacrificed to take ad- vantage of lower flame temperature and the aaso- cuted ability io use cheaper materials in the inert parts. PlMtic monopropeSaste in service use in- dude: M7 is need in the shoulder-fired rockets coe>- monfy knnwn м Ьвпоокш. High rate is attained by using potasetan perchlorate as a coe- stitneat in order to satisfy the requirement that bunang be complete before the rocket leaves the launching tube JPN was widely used during World War II, notably in the S.O-iacb HVAR. X~8 к a more recent high-rate реореймг fees мшМге than JPN io baUhtics chtetge* with chsug Mg temperature and pi sue tai flf/fi is used te a booster for ienacMag миМ target drone airrraft. N-3 is used to ths 2,73-foc* FFAA MMghqr Mow**** O1O is used ip the Hor-ай John rocket and in the booster (fit и stage) motor* for the Nike Ajax and Hercules, Terrier, sod Ts'os mum1'* OGK is used in the Terrier гоммпег motor. T16 is used in * tone charge projector. 4*-XX Prig rfla all far gas gmcnOan. A* con- trasted with rocket motors, gas generator* usually require «natter mass flow of propellant gu for long r timet, therefore tower bwtdag rates. The difference is qualitative, md for q>eci*lwed appli- cations * rocket motor may be best fitted with a gas geaersor-type propeflant and vice versa. Other requirement* for gas generator use an y be cool flame temperature or high performance, depend- ing on the application. Typical of docMe-bate gat generator propcDaat cumpositkms и X-13, used in the Side-winder gai generator i МП.-тМ44, Mfliwr; Standard, NorrMoclontre taA £>гЦяМсч io rtr ^HMuoution 4rm (4 febtoary 2. T L. Db«w. fte CkeMterrv of Pavdtr tad Exfto- otrti. Vol 11, p 392, Jofa WUry * Soot, lac.. New York, I М3 3 A Nobel, Bnlfeb PstaUi 1471/1Ш. 4341/IMS. (See alm T L. Dive, loc. cii, pp. 243 4) 4. JAN-N-244 NUivetttalaM (For Um io Etpiotirri! (31 Jah IM5) ahh XmrWflwM-J (21 December iMJy 5. E. C. Worden, rerfawfao of CtAJott EMtn. Vol I. Fan }, NltmetHuioie—Гйеогу and Proctict, p. 1750, D Via Nastnad Cow*«*y, Nee York, New York, 1P2I S H Mfcwdtagw, Л4» kaekmotefadam му*ч<«гкее Krritedangea. p. M, JsiaM faiagir, Bertie. Ger- unro, 1*12. damwiriiBt ta M L tofani, njrinl frt^trtlu of CtBuloM вя4 tu Dtrivottrot bt tohf rieo. itcMta E. TEoory of At VittoAty of DUmh fofatee of Loo^CEoh Cempeeetab, te R. On. tt of, (adttersl, CrWatew and Cofatiw DorfyoAnt. 2nd edteaa. Part Ш, p. IIX, latmnthari Pvt Vetter i, bic, Now York. New York, l»JJ.) 7. J. Bertha, Oorfooitroi of Cifalew. SetHoo t. He- •гемк fltern, la E, CM, el of. titeunk CrdMaoi •ad Ccfafar OarirePvM. ЗяЛ idtli Pert |L 741 Wunciteiri РаЫкйвга, tee., Hsw York, faw York. 1И4 BtoHMd Г
9. Califomjui InnjCBM of Tecbnoloty. Stabtluanc-n oj Srnolelru Fe*drr by Ethyl Centralite 1 Trcntfor- motion Product! o- Ethyl Ceruraitte tn Double Bate Parade,. OSRD 596’. October 1945 (SFlA Abaract No e)M.wl!sNos !!M J4I2) >0 F. WhltWiHth and С H Rygbv (to Imperial Chetnkal IflJuMne* Lonued). Canadian Paten i Ml,559 11937). li J H Oo&e). Сая Propellantt »i:h Croti tinned Nitrocrihiloce, Allegany BtlltHu Laboratory. Her culm Powder Company. ABL/MPR 4h ip 6 of Moethty Proaraw Report 44), I June 19’5 Coturact NOrd 1(M1). CONFIDENTIAL, Properties of Cross Linked Propellant,. ABF 'MPR 44 (p. 6 cf Monthly Profreaa Report 41), I October 195’ Connect NOrd KM J ’.CONFIDENT) Al. (WiA Abatract No 15565) 12 W deC Crater, Die Vtpor Preaaura of Glycerol Trautratt tad Czruie Giyro! Dini: rate», Ind Eng Cheat.. 11, 474 OW»> 11. F. M Eraaberper. I. C. Wyihe and L CMuo, Physt mi liuteMliry of DcoMe-ioae Propellanii Pan f. Vapor Preuure of Bafiutiie. Navi! Ordnaace Test Station. NOTj z«c, NAVORD I IM. 29 September 1949 (SPIA Abstract No 10544) 14 . MIL'STD-246, Propelitmta Sampbng. Tntpecwoti toad Testing Method 464.1.1—Heat Ted, llld' and 2J4J'C/(2f Juae t»5«l 15 . MU^STD-244, Pmpeilaau. Sampling. Impeerion end Tearing Method 406 I (T) Taiianl Гея <24 lune 1954). 16 F A ZiNrsws. el al. t < nnrel btelnarton of Knon-n Method! of Steb'lir? retting Nira! Pouder Flcter , Indian Head, Techbia! Report 25, 5 March 1950. CONFIDENTIAL tSPiA АЬцгай 102H) F A War. ma. it. L Atadenwn end P. M Ku. Evetearion of Solid PtOttellont Properiiet Part f —А Тьпгу о/ Cnr- rent Methods, SouIhwelt Pmrirch Imtiluu. Report R5 2Г. 5. lapuerj i»’9, CONFIDENTIAL (SPIA Abt’-tect No 19)911 17 . Kcrvufei Powder Ccwpiny. иирпЫнкм! da,» 14 MH-.D-26J49 (USAF). IMta Preeentenon Reqtrire- •neati tor tretr^~mrning Sift Handlott- otoeage .end Shipping Procedn-et Aeonaniical Poe bet M-cnori ernd Coenf-cwui (14 November |95S), MIL-C-25441 tUSAF), Cartridge, Gas Geneemng Solid PropeUant, Airrrafi and Motile, Secondary Poner Зуяеяи, Gen- end Specification For (21 January 1954) 19 A W B*Um. f-ffeel of lariat io v on Toto! ledoftle Content of 7~t Inch Stick Powder. Radford Ordaancc Workt Hercule* Powder Coer,potty, RD 1. 19 lune 1944 (SPIA Abstract No 07’6). The Modified M-2 Forrnnlcr.ori RD 12, 12 February 1945 (SPIA Ab stracJ No 1149). 20 Peteanh and Deeeloftment of an fmprosed Small Amu FropeUanu. Non-ErrOre EjtfmdeJ Double Bate PrcpeUoeu for Cobber .50. Hercaie Powder Com- pany. Kenvil, New Jency. Fisa! Report c< J! De oemh.'r 1956, Contract DA JtM)54ORD-l19JRD (SPIA AbatractNo 17.002) 21 A M Ball (to Herevia Powder Compaayi, U. S P»WM 2377^94(1941
uiariik 7 «OMPOSntS СОММШНО CtYSTALUNI MONOPROPHIANTS IN PLASTIC MONOPftOPKUANT BINDSKS 41. GvwtraL А» was shown in Chapter 5, cryt- tcftine monopropellants have limited feasibility м propelUnu, the itotitations being due to the di® adty to getting crystals of the аи and shape re- qufrvd for many app&abom, and to the fact that pure cbcmicah do not yield a coc&tuom spectrum of thennocbeoucal properties. The force or char- anerotic velocity of a given crystalline meuopro- peCant, while within the range cf desirable values for propellants, is addon opttoonm for a specific uac. These deficiencies are ятгеоае by accepting an available particle azr dtitribution or grist of the crystalline mooopropeOaM, and dispersing it to a plastic mooopropcOanL Such composites partake largely of the properties of the crystafiiae coen- poaent The function of the plank is to act as а мет at ary dthieat to permit enatniag the de- sand yeosBetry with acceptable physical proper- ties. and as a modifier to vary the thermochemical properties. The fidd of gun propellants ri the otdy field in which two-mcsiopropeflanr-ptiase composites have been widely adopted. Only those composites using nstruguatudine have been standardized by the United States military forces, although RDX com- pottles ’ have been demonstrated feaebie few gnu and rocket propellants aod ашоопгат nitrate ccurpcettes* have been studied at rocket or gm generator pr opr Hants. CoateM* three exptoeve taerafienta: fj whrocetaicae, nttrogtycena and nirrogwaradint, these propeBzwts are commonly known as "triple- bnee." 41. FanaainfioM. As with any c ran push t, each phnae asmt be separately fomiiiiirtnrt, aa wd aa (ha total амароаШпа. The (aapertamt cunaidtratioti cf the rrystafifre phase to grist, or putfeclt ЙЖ Md 4» dtotttastaB. la geaml (te Ibmi poo* db* it BMitrnd In Hhm мм лЛ Ы1ПМПМ&- dhw propcBeati foraatatod with dbyi семгаИк, *e aaatraMa tans » ауаМКпе compound with ths аКнраааЫкаа,* which кв&саам that As esntnBto w0 not be fat the Hadar ptrnas. ТШ might ba lam абааащеоза than to have tiu taaMtom to (ha binder phase, although such propeltaats have ям proven unstable The binder will have tn withstand a different set of mechanical forces during drying and tem- perature cycling from those oacouatered to a ptae- tic mooopropeQast, due to the presence of the сгупаШае material The bmden are usually well plasticized, cootainmg roughly equal weights of ortroceHtdoae and oxidant plasticaer. If stabihxen other than ethyl centrshte are used they will be found io the binder phase. Potassium salts, such as the mdtatt or ctyohte, stay be added to inhibit flash. 43. BsMc сЬапкММк». Doe to the low тоВм^йи- weight of the mrobtnrtno products of sitFG^pMofcniiov ргорсОяясв ot due same level cf force wiB have lower flame tempera- ture* T, than singk-pha« propellants. At the sasne level of flame temperature, nilroguanidtoe system prapelltats wifl have greater force than tiagte- phasr propeUanta. Advantage has been taire» «И this situation in the development of two separate series of propellants, for reduction of muzzle flmh and for increase of terr* В। Secondary muzzle flash is due to the rrtnbnstinH to air of the gases issuing from the stunk of the gun after projector exit These gases ab»*yt row- tain combustible i such as H* and CO. Among the factors controflmg their ignition are temperature and composition at the muede, tower tempera- tures and towm contents of combmtibtet decreet leg the tendency to produce astnafe flash. The pieaemH. of amafl twin anti of poiiam'mn salts also tonda to dbnfctiih flank by a ugntive catalytic eCecr on the reactions cf H> and 00 with aanos- pberk ozygia. bfonfiaahtag ataraguanidtoe prcpaitame wests as- pesimantod wM to tide country to (ha IWt, but present etondsrd cumpoeitiom cm bnmd on tin British Cordtis N, ffaetomd to m during WotM War II Tbs AaatteM M1SA1 am about (ba цмвв 44мнЬвм1м 1мвртмм sb Ав мвяврмрй^
TABLE 9. NOSrtASRING PROEELLAKTS M15AI 7)4 Oethte N Deewty. ? • tt !5! IM Fore*, F, fi-lb'lb ?J2.«№ 1J?,OCX? 319.000 3! 7.000 FImk temperature, T,. *K 2 5 Mr IKS 2*4! 2J70 Oat ngfocalar »ri*hi. M 21 1 21 7 21.2 22 € tent M6 and correspondingly greater force The reduction in flash compared with M6 u therefore due largely to the reduction of the rotnbwbbie fraction of the product gas The corresponding German mlroguanidine propellant' H considerabty cooler, employing dtethykne giycoi diwitrate m stead of nitroglycerin as the piasticszer Since M15A1 has greater force than M6, a some» ba! cooler propellant could still be used eflectiveb fen guns chambered for M6 pcopeDant Three non- flashing nitroguaiskJine propellants art shows fen coanparuce with Mt in TaMe 9. Two avenue* arc open for fonmdatiog cooler nitrogwuDdine propetiaat*. O&c is tc increase the fractioo of nitroguamdioe m the propellant « tbe cost of a decreased binder fraction. This may be limited by a coerespoetfeg edrerse effect on physical properties. The other course h to de- crease the calorific value of the binder phase by rcbstitutifig a cooler piasocizer for that presently used. Such a cooler plasticizer may be dsethyletx glycol dinitrate as m the German formulation or a cooler mixture of nitroglycerin and fuel-type piasficiaer. 02. H^fi force -**—-y-- Jwe prapeflaste. For certain field uses it is desired to give a pro- jectile the highest possible muzzle velocity. To a first approximation the muzzle velocity should be proportional to the force of the propellant. The hatitation co attairment of muzzle velocity by increasing propellant force it that gun erosion is a function of combustion terrc-rrature and increases rapidly above some temperature level An eco- nomic balance between muzzle velocity and gun west for weapons of 3 -inch or larger bort indi- cate* that the cost in barrel hfe is too high to pay for added muzzle velocity i! the gun chamber gas temperature it higher than about 3000’ К For rapid-fire »t4xni the economic chamber gas tem- penr»t ts comsderabiy lower than 3000* К Aj shown in Table 10, propellants containing mtroguamdine are cosuidetnbiy better than pro- peSawtt without vitroguanidim in the iWmtoan cd tcace within a permitted maximum gas tempera- ture The ргореИавц Ml? and T36 contain nitro- gusredtne. MIO and М2 do not contain it. High force mtroguamdme propellants were ap- parently originally developed in the United State* ’ Further development of tbs type propellant de- pends or the abilrty to increase the friction of mtroguanidine in the prepeflam, presently limited by physical properties 44. Physical prsomltea. The physical proper- ties of these composite* differ consderaMy front those of the plastic mersoprope Hants They »rr opaque, chalky white in color unless glazed, and exhibit generally lover physical strength. As may- be seen by comparison with the fuel binder com powtes, Chapter 9, the decrease in physical prop- erties is not necessarily due to the volume percent of isDer It is more probably due to the shape of the nitroguastidiDe crystals, which are needle* TABU IB UGH FOfltCB PBOPBLLAfm Ml? TH MIO М2 nsasky,» 147 IM 14? 1 *5 Parse, F, М4ЛМ» jmjoo mow мимо РЫм umparaturs, 'k M17 №40 MW ЭН» Oas awiataiar wsfifSt. M 23 1 212 24* 21» 99
О. Ом» SmHm ef 1м» Ом 6<м. G»<iW №й, Пх MfuJRrKu «О
With an optimum oysl*! shape, a volume frac txx, of Ю percent or a weight fraction of a httie mou than 70 percent should be feasible without иъ.'-us degradation of physical properties er manu f.icturahiilty As the rntroguanidirx-filkd propel ‘writs are customarily гanufactured by solvent extrusion. iKHiparalkl orientation of needles may be expected to cause bridging and interfere with norm shrinkage during drying The resulting residual stresses in the binder phase may exp’ai.n the physical property deficiencies of these propel Janis Nitroguanidine, has bein prepared’ with a tncr. favorable crysiil habit which itnp'oved the mar.-tfacturabibn of existing formulations. It :s interesting to note that in the early American studies, experimental propellants containing up to RO percent nitroguanidine were fired in a Tillery -beces at Aberdeen Proving Ground ' 43. Theraul propertie*. The аума!!|ги mono- propeliarr . «’» generally more stable than plastK riKHWpropdlarits, becsrsing ca-ubli. only near their melting points The aging of cotnpetAes con- fining them is therefore due mainly to the binder, which is a plastic monopropellant Stability Jests dependent on measuring the evolution of oxides »rf nitrogen from a fixed weight of propellant in dKW‘< better siabth’.y for these composite? than for oedinaij nhcocelluhw mooupjopeiUn:^ this indicated increased s'aouii) o>*,r not r* real Auto- ignition temperatures for various lengths of capo- sure may be expected to be higher than for the binder акте, due to this *мпе binder dilution, provided that the melting posnfs of the cry talline moncprupellants ut not too closely approached in the teat. 46> MaaufaKtarHg ргосм». The manufacturing process used for the nitroguarddine propellants in the United States has been uniformly solvent ea- тмкг. The nitrorellulote concentration in the binder рЬвк is low mougn to suggest that a sob rentiew procedure rouid be used The amount of sofveot used is quite low and the propellant dunng «teuriw» is very soft to that ii is tometimes neces- wiay «5 wy twe aSHlwicd toranu ралмяу before cutting, n order not Io deforr.i the cross section at tin cut Removal of solvent from the composites is much more rapid, due possibly to diffusion of solvent within the grain along the crystal-plastic interfaces This does not mean that drying times should be reduced In order to make a good quality grain it is necessary to use lower drying temperatures and times comparable m ihos« fo? conventional smokeless powders in order to avoid steep solvent grad'ents and resulting distortion and cr acting A photomicrograph of a cross section of a intro guanidine propellant grain' is shown in Figure 32. КЕгежЮТгЖЗ I £ J Zander, Developmt di ot Imprond Propeflanli. Ptatinn, Arwtud Technics' Report No 1921. 5 June 19 ’3, Ord Pro; TAI-3601, CONFIDENTIAL (S?IA Ab»tr»ci No 13,23*1. 2 Redslonr Anenst {^uurterfy Report [Solid Propefhnj and Ipmier D:relopmem\ Rep-: No 3M?N24 (Oct.- Dec 1957J. ! Juuity 1956. CONFIDENTIAL (SPIA Abslract No ifc.M'i 3 J N Print tbs mesne мщлтеви ю Imperial Chem icai Industraes, Ltd j, L S Peteru 1.557.463 (1951). 4 R A Cooley. J Waset and К Mulo». Gerr-ая Ptrn,1e~ [><. e lopmr ru Between 19 ft anti 1942 (A Translation of <b* Omas Book Du Getohrttiodeint by L‘ Gall»Ui). Cshfonua I'niiun of Tecbndojy. IS September 1945, NAVORD 43-45 (SPIA Abstract Pio ?5»7|. 5 A W Baum, ) G Ft’ickj and R Winer, PeoJiteoon of h'iirofujnidine Propellent in Seterof Cennon Pondn Grcnnlaitonj Radford Ordaanct Worki Hercules Powder Cornpar,,. Radford RD 3, 11 Jut4 1945 (SPI A Abstract No l«J) 6 V Milsnc R E»n»». S Skohuk and F C Thames Prapurarion о/ H<f6*Ba/3-Denary \iuogw^it/ine. Nasal Powder Fan- rs liwhap Heed. Tech-P.r port ’no 66, hdukb *0ii, 14 December 1953. CONFIDENTIAL (SPIA Abstiacr No 1*0»), J Cobec and R A Henry. А Лгн Ме1>ю4 for ike Preoarshon of Kirrtrfuanidine niih Hifh Bnll Den ary No*! Ordnance Te*i Station NOTS 112 NAVORD 1062 31 December 194«, CONFIDEN TIAL (SPIA Aburacs No 3640, 7 W F Jackaot, (E 1 du Peer de Nemouti a Com- Ray. toe 1 pnvaUe coenmunkation. F C W. Hock HerroKopicei CitmiMlion of Propel mall Coatainiaj NitrofmsnUine HercuHs Powder С-лпраау, Rl 31 12 25 Auguu (954. CONFIDEN TUL tar l А А вала» No IJAHi)
CHAPTV 8 MANUFACTURING FROCfSSFS FOR SMOKfLISS POWtHR 47, GevraL No one manufacturing process *iii produce (.be *!кне spccwum of pi as tic mono- propellap’s As is ihe case v Ji commercial inert thermoplastics, a wide *arnty of manufacturing processes his beer developed io make different propellant gr*i.is Near)) ciery fabrication proc ем used by the commercial plastics industry has been used for propellants >n fact some precesses used for propellants base not yet been used by the plastics industry lor any given process the dif- ference between use for propelianis and use for inert plastics is that the consequences of a fire during processing propellants are sesere and ex- traordinary piecautions mus' be taken to prevent fires and to control them if they do occur Aside from details in the design of equipment, the most striking feature of propellant manufacturing proc- esses has been die requirement to handle the ma Serial in process in batches of &iite size, operated from other operations by dotance- such that the loss of a charge and its containing equipnient will not entail propagation to neighboring operations This requirement has, until recently, discouraged th development of continuous processes, and is «till a problem to people currently working on continuous processes Important processes used lor nitrocellulose sys- tem propellants are solvent extrusion, solvent emulsion, rolling of sheets, sdveiitiess extrusion, the cast double-base process, and slurry casting Since nitrocellulose is commonly manufactured alac at the propellant ladlity, its manufacture too is described here. 4*. biMfuraHstfoee. The process installed in the ordnance works, and also widely used comaier- cially, is the Du Font mechanical dipping process ' Continuous processes have been installed by one or more commercial producers bu’ the details have not been published It is believed that these proc esses are engineering adaptations of the mechani- al dipping process The flowsheet of the Du Pont process is shown in Figure 33 Cellulose in the form of cotton linters is dried on a nt ing belt in a tunnel drier to a moisture con- tent well below 1 percent. Alternatively, sheeted wood cdbtlose’ may be dried in the drier and then shredded. The dried cellulose and mixed nitrating acid are introduced concurrently into the nitrator (Figure 34; where the cellulose <s converted to nitrocellulose At the end of the nitration cycle, about 25 to 30 minutes, the nitrator is discharged Try gravity to tbe centrifugal wringer (Figure 35j where the spent acid is removed Part cf the spent arid is sent back to the process for reuse after butting sp with fresh acid The remainder is re worked to remove from the system the water picked up from the nitration The wrung nitro- cellulose, wet with spent acid, is quickly drowned and transferred to the boiling tubs (Figure 36) There, fur a period of several hours’ depending on the degree of nitration of the nitrocclluloie, it is boiled in the weak aetd resulting from the dilution of the spent arid nc< removed in the wringing operation This boiling treatment serves to hydro lyze am sulfate ester formed during the miration The niuoceuiuose i> next pulped, ir. one or «црмте И NkrwcWhdaM Atemfaefvr* 62
V t Алнл I >4 ^aJL*^** М^^Ьм; w^> ^Iw^wjw *>
г a лжи*.' fif/w* 35. NUrocoKvfaie W/ingeri 64
iiivil niiuin eng r ' F Simitar Ю tK,”SC Us^-d ;” the papermaking tiKiusti). and final!) “peached’ 01 boiled in a slight!) alkaline solution to ncutialize and remove any residual acid. Thorough washing completes the purification cycle In ordei to accu mulate lots of sufficient size, or to produce a mixed nitration grade such- as military blind, poacher batches are blended in blending tub=. 1 tie (inishcd nitrocellulose is centrifugal!; wiuiig io a water content of abeu! 25 to 30 percent for tr<m*fe: '_> propellant operations 4»L Sttrotr» corkiest. The degree of nitration is controlled by tbe equilibrium between the nitro- cellulose and the spent acid 1 As :hc acid pene- trates the cellulose panicle the surface is first nitrated to equilibrium with the f.esh acid The toid, bcvurrnrig utiuteo 0) the residual moisture in tbe cellulose and afxr by the by product wa'er of the nitration reaction perseuates on trirough the particle, leaving behind rutrocellu.osc of slighGy decreasinj. dcjie* of substitution 1 ne first rntra tiori rcacuon л qui” r^piC. but subscqutni equi- libration in acid of dJlerent composition is much slower and is not ccnip'e'j by the end of the nitration of-.ration For this reason, csiefui frac Uizaation of mtrocd'ukzK- reveals a spectrum of nitrogen contents in tire niriex cliuios*. Cotton hnurs. finer» -4uch have thin cell walls arid enough twist to keep them essentia’!) apart in the nitistot produce a r>iUtXtllulo>i. of a narrower substitution sp>eclruin tian wood cellulose shreds where regions of compaction are found The cclin- losc-acid <atio for wood cellulose is high.i th*n 65
that for cotton, resulting in a greater change of acid strength during <hc nitration operation This adds tc :hv ‘.s'dth of the nitration spectrum for the v.ckxj nitrocellulose- I inaih . * hde cotton cellulose ts almost pure polymerized dextran. wcaxJ cellu tose usually contains an admixture of other sugars such as xylan and mannan These become nitrated and their nitrates burn like nitrated dextran, but they have secondary effects or, the physical strength of the polymer and its solution properties. For most purposes wood nitrocellulose is a com- plete substitute for cottar, nitrocellulose Transpiration of moist air in the wrutgn can cause a lowering of the nitrogen level by denitra- tion. A Jight hydrolysis Occurs also in the boiling operation Poth of these effects ar miner in a well-conducted operation 44-J. SohtbiMty. At 12 6 percent nitrogen or 12 2 percent nitrogen niiro~?i>uk4c is miscible rn all proportions with ether-alcohol Since the nitro- gen content measured is tne average across a spec truin, a poorly nitrated cellules: with average nitrogen content in the. soit'bk range may contain fractions either more or less highly substituted than art completely miscible. In such cases this weald be detected by a residue in the solubility determination 1 Guncotton contains a small frac Iron that is soluble, either by re&son of low sub- stitution or low degree of polymerization. 4S-3, Viscosity The viscosity of nitrocellulose is determined by the viscosity (degree of polymeri- zation) of the original cellulose and by the nduc- lion of the degree of polymerization incident to the nitrocellulose manufacturing operations Most «.h il.is itU'.^hun (xvuiy duitiig inc niiraikm мер «here n is. ik-pcndcnt on the niimion tempera- rure Higher nitrating temperatures result in Jowei viscosity nitrocelluloses. 4S-4. Sigwifteaece of aitroceMote properties. Of the three properties discussed above only the degree of nihation has ballistic significance, affect- ing the molecular weight and temperature of the combustion products In order to manufacture a propeiiani of a specified force, r, (nr specific in, pulse) one must either have the proper nitration of the nitrocellulose от compensate for the differ- ence between the prescribed nitrocellulose and th? nitrucelluJote ri band by adjusting the proportion of oxidant plasticizer and fuel plasticizer. In a volume production operation it is preferable io maintain ihe nitration degree of the nitrocellulose constant, by- control of the nitration operation and by blending, rather than to adjust the foimula The viscosity and solubility have secondary efftcc- in the rr inufaclunng operations in th?t they effect the amount of solvent (and plasticizer) required to work the propellant This is particular’' 'rue during the solvent extrusion operation wi be applied pressure is constant and requires approxi mattly constant plasticity of the green (solvent- >ve: I propellant The finished di-nenvons of the propellant are determined by the solvent content and the die dimensions, so that if the plasticity ii controlled by varying solvent content the dimen- sional control is forfeited. Similarly for solventleu extrusions the finished dimensions arc controUed by extrusion temperature and die size, md if tem- perature i are changed to control plasticity during extrusion, control of dimensions is less good For these reasons nitrocellulose specifications cd) for control of solubility and viscosity aa well as con- trol of degree of ratratiun 49. Solvent i sfradin In Figure 26 (page 45), the line S3 divides the polygon PABC into two regions. Below 55 the physical properties of the system are such that the composition can be worked and formed at tenable temperatures Above the line 55 they cannot be so worked. A composition X in the upper region can be made only by a process using a volatile solvent which is subsequently removed. A prop:I)ant made by a volatile solvent process always contains some residua' solvent, and residual solvent is one form of fuel l?*.!r!zcr Op? first cstsWish в cumposiuon X' such tha: thv addition of the re- sidual solvent to A" will produce X. To the com- position A" is added enough volatile solvent to enable the propellant to be processed. This results in the composition X" in the mixer which is well below the line 55 Composition X" is frequently so far to the left of line PH that the mix will not bum without air, and the hazard situation is thereby somewhat diminished. Solvent evaporates during procevsing and the composition ot the ma- terial in process creeps back toward X it must not cross the line 55 until after the last forming operation has been completed Final drying leas es ihe material a' composition X. Note that X', X. X", and P art collinear 66
Hfwr >*r. Лч'лннж гюпятоп rrwwi For nitrocrlhdoses used for propeliwiu m the United Stales the position of the hoc S3 corre- sponds roughly to а mtrocstOulftr coocen (ration (weight fraction multiplied by propeibult density) tn the finished propellant of about 1.0 g/cc. A volatile solvent process must be used for aJI pro- pellants with a greatc nitrocellulose concentration than this. Tbe solvent extrusion process is some- times used for propellants with lower nitrocellu- lose concentration in order to reduce the calorific value of the mix Because the residual solvent con- tent increases with polymer content and with the web, the «olvcni extrusion process can be used only on grains with fairly thin webs. It is widely ur-ed for propellants for guns, including small arms ; nd sporting pieces The flov sheet of the solvent extrusion process :s r>hown in Figure 37. The essential operations of the solvent extru- ion ргссем are mixing, forming, removal of sol- vent, and finishing. To these operations have been added a number of auxiliary rjr»-r»tjr«s ****-*£" d to save operation time and improve the quality of the product As indicated by tlsc dotted lines, these auxiliary operations arc not invariably used. 49-1. Mfartag. Tbe heart of tbe mixing opera- tion is the sigma blade mixer, shown in discharge position in Figure 38 To this mixer are added all of the ingredients and vetvents used in the par- ticular propellant, and it is the function of the mixer to mix them thoroughly into a tingle homo- geneous plastic phase. The sigma blade mixer ir. capable of a good mixing job but it has certain disadvantages. The shafts of the sigma blades pat* through the end walls of the mixer below the upper surface of the materia! being mixed The treat- ment of the glands through which the shafts pass is different for different types ot propellant being processed For double-base propellant it is cus- tomary to remove the packing, leaving a cle*renc* between ’he shaft and tbe wall aperture. A small amount d the mix leaks out through this clear- ance and must be collected and destroyed, ft is recognized that a mixer «• ithout submerged glands would be preferable. 49-1.1. Pr wiling upuatiuw- Tbe ingredients may be added singly or in combinations, if a combined add is made, a premixing operation is required. Thus nitrocellulose is premixed with alcohol by displacing tbe water, present in tbe nitrocellulose as received, in a hydraulic press equipped to pass alcohol through the block under pressure. The dehy press has two rams The basket is first filled with loose, waler-wet nitrocellulose Tbe press is then closed and the nitroceUuioae compressed to a "block" tv express a portion of 67
V В Алку Агмямр Fvur* 3g. Ярм 6bMk MiMt the waler. Alcohol и then pumped through the Mock, disputing the remainder of the water. The drarydnttrd block is broken, sometimes in a "block breaker” or picking roU, wmetuncs by hand dur- ing the charging of the sigma blade mixer, some' tares by the sigma blade iteett during the mixing operation. Addition of rtf’ ’ogiycertn or ether oxidant plac- bciirr to the dehydrated rutroceL’ukne it usually, tat Got always, accomplished in the Schroeder bowl »bo.t> in Figure 39. The purpose of this is to avoid the presence of a free ratroslycerin phase in the sigma blade mixer at any time. NitoceUu lose and nitroglycerin an sometime* mixed in water starry, followed by drying and re-wetting with solvent before mixing tn the sigma Made taxer. Fuel-type plasticizer' and solvent-soluble addi- tive* may be dissolved in the solvent before adding to the sigma Made mixer The sotvents used tn the united States tor solvent-extrusion process propellants are usually 3 ether: 1 alcohol by weight for single-base pro- pellants and about I acctooe; 1 alcohol tor double- base. Other solvent system», including esters, are feasible 49-1X Fist sepsis Mads miltag egwrataua. Fost-sigma Made, mixing epervtion? are also scene- time' employed to shorten the sigma Made mixer cycle rad tc '«tqxvve the quahty of the mix. The maceratar, ».«o*n in Figure 40, works the mix on toothed roils, subjects it to a vigorous tearing actao, and reduces the talk density of the finished sigma blade charge, particularly if the fiber struc- ture has not been completely destroyed at that
69
и а. г*> Htinri 40, Ммагвавг
»•- — 11 и------------* 71
potot The macaroni or screemng press wort» the ргореСам by Ito* through screen» aod die», wb- jed>4 it to shear force* It tcrves also to filler oat iammptetcly ctetaided partirlr; of tKtroceSsfcsc remaining after miring at weD a* foreigB bodies. 49 2. FsraBfog. The cytindr al surfaces of the •nan are fanned by ettrarioa thrnpgh a die, ming either hortocutte or vertical fcydrufir presses. The the dhtemscm mmt be tech ta to yidd a green (toiveut-wet) strand of sncb cross section thee on «obsequent drying the final dsmemiom wifi be m designed The shrinkage of propeflant it atm rar entinfr n the став aecrion and the volumes of prnpiflnil bj wiwet are approsimaiety аЛЛ- ttvc, ao the desired preen dfoseuteoao are rendfly The charge far the fcfabmg press a prepared by corseting в a btockiag press wfoeb s a hydraulic pres working «gainst a dosed cad. A «waiter blockfag operation known as prbbio^fag precedes fas macaroni openaion if med. fa Rgjara 41 an shmm steanfa санц^ар from the UMcartwi press and entering the blocking press. Banded strnedb accent to length, nocafly «fide stft ccetataang sniviwt The equipment far thia vurie» *M the grata kregrt A orttiag я schist- med far gon propellant is down in Figure 42. The caning knives an monneed on a rotating Mk, and the strand is fad into the ararhinr by feed rofls synttaoniaed with the mrnng head. 4M, ftsmeval ta sefranL Ute mirheteun of rttivsni removal invoives ddfasson of the solvent <a ifte ratface of the pans and evaporstioo from me green 1Be rate ta Мшив controls the drying rase, the amCaee of the grain being aonmfly dry. Ftastictasd compctetiom dry more rapidly dhan unpfasticiasd, ааЛ thte webs dry to lower residnai nfac* ccflBMt Айв Afak wvbv wtAin tAnMt fa the amsadsetmt of triads hmr propeflants She «atoms» are recovered far ream. Ufa is not oedtem* done with h nksdr ban propeflauta be- come the recovered solvent» would be contann- ntata with atauglyceto. Capital and operating nosh nr rectaua item steely far reme outvvigh the vtitas of fce recovered soiveam. The smonm tf aahnm need with these arose highly ptastictoed it coesiArtbty 1см Abb Abk tied fat After omet of the advent hm been removed from stngie-baoe pevders. the final stapes of sol- vent reaeoval may be accomplished undsr water in order to shore» the total elapsed thne. The water aasiste sotwHit dtfesioa by preventing pre- mature formation of an napcrvfaws fata an the propefited surface. A final air dry re mum the, water. 4M, Ptefahtete. Frcpetiaats tor meal! areas аму tn coated wbh e dsteneat pfastictaei to resard Bn evutatim dretag early tnreri of the psinjistih. This operation is performed in a rotating "sweetie** barrel, sfasdar to equipment med far mgar-oosting flflfa. wiBBce Ab hik bombmI it Adwb in Hgure 45. The barrel is equipped with a ware- water jacket to heat the cLn-ge to a tomperatare where the coating agent wiB flow evenly onto the grams and be driven into the outer Iryro The фш shown in Figarc 27 (page 47) has been sc n Uli. Some prooetimte are “gfamd” or coated with graphite to decreme the accaaaafattoa of static etectnrity during handflag and to tacnaoe the baft density through better parting Thto apur- atioc is also psrforeed in a rutteing barrel, wbfah may be m aUjackoted sweetie barrel or a targre barrel on ahoriaantal asfa. fiupoflatti a* this stage ему contain taflaigs from the cutting operation, cheaters cf gnim from the drying opt r shorn, and duals of vartom do- are removed by ocreealnp. Beremuog is wmn^y arrnrapWirii dry just before Mradhg As res alter- aate procedure aermmpg taagt be done wet with water tioftowing the coating oparatton. Al MtWBr<HHra0M propn- foots art afosost fovarioMy mad to maltipfa-grato charges, they are blended toto toteepmatafag up to 500,000 pounds. Thss btatefing asap he done л a tower, to which case the entire lot fa Uton to the top of the sower and aftosmd to caacado oner hori- somai balflri. Aternotively bitndfag aaaf be done in a barrel, in which cane a widiir of prwbfands art mode, о barrel dsarge at a dace, and the flute oiead is accosspnaaed by Maadfag to toe bonti of айфкт from each prebtemt For barrel МиПц, Ав jfaflMA сфсоАсв bmqt соввйМА dfad. Vtopsfanfo rente by iterate reteaafau. Praducte cd the mired estemfan procure toafade sporting powder ta fore of dbfts anti chest tubes; stagfe-bere prapeflaato far imtel sems amb 72
и в rtaMTW* Ял#*'* Алтм» Figpr* 43 CtHUng МкМа» 73
ап ПЛ; for rananai, to i tiling Ml, MIO, M12, М», Mt4, iX-ei; dowwr hnw gea пгт^кп йь ctadkw М2, MS. M9, tbe British Cordate» CD *d WM; douMe-bsne rocket propelbot M7. Data sheets far ев al these propeOants nay be found in the РюреЛвм Манна/ SMA/M2. Casting pew den weed as interim Даю in the cast double-base process may be made by solvent extrusion, as are atao the tripie-beae gun propeUaot» riiemrrrl in Chapter 7. 96. SOhaM лттТгТтг r»r.dg) A second aad ladktoBy dtflerect process* ’ ше* a **?***a» eoirenf to tons propellant as spheres and tested shaoet acid as Bah Powder * The Bow- sheet at this process is shown to Figure 44, and the product ш Figure 45. °TV*dww*£ Ы Ota Ммкамм Ctatacal CwjvratiM •B-L Faenhqi apanemna. The process staets wiw me forwwnon o# spheriroi purtiem of ичго- ceSufoee. The equipment for this operatiuu com priaes a dosed, steam-jacketed vessel or “still," shown in Figure 4b, equipped with pnddie-befle or double turbine pgHatioa and an auxiliary ad- vent recovery system Nrtrocelluioer. is dispersed in a nomoivetit (water) and a sotvenl (ethyl ace- Uta), a ttsbiliscT (4фЬшу1в8ШМ) sod pcrittpt other additives are added. Additives introduced at this point mist be insotable in water and if oystal- hnc they must have a particle size that is maO com- pered to the size of the finisbed propefiant spheres When mixed and heated the ingiedieut« fora sepa- rate water and Iscquer pbaaes. St^abzation of redasaKd nitroceOutase' or even at inctanpietefy atabttaed new nteoceDuioae stifi contafadng asaB nnstofs of iningtoBc acid can be ncconsphsbed in 74
Figvra 44. Sotvvnf Frocau this low viscosity lacquer phase, «-ring chalk as an additive to neutralize the acid When a smooth lacquer has formed, a protective colloid is added to form aa eaiulsioo The size aod tax distribution of the lacquer particles in this emufoce are con trolled by the kind and degree of agitation. A salt is then added to draw dissolved and emulsifies water by osmosis from the lacquer droplets Omis- sion at the salt wilts ir a lower density product. The solvent is distilled off by raising the tempera- tore ard is recovered for reuse. When solvent re- moval is complete, the slurry is cooled, dew Hired, and washed to remove the salt and protective col- loid. The washed product is reslurried and pumped to the screening operation. Screening is done wet on a series of vibrating or rotary screens, yielding one or more sizes for further processing to diflereot end products The grain size range of any cut is within about 10 to 15 percen, of the average of the cut. Larger spheres and more uniform sizes may be produced by a modification' * of the above proc- ess ut winch the lacquer is made up in the absence of nonsoivent, extruded via a metering pomp and orifice plate as strands into л proportionate stream £% nc&sdvmt Cvtitatuaisg the p-'Dicctivc cvutnu, aod nit io square cylinders. The cylinden assume а spherical shape during transfer to the still where denaty adjustment (salt) and solvent removal an aowwrpiishrd as described above. Sphere* 50 to 75 micros» in character suitable for slurry casting, described bekrw, are made" " by emulsifying st high shear, heating the emulsion to a temperature well above the atmospheric boil- ing point, and flash evaporating the solvent. These spheres may then be plasticized as described below They are usually coaled with a smah amount of casting plasticizer prior to drying to minimize accwnulaticn of a static charge when dry M-2. tecorpanMan of pteatteiaen. Screened cuts, still in water slurry , arc weighed pycoometn- caiiy and pumped into a second stili The slurry is again -teated and plasticizers (fuel and'or oxidant) are added." " If nitroglycerin is used it is added in the form of solvent sc'ution The plasticizer, or plasticizer solution, is emulsified before addition tc the slurry Penetration of the solvent into the nitrocellulose spheres is я time-temperature func- tion and may be controlled to leave a plasticizer gradient within ihe granule. When the impregna- tion has been completed the solvent is removed, having a controlled amount of solvent in the granules tc facilitate the coating oprratinn Ftadshiag aperatfows. Coating agents are again added as emulsions and the operation of coating is performed at controlled time and tem- perature. In order to get more closely controlled web, the coated propellant may next be passed through sizing rolls which flatten the larger bails The prod- uct is then dried and finished in the same way as the corresponding solve nt -exruded propellants 75
76
figura 4f. Still XVgrM»yi£j4iti^’C2 to w*^«i d'Jr'."r the slurry operations, may be applie. to the sur- ioce of the grains ri'inng the glazing operation SI. ReAed «beet preen». If the propellant is to be used in the form of she.tx, strip, cubes, or sense other font, of rectangular geometry, it may be suitably made by a rolled sheet process. This is basically the process originally used by Nobel, and is oore extensiseiy used abroad <har. in the United cnatl) tin, tr-.’WjlriA I IVJ LU29 ^ZIVW33 r3 SUU«lt III Figure 47. Sl-1 Mixfag. A great deai of Pexibility is pos- wbie within this process Mixing may be accom- plished either with or without the use of volatile solvent in a Sc’ racder mixer or in a sigma blade- mixer, or it may take place in wa’er slurry If slurry mixing is used, the still fibrous mix, ш paste, m<>V Vw' rli- ”i'«*е»Л Vwt -i оеп‘«Д|'«о -”S' jifsinr. • /-«T лл j *a V к> К - -» Оа • - - V- W 1 * К S-* 1* ** t *-* * Mb kJ , |Ъ M к I through a fiber 01 a nutsch Further eUrainaUor, of wa’er may be accomplished by air-dry ing Final ebniinatior' of water or volatile solvent is usually accomplished durinт the tolling operation at the time that the oropellam is conso’idated to a sheet, although dry и s operations may be used between passes over the rol's or after the conclusion of the rolbng operation 51-2. RoUiag. Ъе loll milk may be eten-rneed (both rolls rotating at the s?me peripheral speed) or diftercnnal (o.-.c roll faster than the other), or a combination of differential and even speed mills may be used Outside the United States most tolling operations are conducted on even speed rolls Iо this operation ths first pass forms a sheet, which it folded and or rotated for each succeed ing pass In the United S'ates differential rolling is
TRENCH MORTAR tHCREMENT WATER SLUftRV even-sheer kw SCHRAEOER DIFFERENTIAL SLIT •КМй RLAOE CHOP HUNCH Яуц> О. Rdbrf SkMt й*вам ETR1R CURE V. A. МчАих» O'A i i W«Mv MMK 7«
V 9 Va, МгФ» ММ 79
«MuMtwfr read. Tbe charge Wtem to the cooler rail and ранга nepeniedfr throngb the bite мйН it n (tripped off. Л daflenotial roO cycle b that property idcntM^ by tine sad rod Ггшрггатше mite ad of by natabar of perms. A typical ratt odD is shown to Fjgore 4g. Я-1 П*М* Strip powder b nude by to- ting the sheet *4 epnipmto rirattar to that shown is Figure 49 in which rotating knives bear «a the sheet ra it patera over a feed rader. Cobra BBB7 вв В9ПЯ00 vf CwMg рвекфм <ж опрв wrd a gfattotiac. or by feeding sheet slock through a direr in which dtafag and chopping an done in CBO epCVWMML nmVBVNN ИИ^ВВ WEB BB «MBS may be poached from the sheet» with a rale dfe. Daring World War 11 trench mortar facranram as dhsatratad m Hgsre 30 were trade bora toet powder by the segoeace of operetta!»; tewing • рвсЙ^в <rf ilMtt togBChtf 1ов|й1вЛмЦр BBtay a яНм xbiL вмаВа! k> fte ямам. юВ> dng астата the aeant, and riaratanooedy pouch Wg hotel with a poach pram. 49» SotasMtere ^^taarion ^naeanu Propettants with a ohrnorlteiow coaocatrattai bataw 1 g/cc, pantadarty at webs over 0.4-tach, aad in crore wethras op to abean 7 jacket dunrattr mrqr be ode by the eotvoadcre ettrarioa promm, shown in Прага SI. The csbtenre of fastatted capacity aad wo abb of eaperirare on the aohwat catro- mob jvocttB Imb Люоогв^вй Ufliftcd SMbi boc of the etrivetatera eatrarion proems tor wto tern than 0.1 inch, ahhoogh abroad webs conriderabiy saa&r ha*c been e&iradtd withewt aofrw. The upper to Barit has been set by the abtoy of a dfe in a 15-iach pros to fam a pesfacdy coaoottdMed Wssl tore Worid Warn work both fa to Utoed States and abroad hat indfcotad to pnstotoy of omradfag oonridewbiy hngnr gratae, even eroeed- fag to cron tecton of to powder banket of the peats, by incorporating an aepanetan choate be- twean to basket and the dfe. As with most sx- trasion processes tbe prodaett here tylindrirai geometry. tn to cate of aofrwndaa» nliraliw to word cyBndrictd amy be very brandy orantroed <Hpne 52). fltare an votafllM are ремам daring to ailiiMliai to dfe has atnriy to rente tope and dtontom at to strand, and cross toctiaaei 4вввйв todedfay якмр в^йвв cmi be twprodBQBd wtlbhtoiy. *4-L Stonriara The process starts with udted sheet, which is fanned into preot cfanpes by carps* rotting (Hpree S3) or by slacking dtafcs cat front to sheet. United totes pracsta w ю are carpet rods The charge is brongbt to mtaorion took perreore befara porting into to pmt (Нраве 54) «Meh b egpfpped with mmpentwe connote on both to prats baaknt and to dfe. The pram baahrt b evaonared befare entrntfen starts The ascended attend may be can daring to i rtnato by a flyfag enter which travels with to abend daring to cat, ar the whole strand may be «xtradad tart cot to grata blanks between pressing eyefes. The per- ooa of to taraad ranaiafag in to to between cxtnnion eyefee a known as to neck and b aaaen- МЦг СавЦВСМКЖ'ЯКВ0М» П ВМ <ИВИВВВ (ВВг* ВКЯМ ШИВ ШВ ВППММ BQEBM ВВВ м> BBBBHMg in to to btewaan ratnaaora, and iirftaarifr b iwaortad. In going to feryar craw seettan, one may ranch the petal where an mtoe ctarnaian weald be contained widto to dfe. Ftato toe ptot on, the whole cKireafon woota be neck. Thb shooid rondl fa even hr its r dhncnriowoi fldahty than fa attained in riwwnrinaai niiorioa. ПЛ. PMshfag. As to caae wkb to rotted sheet process, floiahtag optratfone are developed to meet to iwqtanwnts of the proctact. For a gon prapettam no dabbing operations (horrid be rajtarod other then ooottag and aqeSbratiog with an ataoMphare of the standaod raitaive borahttty. For a rocket or gae gnaentcr gram with tight dbnesnioaci toteranom the flnt floithiqg operation b anaealfag to stove raaidto atremm is order to stahite dtaenstans. This is done by heating to grain blanks to perhaps 120*F far several hoars. In ite ttorarinn to grata binoani a Bate sharer ano а пак toner, vntrarat me anneamtg opera- tor to same changes moahl take piece riorafy, canstag the finished grata to gt> cd tomnsfans. Alter aonealfag to ₽tea can be raachtaed to length by sowing, and to dfeoaeter by rniag ateto or dowsl rod machine. Batol hates aay be driQed toongh to web or slot» aatod m rayritvd lahfabor pntehra so raatrict to burning may be comenaed to to grata at to ends or along to taaerai rarface. hMfan that cow to entire dr- caandsresnfei carfare ate oraatty wrapped. Cettn- kne «etale ptato to with acetone and ethyl rrifajrer ptoeife to with a aeixfare of ethyl fec- «re and tarty! testate an to ooasaecn taMbteora
и а. линт»* ымнйяяяч Явшга Л Тгамк ММ» Ьигаамй П^вП 99, М0ГМПСМ CSRVWtM HPQCMi 81
«2
V. в. Лп* ’ а * I ЯрмЯ. CaqNf «•чв «3
aed with аЫтаМкм extruded grams. The aoi- VMtt are subsrajuentty removed by difiusion ami auaporation. С2-Л Itaw. Any tn^eriection* и the propel- lant tend to be elongated in the axial direction as a result of the exlrtmw cwersfcr.. Thb n ;•««£, ot Mriott* when bummf of ibc grain < >n the radial direction becaus-.- no f it amount of us- ptaoaed additional surface n exposed when the burning surface meets the fiau inspection on a ata- tistical basis coupJ-i' with quality control tfaraugh- out the operation is ariwpiatr to maintain such Oawi at an acceptable mimmuat. When the grain produced is an end-burner, however, no axial teas may be permitted Great care must be taken to reject any grains containing anch flaw». Flan detection вау be done with X-rays or ropersoaaca *3. Cast dahhke-Ьпж preeem. The cast ddobfe- bese praneas is used to form propeBaots in ac?' grfcrmrtry aod in soes trout about 1 inch № diam- eter up to untimited stie. It me» as tnternscdMrte» casting powder, which may be made either by sotirent extntnon (short cylinders about 0 Q3-inch in oriwncwr by 0.03-inch iongj w by the Ball Powder process I spheres of tiunbu dnnemaonj. and casting solvent, which is a mixture of pfaksti- daera. The bufc density of die casting powders is bmn ? Vrad die finished fkupcisaSri <a< ibises the same volume as its casting powde; This re- suiu in a Baxsamm aitroodhriose concentration in the cast propeQant of about I g/cc Cast doubie- base propeUsatts ere therefore possible in the same range of compositions as sobentless е<£лшеб propctati. M
The fiowsheet o( the proem it shown tn Ftg- «are S3. U-l. Cafaf. The ctuting ponder » first loaded «to the mold and evacuated overnight. The casting «font, ito previously evacuated, is then also introduced into the mold, ususlly by air pressure, where it fiBs ihe interstices between the individual casting powder grain». The casting powder imbibes the solvent and swell*, causing the individual grains to coalesce to form a smgte grain within the mold Due to the tact that the casting powder is glazed to dissipate static elec- tricity and to facthtate charging, grain boundaries are visible in the finished casting, but fractures produced in lenuie strength testing do not follow the grain boundaries. This indicate» that the cast propellant has become really homogeneous. The dreumferenud inhibitor required of car- tridge-type internal burning grams is usually 83
и
v. a. Я. CM Ой »7
praabricsdcu йпи кйимй ш use ucakvi. It is tincu а* реп of the пюИ If a cawe-bondcd gnuo ц called foi, the сек n first lined with any required nmda- tion and with a surface to which the propellant wffl bead The сак then becXHB t part of the mold Typical mold parts are shown in .'igure 56. The assembled mold and a&xtwxiet are shown i i Figure 57. The flow of casting solvent may be iq ward, downward, or radial through the mnM. Ai r result of Mending giant tu of carting pow- der and carefully coctrcffing the compoaitioc of cutting solvent, large lots of cast grains can be pre- pared with an excellent wilhin-kx rrpnxLiribQity. fifi-2. Curing. The curing operation, durisg which coalescence is comptemd, u done at de- voted temperatures (about 140°F) and require* bt<m 3 days after the grain baa come to curing temperature After the comptetioo of the cure the акИ is dKawrmhtrd and cleaned for reuse The grain is fimshed by sawing to length and machining any designed surface* not produced by the mold. 4JJ. Floated stoangfo. Physical atmgfo of cart double-base prop. Bant n comparable to that of propellant of the same composition produced by soiventless extruston. Flaws if present are ran- domly distributed and not dengaeed, so that the Kaleraaoe of Saws for end-burning castings is con aidecabiy greater than for end-bunmy extruders*. A finished grain is shewn in Figure 58. fiX Uses al prepsftsnb made by cart dunMn- base precsen Examples of propellants produced by casting are OOK, OiO, and BPY foe cartridge applications and BUU, a case-bonded propellant Note that three сопфсшйош must be broken down to a carting powder comporilion aod a carting solvent in order to manufacture them. fid. Stany caafoag pmrem. When the total vol- ume at the liquid ingredients exceeds about 30 percent of the volume of the competition it be- comes possible to suspend the solids, including the polymer, in the mixed liquids and pour the result- tag liurry directly into th. mJd. In this instance the sofids must be supplied in a shape that has good packing density, such as sphere* As tbe packing density of foe solid* decreases, foe re- paired volume fraction of foe liquid ingredients iaerrasr*. It is further nc ее магу, for foe sake cf pot life, that foe polymer particles posses* a sur- face font relatively ,mprrvsaus tc foe Uqusd components ar tie temperatures of muting and casting and yet readily soluble ar curing tem- perature. At least three such processes have been described?'" IWICU I J. R. Do Post. “Manufacture of CaUatote №t,alc far Pyroxylin Plames? Ckrm. Mtt. £<u.. M, 11 (1922) ILL 3шт (to Herarit* Powder Coeptny). U. S. Patent 2,02*.Oto (19361 3. JAN-N-244, Nbrocrtlniorr (For In m kiptoairtf (31 July IMS) with Aewadmrxr-,1 (27 ITecerabe- IMS) 4. E Red, K. R. Амсем and E Eacaka, Srdrdfr rar Xeaaarab drr AfitcAjdfere, P 32. J. F. Lchaaan, Muaah, Gtiman), 1937. (5«MMB*riwri in J. Bartha, Dcrfrarlvti of Cranio*. Strtioa В /«wvjptow- Earn. in E Ou, et al. (edito**L CeSnicw «Ы Crtlniosr De- rivnrhvr, 2nd editto*, Pan 4, p 720, laknciiwre PuHnhm, Ък., New Yort, New York, 1354 ) 5. F. Otero. С. С. TibbrtU and L В W. Kero* (to Western Csriridt* Cocnpsn)), U. S. Parent 2/127,114 (19M). 6 H F. Scfcncfcr (to Western Cartridge Coamaay), U. S. Раки 2 16OA24(1939) 7. MIL-P-3M4, ProMtamr, for Small Ami Amrutii Лт, CaUbm JO to 30UH Imhulv*. Eistft BlsiU MfCchher <5 (W November 1954) С. I 1 O’Meja, Jr and G R. Cox (to Otia Mattoe aja Cbwnscal Corporal»*), I'. 5. PrlriC 2,740,705 (I9W) 3 J J. ОКеШ. Jr. and G R Cox (to Otto Mathie- aon Cbertucai Corporetiua), U. S Patonl 2X3QAS4 (19ЯХ 10. It L. Cook a*d E. A. Andrew (to Otia Майоелм CWrrucal Corporation), U. 5 Patent 2XM,713 0 9591 II. E. A. Andrew (to (Min Mathieses Chemical Corpor*- tioaX U. S. PalcM 2323,107 (I960) 12. G. A McBride (to Western Cartritfne Cornpea)), U. S. Paleal 1355Д27 (1334). 13. W. E. Wasser (to Western Canridpe Qaapany), U. S Patent 2,00sXX? (1335). 14. С. E. Selk (to Western Cartridpr Company), U. S. Paleal 2.735,ST4 (1343) l’ i J. O’Neill. Jr. ‘to Oto: Mail)маги СЬезка! Сое poraixwo. U.S Paleal 2.314.775 (1933), E A Andrew (to CH» Ma&ivsoa CliemscaJ Ccrpcrattoa\ t). 5 Pateat 2,929,И-7 (I960). It. A. W. Stoaa and D. J Maas (to Atlantic Research Cortaratioa). U. S Paieats 2.931X00 anJ 2.93IXOI (1W) 17 J. Rcsahart, W. E. Sttunp, M. L. Bcvee, F. O. SutC and A. T. Салр, Nitratol Prvprllaui—Compoiitr ProfrUaat Formalatiotu 9a»tU on a Piartirol Nitro- te&aiore-Prntacrjrtknlol Trinilnur Bindr r. Naval Ordaaoce Teat Staritwi, Bulletin cf Tbe Fowuealh Meetssg of Tbe Joist Алпу-Navy-Air Force Sofa1 Propellant Oroop. Vo’ IV, p 3. CONFIDENTIAL. Sohd PropeBaat laformalsoa A*eacy, Applied Fhyna Laboratory, The Iotas Hopkins Uarrerwty. Silver hpna*. Maryfand.
CMAPfM 9 нт nndmi coMFQsms S5. Gmtni. The fuel binder cornpoaite* ?n the United State; were developed dun ay Warid V u П in response to a need f« grcns for use m aircraft jato* Smokeless prrwden frad been widely used for gun propellants and had (wen made abroad by sdventiess cxtruscm into grain: for artillery rockets, and aohtnUea* extntaioQ was being de veloped in ti.it country It was, not типе* diately apparent that smokeless powder could be fabricated into grain стон sccboas of the die required for such jato иге, such стой jeetkaw being beyord the capacity of existing or cootctn plated presses The black powder art had demon- strated that a solid propellant mxi not be a monopropeJlant Existing black powder manwlactunng tcch- niquit would do. produce large grant The exist- ing black powder formrla was less energetic than deairtd Substitution at a hydrocarbon tor the sulfur and charcoal of black powder put aQ of the fud into the binder p^u. increasing the vol- ume fraction of binder to a point where a casting operation became feasible. At the same time oxi- dation of the hydrocarbon led to products (includ- ing H2 *.kJ HZO) of lower average molecular weight than those derived from black powder. Sub- stitution of potassium perchlorate for potassium nitrate increased oxygen content per unit volume of filler and decreased the weight of solid residue per unit weight of propel'ant. The arphalt-potes- aium ретсЫопие interim propellant successfully eatablisbed the position of fuel binder composites *» the propeucnf beK and encouraged further development The first таЙ* improvement was the substitu- tion of a polymer system for the asphalt The filler wm aahud with binder in monomeric or partially pofytr.staed form and cast in that condition Poly men. 1km was completed in the curing operation in the BKtid, resulting in a grain that would not cold Bow under moderately warm ambient condi- tion* as • "Ouid the aspbah The second nayor improvement was the sub- stitution of ammonium perchlorate for the potas- aram salt, rimrinatifig inorganic residues and dense smoke. The gaseous combustion products, huw- em, now contamod HCl winch is somewhat cor- rostvt under renditions of high humidity This condition has proven entirely acceptable for condi- tions in rocketry where the engines arc expended in a single firing. It is leu acceptable for some gas generator uses where the combustion gases remain in contact with metal parts that will be reused. When considerations other 'han maximum per- formance, suc<; as freedom from corrosive exhaust or cheapness and availability of raw materials, take precedence a nmonium nitrate may be used in place of the ammonium perchlorate The third major development was the substitu- tion of an elastomeric binder for the hard polymer binder This permitted case bonding of the pro- pdlant and elimination of the inhibitor from in- ternal burning grains Replacement of the inhibitor by additional propellant increases the mass frac- tion, or ratio of propellant weight to ’oad"d motor weight, and thereby the performance of a rocket Continuing need for thermal insulation negates this advantage of ease bonding for end-burning grains. Si. Choice of vxiduer. The differences among the three oxidizers that have been widely uied in fue* binder composites, potassium perchlorate, ammonium perchlorate, and ammonium .iitrate are shown in Table 11 As a matter of interest, TABLE 11. OXIDIZERS FOR FUEL BINDER COMPOSITES xc»o< NHiMig F.NO* Molecular 138.55 117.50 so os 101 10 Specific fr»vit>. t 2 52 1.93 1 725 2 11 MCI., 0.0034 0.0043 —. S4H„ — 0.0170 0.02 SO — MN.. — С(ХЮ 0 0125 00049 O., o.o’M 0.03*0 0 057? 0 024- _ .. i Specific vqImbs, “ 0 397 0 513 0.580 0 474 figures arc included for KNO3 Following the somettdature of Chapter 2, the items Ci*, is the number of gram atoms of Cl in one gram cl oxidizer, H*, the number of gram atoms of hydro- gen, ex In the case of potassium perchlorate part of the KC1 refilling from pyrolysis of the oxidizer is found to be vaporized, and part remains in the 99
condensed phase. For it ршрок < tbe present argumtiii it u assumed that half of u is in the gas yvif . In the C£S£ Cf gmmranturn pgrrIM eM at tbe chlorine it in th git phase, and its con tri butwri to the (to volume is ViO^, Any hydrogen will be in the form of either Ha or HaO, s? the contribution of the hydrogen of the oxiduet to tbe combustion product volume is V&H». The exyger of the oxidizer will appear as CO, COa, ot H;O and makes no separate coatribuboo to the gss. vofunx. In the саде of potassium nitrate it is assumed that a solid retuduc of KaO wU exist «мкг operating conditions This removes one-half stout of oxygen from the quantity avail- able for oxidizing fuel, and tbe value at G„ under KNOa is corrected for this. A more significant exapwrion « tbe oxidizer* appears when they are formulated with a fuel As Mi example, consider s series of prcpzllanU formu- lated at 75 weight percent oxidizers with a hypo- thetical fuel of composition CH, 6 and specific gravity 1.2 Data concei ting such й fuel are shown in Table 12 and for the propeQa&u in Table 13. TASLt IX HYPOTHETICAL F”^L BINDEk CHi 4 Molecular weight 13.5 ИН, 0.03% Cf 0-0740 Specific «faa<, 0.833 TABLE 13. HYPOTHETICAL PftOPELLANTS К ЧО, Ъ'ЩСЮ, KN0» Oxidizer *eigtu 0.75 0 75 0 75 0.73 Binder wtitfu 0.25 015 0.25 015 xc 0.0185 0.0185 0.0185 0.0185 HN » « 0.0032 0.009* 0-0037 — 0.0128 0.01U VIH, 0.0139 0.01» 0.0139 0.0139 vjZG CuG27 M-wGj2 ,w— — 1 0jM51 0.0516 0.0606 0.0341 to 0.02 If 0.0255 0.0282 0.011' SO-XG 00031 0.0070 0.0097 n Oalduzr volume 0.298 0-M5 0.435 0.35 3 Better vclurar 0.209 0206 0.208 0.2« T&cal tolaev 0506 0.595 0.M3 0543 Spscifc gn 1Л и» 1 54 l.?l Butdj voteow. * 41 35 32 37 The polar*ium tuti.ue member of this series of propellant* is cap/uk of product^ as much gas ax thr potassium perchlorate member but tbe total available oxygen is only enough to oxi- dize the carbon to CO This propellant is badly undcroxidized, a.,d potassium nitrate hai properly been ignored in the development of fuel binder composites. Sd-i. PMaastaas porHrnste Potassium per- cnkxiic has the considerable disadvantage that s mayor part ol tbe KCl formed in its pyroiyus remains condensed under opcsairog conditions, re- sulting in a low gas volume ( У rcKl KCl condense» ui the exhaust, and any propellant formulated with potassium perchlorate burns with a dense white smoks Linear burning rates of potassium perchlorate propellants tend to be high, 0 8 to 0 9 in/sec az 1000 psi Propellant densities also are high, ’ .8 to 2.0 g/ec, reflecting the high specific gravity of potassium perchlorate. Specific impulses are generally below 200 Ib-sec/lb, re- flecting the to» gas volume, pt«*sure exponent, n (Equation 31 a), tends also to be high Due to the low specific impulse and smoky ex- haust, potassium perchlorate ptopellanis are no longer in general use. 56-2. Aaawitus perchlorate. Ammooiuin perchlorate avoids most of the disadvantages c! jMMK .siuui pcrvlik/» iiic riuyctiwis cvuiiuUiug «iu- tnoruum perchlorate burn substantially witnoui residue or tn tote, and the oxidizer makes a sub- stantial contribution to the gas volume. As a rew.it of this, specific impulses have been calculated to about 250 and measured to about 240 Ib-sec/sec. Tbe (measuredJ specific impulses and the flame temperatures of selected ammonium perchlorate propellants taken from SP1A/M2 date sheets are shown in Figure 59. As theue propellant* were made up with a vari- ety of binders, it is apparent that specific impulse and tame temperature are largely determined by the weight towdmg of the oxidizer. Orer the range 55 to S! weight percent oxidiser, the flame tem- peratures seem to be linear and nearly propor- tional to the weight fraction of oxidizer. Tbe specific iapube also rises with вдынвл weight 90
NH4C!04 OXIDIZER, WEIGHT PERCENT figure 59, Specific taptdaa, and fiame Temperature, Tf, ct NHtCIQlJnl tinder ComparHer fraction tit oxidizer but apptari to approach a maximum of about 240 Ib-sec/lb. Comparing the two examples of potassium per- chlorate propellants (ALT-161 and AK-14) with Fgure 59, it appear» that the potassium perchlo- rate propeflants at about 75 percent oiaiianr arc equivalent it. specif*. impulse and flame tempera- ture to ammonium perchlorate propellants at about 60 percent oxidi «у Burning rates of ammonium perchlorate pro- pellants at 1000 psi and room temperature are plotted tn Figure 60. They also seem to trend upward with increasing weight percent of oxidizer but are subject to other influences. It is. recognized that oxidizer grist has an effect on the burning rate, tiatnt oxidizer leading to low burning rams in a given compositkxi. Burning rates of ammo- nium perchlorate propellants have also been in- creased by substitution of potassium perchlorate for pan of the ammonium perchlorate, but at the cost of a smoky exhaust. Burning rf . may also be influenced by catalysts Ammonium perchlorate it a tnoaopropellant. Iu pyrolysis starts with dissociation according to the rescues’ NHjOOr -> NH, + HC1O4 (57) leading to a combustible mixture of NHt and НСЮ, in the gas phase adjacent to a NH.CJO, crystal.’ Subsequent features of the combustion re- actions are a matter of scam dispute. Accordmg to the two-temperature theory’ the burning sur- 91
NH4CIO4, weight percent figure 60 Оде-пиф Kofe, t. cl Itw fni, Ambient Teo^wcUixe of femfear Corapci* n fax retreats in * plane, the linear burning rates of the binder and oxidizer are the tame. This requires that the turface temperatures of bv-ning oxidrzr and binder be difierent. The thermal Layer theory,* on the other hand, states that the rate* coetrollmg step is the redox reaction of the tnooo- propeUani, in this case between the NH- and HOC,, that burning surface is not plane, and that rfiffoHon of binder pyrolytic products into the thermal Layer where the redox reaction is goiiig on may Lead to perturbation depending on the rela- tive rate* of reaction between the oxidizer-binder pyroiyus products and the cxiduer pyrolysis prod- ucts atone. The reaction products of ammonium perchlo- rate fuel binder composites arc Ns, CO, COS, H2, H2O, and HC1 Of these products only HC1 de- serves special mention, the others being common to smokelex, powders which have кч^ be .n used in vatious heat engines. At relative humidities above about 85 prawnr ИС1 tends to condense to droplets of aqueous HC1, giving rise to smoke and to corrosion of metal surfaces. The wide use of ammonium perchlorate fuel birder composite propellants in rockets й an indication that for rocketry HCi tn the exhaust is not a aeriouvprob- lem. If other atomic species are present in the binder, their compounds will, of course, appear 92
fq/vr* 41. Spacer йфмЬм, eW Лин Гаифагайга*, oi HH4t4Ot-A>el Bmdw Сояфовйн in the exhaust and may be addtorcxiai tosnr ч corroeioo. M-X LMMmb parcMarata. Labia® perchlorate ha» received кжк atteettosr as as, гиы&вй to these composite propefianrs (e<-, GCR-300 m SPIA/ М2). Thi* oxidiser should be superior to potas- кш perchlorate tn that thr LiC! should aS be vaponsed and fores part of the woriuag field, with the amount of available oxygen per met weight of oxkLrer higher due to towrr molecular weight CondematioG of LiC in the exhaust should lead to dense smohe ns in the ewe of the potassium salt- PropeUatns ccoUumng lithium perchlorate have higher density but arc sort hygroscopic than одтпропащ» itwmctHoa perctJcrste propcSsab. num nitrate as oxidiger in hid binder composites avoids the probtem d coiNtm exhaust due to HO, at the coat of towered specific impulse As indicated tn ТаЫе 13, the votwne prod- act gu is higher than for a oonespoedtog аимгю- шт percblxite propdlani, so that the lower specific nacube must result H*» fee** £±se lemperarure, Tf This » infeed the case, as may be веса in Figure 61 The maximum specific itn- puirc appears to be to the neifhborbood of 200 fis-sec/Ь, and this n attained at a Same leapt. >»- bare seme hmdrub of degrees lower than for cfiknle system. If maximum performewe is no required, quite low ftaose temperatures can be attained by decreasing the ammonium nitrate load- ing or by incorporating thrncaliy decomposed diluents such as Qanoguanidinc. Buntusg rates appear tc raege from 0.05 to 0.27. The cosnbinatM» of few temperature and low burning rate is attractive far gas generator uses. The higher rales are available through the ok ot catalysts such fa Prussian blue (ferric ferro- cyanide), ' Mikxi blue,' chromium compounds such as ammociiun dtchromate,* cobalt com- pounds,1 or sodium barbiturate." The higher burning rates so produced are useful tn sustaaer nwjmi and even booster rodeeu.“ The bumtog mechanism of ammonium nitrate propellants has been extensively inrcsttgated. Am- mocMum nitrate is also a monopropellant, and its first pyrolytic product is a gaseous mixture of NH, and HNO, The rate-contrdhng readies is pre- sumed’ to be the redox reaetton NHj + NO, -o NH, + HNOj (58) a»d m the uefnai layer theory the rca.doos ot btDder pyrolytic products with the аллгкиилп totrate pyroiyuc products occur so Utt (so from the burning surface) that they do not com- mutCcate heal to the burning surface This would expfefe quahtativeJ) the slou buntoqg rates. The агсЬашяв of catalysis has not been explaioed. •3
The combustion product» of юшюоЛмп nitrate cornpobhci аге r>';. CO, СО,, Hj, and HjO, the umt as from smoke к si powders, and present no new problems They are generally ir a compara- tive!) high Mate of oxidation, so that even the cw formulations burn without producing much free carbon Ararrrsu^r, nitrate a hygroscopic агД m a&k- tion.exhjbiu phase changes at several temperatures. Precautions must be taken to keep ammnmus ni- trate propellants beta* 40 percent relative hratid- ity during manufacture and subsequent handtag Processing is preferably drew at tempesatures above 9GrF to avoid cycling through the phase change a; that temperature. The higher pefcnt- агм aamoatua nitrate propellants are so foerai- tateu that their volume fraction of trader is too tow to permit casting Exmanon sr compreaticn molduig processes are coamoal) mod as fabricate such propellants. SO-S. Mtetd «Мм. Totirtradtians ef ote- dirers are sometimes used to get huamaag nan outside the nonMr range* for *4^e naudaasn The cxribination of poomnra peackforate11 with enure nium perchlorate leads to higher tnuxsog rates than the arithmetic moan of tbe noraud rates «tic two oaidirers measured separately. This oosnbiaauoe preserves the high pressure exponent (e^. T10-E3 in SP1A/M2J of the potassium per- chlorate prapeUanu, indeed w some proportions of these two oxidusen value* of я approaching or evert eaoeeday 1 hare been observed, Аливсевшп nitrate, wtroguaaidute, ot cyctoteaamcihyieae- aetnsitnuame (HMX) may be used as pan of tbe oxidan’* to lower the bsnnig rate of aa mraao- ИМИМ pC*VMoO«№V pB*Vp^*aS£*w AteateWMMMM pVteaFfoW comprises part of tbe oxadsacr to the British plastic ргореОми. S7. Vatamafcfc пЫн «f wsWtar Sa btefor. As shown itbove, the ballistic properties of a fuel- bander composite propellent are determined by the weight fraction of oxidizer. The physical proper- ties including fluidity during mawdactore are de- texfflined by the volume fraction of binder and on rite/> f ff kte*vjU*r! **.»* lly сНтач* Jbf tlfon ArjAsar particles aad their gm: playing a uippoetiag role Roughly spherical solids caa be dispersed in liquids ep io about SO volume percent without having much <®k1 oo tbe fhddtty of tbe system, aad with favorable grist and sohd particle shape the volume fraction of the continuum may be Oe creasro to 40 or crea 35 volume percent before the presence of the solids is strongly fell in the fluidity of the system. Beyond that point the vis- craity of the system increases rapidly, and a rex? ccotraram is soon reached where the system will not flow. 1л the fuel binder composite system, casting tote* Ft* feasibility when the volume frac- tion of the binder goes much below 30 percent CwKurreudy tree with е1амоякгк binders the distortion M rapture approaches a low value when the voIwk fraction of the binder decreases beta* this regioc For case-boudcd systems, therefore, the fraction of binder must be mmntamcd above this a&risNMS in order that tbe grain makrain its integrity over a temperature range Tbs means thst when one is formulating a high performance grain, winch witi therefore require a tar weight fractioo of binder, the preferred binder will be a tow density material in order that the volume frac- in at the tender tee simsftaaeocety kept high. On the «ten hand, at to* etodurr ioadfog such aa gnAened for low flarae-tempentnre gm gm- crakx penfir 11 anta, the binder wright fraction will be natwratty higher and one iwgtu well choose a dense binder to minimite the envetope. Table 14 tabu ja сгивета loading vrasus BINDER DENSITY PER UNIT VCC’ ^ffi Wader drawt) 1.0 12 t.4 Voteeae OK 0Ю 030 Wetfu «Л0 034 0.42 NHjOO, voteae 0.70 0.70 0.70 Wexalu IJ? 137 137 Рпфе0ав1 draaxy, * I.S7 1.73 ITS NrieCIO*. wefote percent К 79 74 Bueder, wsi^t pcevna 18 21 24 №ЦМО| volume 0.70 0.70 0.70 Weiab: UK 1.21 121 PropdteM daaaty. p IJI 137 1A3 MHtNO*. veste perceat 80 77 74 fonder, wtifhi pteraes 29 23 24 illustrates the effect of binder density on the weight perceut oxidiacr loading at a ccmstam M1 votuase percent binder basis. S*. Ctetot *4 Made- fcnd4ie<n use may re- quire either a cartridge-type grain, for ease of ia- spcctoD or for repetitive use of the chamber, or a case-bonded grai n fos high performaoct If * cartridge-type grain is celled for, the propehani «4
f дыгв 62 Slurry СмГйв Ftocmi muH have high modulus and scene comprcsuve strength If the grain is to be case-txwted tbe sb act to which dte grain will be subjected cah for kx modulus aod high rloogition £*>1. АфЬек. Asphali, tbe first bmder used tn • faei-bindtr composite, profaned a case-bondable prcpeHant. As ir*ay be wren from tbe data sheet cc ALT-161 (sec bFiA,M21. the sspl att was srx'tetsed with 3 piastxr'.ui to decrease the modulus so that the propellant could be used over a suit- able but restricted temperature range A*, tempera «res below about — 20cF the pr-yihwn became very brittle, leading to fracture and explosion on фхгОос At temperatures above about 120sF tbe propeOant became quite soft and Sewed s»ay frpm its design gecaartty Asphalt had the advantage of being cheap and avadaUe The propeliar, manu- facture was simple, the oxidizer was incorporated into the binder at elevated temperature using a sigma Made mixer and the mixture was pouted into the mold or case and allowed to cool. S$-L feiyiiwbim x«. Fol\isobutene, med m tbe British “plastic propellant/ ddleis free» aspbai: chiefly tn having a truer lemperature codficratt of pby*rCai properties Au с паттерн: o< Mach pro- pel tnt is RD. 2312 (see SPiAW; The cut- dizer ammonium picrate h readily ddcnnable and hen л permits a fowe.' than normal binder votiMK fraction It also affords a lower burning rate thaa ammonium perchlorate would gi>t as tbe «ax oxidirer. Mtiti. ЕкМоиНс Mbdm. Tousle stwagnh enough to eroble the ргорсЛпы to withstand handling and firing accelerabcsa h. added to tbe binder properties by incorporated of a polymer, often cross-imbed, inw tbe binder. Th' polytec: may be one of the rubbers, used with or with- out a piasbarxi. or it may be one of the non- rvbiscry themopiiwocs such as сеНикже acetate or polyivinyl chtondc), used with enough plastscizcr to bring ‘hr modulus of the propellant into the proper range Sfi-31. Pnlyndfcfc iwMih The fust xuch bi.rter was formulated with polysulfide rubber.” and pcriysulbde rubbers have remained important con- abluents cf case-bonded composite propellants “ The polymer is introduced as a partially polymer- ized prepolymer (liquid polymer) and Ktiymcnz»- tion is completed during the curing ope «non in the case or mold at elevated temperature and in the presence of a pcfymenzatioo catalyst such as p-quinonedioxitn.-. In order to accelerate the cure or to accomplish it at a lower temperature, a pro- moter such as diphenyiguanidinc is sometimes tJso used Magnesium oxide and ferric oxide ищу be rased io modify the bunting rate, and other addi- tives are occassonaiiy used for various reasons Poiysu&de propellants ar. fairly dense, reftecl ing it» density of the polysulfide polymer. This feature restricts the allowable oxidizer loading. In the moderate performance range, on the cthe. bead, a grvee total impulse can be contained within a smaller envelope than with a less dense p spcl- (UH As ir Minera-urcs above iwtn iff the l.nsiic (trass a! rapture is typically 50 to 100 percent, beu^ to*u with the higher loading density. This ’’wtl is genera^y adequate for case-bonded appti cations Id more than 10 years of existence, pMysulfide propellfcau have not shown senousiy deleterious ag-ng effects except for a change oc the exposed surface cf the grains that interferes with Ignition Г. i> believed that this property has been over- come tii User fo mulatiuns. but this can be demon strated oah when the newer propellants have bet., agev' The m«oufaciuriqg process used for pdysuifide propellarth is the slurry casting p ocess,” for which tin. fiowsbeet is shown ir. Figure 62.
tf ПшШ Cl—mW g—г Paw* 5<s-ur* <53 Segjeo Uada M>*ar (300 GoiicmJ Reproducibility of the охкЬхег grist is one of the most important qualrty control measures tn the ел afacture The nuxer mas be a sigma blade •Ma. equipped with Ivutocn nutlet, «hew»! ir Figure 03, or, alternatively, a vertical miser shown in Figure 64. The io^rcdaesU are added сошесс tively to the mixer, darting with the prepoiyc л. A: the coocluoo.j of the mixing dr charge is de- aerated by evacuation or other meant and cast into the motor сак. Curing is acoompbthed by •ubjechng the leaded сак to elevated temperature in a heated space (a pit is used foe huge charges) The mandrels гт removed after the cured charge d мм3—1, айи шё Coargr is usisned by rnaciwimg assy des^jSod «ufwv-» not produced by the mold, in general, such surfaces are chic Sy the aft end of the graia. A typical maedrei is shown in Figure 65, and a motor with case-bonded grain in Figure 6f Foiysutede-aaaEKtoum peichkxate grains from 1J indtm to 40 mebes m diMMer, and in sights from 0.5 pound to 8700 pounds have been manu- factured and flown in rocket melon. Examples of polysulfidt-amiboniuin perchlorate composites in T14 used in early experimental work a h Urge engines, T17 used in RVAI0, Sergeant (XM-12), Xi7, reentry vehicle (XM20), and various test vehicles m the Polaris and NASA high altitude programs, T24 used in the Honest John spinner rocket (M-7); 11 ’El 1жи iii Vivrvui aerodynamic rest vch^ici CI 42;, T-22 used ir Loki; GCR-201C need in Vaqgrard third stage rocket, and T27 used in Falcon P'/4-46) two-level thrust tnctot
O»’Mv 4 ГМй Сконто Сафплм. ttrn, town figvn 64. Varfecoi Mtaar f300 (Мтл) 97
Ы ТЪвЬЫ Сличит! F«jp.« 6$, Mandrel for Madwm Site fodtM Motor $*3.2. FuijimrtuM пЫйг. Apart from the poiyjulfufcs, roost synthetic rubber's ti' formed by vinyl-type polymerizabon, or addition at doubie beads. Other polymerization reactions not involv- ing p-. sduction <jf volatile by-products are known and n ftbe useful in preparation ot propellant budu Fo. rump»’, it an isocyanate is added to a compound containing an —OH group, a uretkme u formed according tc the reaction RTsvO + HOR = RTSHCOOR' (59) Rea. dot i of a dr isocyanate and a diet thus fives а tong chain linear polyurethane, and the presence of sortM polyol cm polyisocyana% should cause the polymer to cross-link, in order to mtnirnizc the he t of polymerization during the core it is cus- UNoary to use a tong chain did such as pdy propylene glycol, HKXHa-CH].-OH, with a CH4 simple diiiucyanate such a* toluene ditsocyanatc There ate many toti£ chain <hd> available but only relatively few diuocyanates are on the market The polymerization reaction must be catalyzed, as by ferric acetyl acrlonale. and accelerators of the polymerization are known. The polymer may be used with or without a plasticizer. The physical properties are similar to those of polysullide propellants at the same binder volume fraction. The density of the polyurethane propel lain is naturally tower than that of a polysulhdc propellant at the same oxidizer weight fraction. The menufactunng process is the same mj that for pdysulfide propellant, with c.se important pre- CeuuOu. Stfiuc inc гмКуаот«1о rv«Ci with -Cm groups, it is particularly important that all ingre- dients be quite dry. Addition of waler to iso- cyanates results in -NHCOOH groups which tend to decompose Polyurethane binders have been more extensively used in the aluminum-ammo- 98
Сеопагл о/ TbmWi £«й*мм ХИпмя ftgvn 66 ЛДОаив Size CoM-gomhd Grein Wih о Ь-feint Star Config-zron&n nium psrctdoraic-bindcr propellants described in ORDF 20-176. 51-3.3. IBHuJmiii atfjlir add йугг mis- ter, РВАЛ. When butadiene is copolymeri’ffd with acrylic *ctd and cured with ac epoxide, ar. e'astomeric binder results with properties fairly similar to those described lor the polyurethanes Tin's binder system has а сошрёгаЫе density to that of the polyurethane binder, toJeraxes about tbe same weight percent of ox&zct in a case- bcnd&bic propellant, and gives perfonn?occ in tbe same raryje. Tbe manufacturing process is essen- tially that shown in Figure 62 РВАЛ binders are receiving eonsidcrsblc sucnuOti in inc newer aluBiinum-amnsoruum perchlorate propellants, dis- cussed in OR DP 20-176 5В-ЗЛ. Polylsiajl cfcterife). A nonrubbery polymer, if, sufikkntiy pusueixed, may develop in a heavily loaded plastK about tire same ultimate tensile su.ngth, elongation, and modulus as a ruixbery polymer with little or no plasticizer This situation is taken advantage of in the polyfvinyi chkMide) propellants such as Arctic Зов used in dk Aicoo sounding rocket motor At a compara- ble density to that of the polyurethane propellants, a pdy(rinyl chief ide) propellant permits about the same weight fraction of oxidizer and develops about the same specific impulse At a k* ‘t: piasti- cizer level a siiftet binder and therefore a more rigid propellant results, with properties of com- pressive strength and high modulus required for a cartridge-loaded grain. Cross-linking may be ac- comp>ish*d by formu’giior. -xith agents that react during the cure. A nove' feature of d e poly (vinyl chloride) pro- pellants is ,hetr method of manufacture. Tbe poly- mer, already complete!) polymeiized, is suspended in the plasticizer together with the oxidant and additives during 0>e nwung operalioo. At ambtent 99
л? > f «-J-fv--J Ctsi-rids) ftsssltsri и * 4^ • • /* V V W V 1 • *r» * jf T * ntrri • <x< ^*4F/ • rvw^’rwrw Centf ft M^ar >i«»wr» C^F»^nm 1. Hopper for inert prttpeBani ftid 2. PreMurin^ KUing pot fot Arufo propettom 3. 'HcT propnUoni food 4. Hartei at exkvrS-M i Die 6. Wsrter trough 7. To«»-ofl roHott В. Л-!*егкс$ге Jens' P. fx^'uefod propeUant 100
Ajiaarir C&rpaf&vn 6(L E^rvuM t>f Wr*c Grain temperature. or perhaps аг ь chilled mir.’^p tin', pemurt, the ро1ут-ч;г does tot imbibe tbe plasti- dzer, sc that good pot lif' is attainable Tbe sub fcuid mix, called plasuiol, is transferred tbe case <x mold and tbe grain is cured and fuusbed The curing operation is mechanically tbe same as for the synthetic rubbers, shown in Figure 62, but it is chemically quite different. These propellants may also be extruded A snail extruder is shown in Figure 67, illustrating the essenuals of this piocess The extruder is operated »i a temperature above 35O’"F, and curug takes place during toe extru- sion. Grains corytming vires strung parallel to tbe axis may also be extruded, as shown in Fig- ure 6Ь. Since no polymerization lakes place during the cwt, there is no exodirrm and Utile, if any, volume usange auc to curing On tbe other haad, the high temperature of Use curing opcr&uor en- tails appreciable thermal shrinkage when the cured grain is brought to ambient temperature 55-3.5. хдемиаветн. еиип for ortvegt-iaaded grata». Although the case-bondable binders do not in general contain so much plastic her that they can be stiffened by eliminating plasticizer, there are at kasi three ways that elastomers car. be adapted to such use One such way is to bond the grain to a relatively rigid mechanical member separable from tbe case, which may also serve as an inhibitor. Another is to cross-link tbe polymer to a greater extent than is required foi the readily deformable case bonds Tbe third method is to decrease tbe volume fraction of tbe binder to below 30 percent so that interaction of tbe crystalhoe particles carries part of the imposed load and helps resist deformation. Tbe first two alternates ~voudd stili permit fabrication of t'x grain by cast- ing The third would require other fabrication techniques. In tbe case of propellant CPN-127A (see SP1A/M2) used in aircraft jatos, the binder employed is a butadicrK-Z-nuTi/l-S-vinyi-pyiidirH.- IO I
copolymer plasticized with the formal of dKthyicae giyco) monobutyl ether (Butyl Cartxtol fennel). The volume frarton of the Ькмкг, calculated from the composition and 4“ja*ztk> of the crystalline ingredients, is about 7.6 percent. "Пи tnamdnc- rwing ргосс'ч lot tl>u propellant и outlined in Figure 69 Mixing >c done tn a sigma blade mixer. The completed mi?; i« blocked in a hydraulic pres», shown in Fig^.. 70, to form a press charge for extrusion. The extrus.au press is shown tn Fig- ure 71. The extruded strand is <»t to grain blanks which are then cured at elr.vtmd temperature to complete the potymtnratioa. The cured grain blank, are Crushed by machining to Caal dnccu- rioos.*' I£ Still another fabncatkic process .. used for pi o- peliant CBS-128 К (set SPlA/M-J, ^t-^ург-а for the Dart and Sky Dart miariks. This ptopeliant uses CR-I rubber plasticized with di-(2-ethylhexyi) wylate, and bat t binder volume fraction even lower than CFN-127A The flowsheet ter this process is shown in Figure 72. Co'pounding and simultaneously curing is done uu a oil null. Dirks «re cut Iron, the rolled sheet, stacked, and v W»< • Л.Л- »• л.» - Ж»-- t « T T fan. 44 • 4 iu^-пм >* fr*-"—»* blanks. The grain blanks arc machined, as shown in Figure 74, and then inhibited S&-4. Ул», (imipteitir «yrrthnrir роЗуамг btefan far cmtrldgk Ins Jiii grates. Tie use of thenno- pUstk pt4yroejs polymerized in situ predates the we of tic elastoaxrk. polymcra The binder ryi- tet'ts are selected to give corny retsrie strength and high modulus, thereby permirtidg а.гакшича of fbe r quired physical properties in a grain prods vied by the slurry casting process of Figure 62. ТЪе prepo'ymcn or rncnranc» are mixed with the oxi- dxrera and other additive* in a sigiua blade or equivalent miler and cast into moku. Pc^ymrriza- boo •* compsvted st elevaied temperatures in we «sriJig operation in thr molds. The molds arc thr t dtsattembted and die grams brushed by macte.- ing and/or inhibitor Figures 75 and 76 show cocuptetod grains and fcsM'rv" Jrttti. 5*4. СеОДем «ОШ- Cellulose acetate is xrxde from a uatural polymer and is MX available in a monomeric or prepolymer state. It has a fairly h^h softening temperature which can be towered by compounding with a plxsuclzer, allowing the priptilaai to be arid (or med at a moderately elevuted tauperaUixc. In propellant LFT-3 (see SPIA/M2), used in the GAR 3 Falcon AFU, like ccllukae acetarc it plasticized with acetyl tri- ethyl citrate and dirutiophtnoxyethanol, and sta- bilized wi h to'uencdiami&c. T he oxidizer loading is fairly lew in order to maintain a desired tow flame temperature. Mixing is done in a sigma blade mixer, and the grain r. formed by comprei- tton molding Larger grains may be made by bond- ing segments together using a polyurethane layer between the segments as well u for the periph- eral ir.hibitO'. A 50-pourtd individual segment as rt ov'Jed is shown in Figure 77 and a 100G-pound segmented grain in Figure 78. 5*4. Otter btetor ауинмч The above toting is by no means a complete roeter d bunder sys- tems that can be used or even cf systems that have been expetiinnited w?±. А сойяЛепЫе tSan has been expended on binders containing acetylenic and other endothermic gro<sps winch might add to th. beat ci exptosK/n, Q, ot the propeliast at * gives oxidizer folding. Tbeze is *ti2 room ta binders with anproved physical properties such as coeffictenu cc expansion doser to the expaauor cnefikkau of the materipts rued for rocket moto caw marifrftfture, tower brittle temperatures, aitd It»» temperature dcpcodcact of irooduisu, oom- preMrte and tensile strength, and eksigubo »r rupture. It n expects that new Ъим&ь ;уг«аг will continue u> appear. J 02
103
Сввгаадг W i><i ' я>ми» г/ Них* Антии» Линия It*. Ндип 71. Еиймдол PREPOLYMER PLASTICIZER ALd/HIVES 72. Союргешсл Maiding Ргссны for Fool *4м^«г CoM^ocitHi 104
Cwtm W M CmmI Cw>*o«j F®4#* Vi. C^nprtaatig Slatiti Dub >05
901 «ewj ft м'ймед «доо
LMtrtsj af 4a**/*t Gtartl figvn 7S. Jefo Grow 107
1(№
<МЛШ} ai Лт»ч СйммаЬ СауШм figure 77. UuiiriAMl itgunnl 150 Peun&t) ai 1000-PountS Seguwttd Groin 109
Савву «Г *»•« CU—l4l Омрачай* Плит ?&. Sqy—HiW Grain (I 000 PovndtJ И0
штмкж I t D Sctoda aad А, О. Огккж, Тлинама-Шые Theory erf th* liner’ Rat« et Decompoairioa of АпмпййЛ1йг rvrdniwate, ~ SLur Sympceiam (inter- ngdonol) on Comteaicn, p. 6 It, Reinhold PubbtoiMC Corporattoa, New York, New York. 1,57. 2. M. SumsaerheU, E. S SutbnAod, M. J Wabh, К > Tabock «ad K. F. Hall, Bsmhy Mechotfam of Am- тоМшл PerrHoeae PnopeBenit, paper pnawlad al Ancricaa Каска Society llct Aaoual Harttog, 17-21 November 19 St, New York New York Э. Л F. Caaiira aad W H Aaderaoa. The Hott of Binder /л Composite Propetlens Comknueioit, Лао- jet-Gami Oxportatioa, Report TN-30, AFO6R TN 59-540, Jbly 195»,. CoaUwa AF49(6M>566 (SPIA Abatract No. 19.Я 0 4. N. A. Labrt, Hjutrochlcric Acid enA Sodom Seilftite, p. it, ChrgriraJ Catalog Company. lnr~, New Ycat. New Yak 1927. 5. W. A. Frnii, Devetopmenr of Anunanitm Hitrat Лем Solid PropeHeni. Standard Oii Coaptsy (Iad>- •aU Bmioachiy Report No. 3. November 1951, Coe tract USAF ЗХ0МИ7М1, CONFIDENTIAL CSPIA Abstract No 12,4(3) 4 J. LumX aad R. W. Todd (to Standard Oil Company IladbaaJ), U. S. Fates! 2334225 (19ОД 7. РЫКфе FetrpiraB Смари>, ПееНорепем of Com- pads» РгореИагв !ao Units. Final Report се Supyit wtal Адгошх-и No I {Report 722-F54RF). I July 1954. ChMract AF ЭМ«Ю>710 (SPIA Attract No. 14,254). t Ficatxnay Anenal teaic ЛсматА on Наше Rocket fropiUenti. MB Jew-Dec., 1946. Jml-Dec, 1947, Jm>Doc_ 1941. Jan-Miy, 1949. CONFIDENTIAL (ЗУ1А Abacruot No. 10,073). 9 J. L, Jooee, Рпцтелг bt ike Otnlopt.itr- of An Awnmium Hinas Smokeless Solid Propeliasu, let Fropolaion Laboratory, Ci Йогам hutkutr o4 Tecb- aotogy, Bulktio erf the Fourth Меешд of the Алву.Navy SoUd Fropefiaat Group, p. 207, CON FI^CNTIAL, Solid FippeBaitt inlormax^ta Agency, Awbed Fhjwca Laboratory, The lobar Noptoaa Uat- varwt), *Mr Spruce Mary'iMd CSPLA Ahatract No. 37ID. 10. N. 3. Bowman. Developnusu of an AawnoaiMM Hi- not Ben Soiso PropeUems, Suadard Oil Coag*s> (larkanaj. Qawneriy Brpon No. 29 (Attf -Or. 19M). 15 laaaary 1957, Ccecrac; 33(031127541, OONF1 DENTIAL TSPIA Abatru* No. 17.1521 II. Standard Oil Совп алj (ladtatMl, private ссвамаи- еамж. 12 H. V Кгюйгу (iktMiM Criirai-ni Согропдшал pr>- vaU «OBtawacalMK. 13. A. M Jacoba aad !. H. Godtr*, Burning Bae Modi JSearioa of DoebieSea fropelionu, Alkgas) Ballis- tic» Laboratory, Herutlra Powder Сощраа/, Bulkiia Ы tbe nfieeatb Mattias orf tbe Joint Amy-Navy-Air Force Solid FropeUiei Group. Vol IV, p 41, CON- FIDENTIAL, Solid Prope&aBt lutorBatioc Agency, Applied Fbyrica Laboratory. The Johat Hqpkiaa Uei- wraiiy. Silver Spriag, Maryland. 14 С. E. Bartley, A Preliminay Investtgaion of Ле Лек- BerdloM SoM РтореОям OBDCfT 2i. Jet Fropui- atw Laboraioty, СаИсаш lorutuu al Tech*oto*y. CTT/Jn. FB 4-it. 26 Auguat 1945, CONFIDEN- TIAL (SPIA Abstract No. 2990). 15. W. C. Ayaxck, Deeifn end Internal Bafiuric Data tor PoIrtullUe-Perchlowe FropeBanu, Tkiokol Ocsm- cai Corporation. Report No. 24-51, October 1951, CONFIDENTIAL (SPIA Abend No. 11,247/. 16. A- T. Gnxzo, Drvetopmnu of Standard Operating Procedtm for Msuutfactitre of Fotpnrlisde Perchlo- rate PropeUonu, Tbiokol CtexoicaJ Corporation. Re рол No. 2^-51, November 1951. CONFIDENTIAL CSPLA Abetnd No 11,361). 17. C F. Dougherty, *YrocesBg Hebber-Baae Onrapoa- hc Rocket Рторейын,* Скат. Eng. Progr. S3, 439 (1957). 14 R S Dobynr aad J A. McBride, РюАпакт Prob- lems on Solid PnrpeHsuu Rocket Motors papa prseeotod a: American Rocket Socieiy Sminuraunl Наград- 10-13 >UM 1937, 3aa Fraachco, Califcraia Ill
CKAPW. W fNBtl SIMULANTS FCK HtOPBLANTS 39. Gmeral. Propellants arc fouardous mate- rials, necessary for functionii>g In their engmes but undesirable for many uses such as display and break-in of manufacturing equipment when ftmc- tiocinf is not contemplated Tc meet the requirt- ment for materials for such nonfuncnouing uses, inert tiintslauis or dummy formuladoDs have been developed to represent propellants The ideal inert simulant for any propeBaat should duplicate tbe propellant in all physical properti»—appearance, density, trxtuit, hard&e&i, physical strength, and ptasskity over a temperature гаедг—without being a propellant. Сой»«ктаЬк «йргскж with tbe ideal is permissibk and usual to save time and devetopajctit expense, depending on the use to which tbe dummy is to be put. M, Mack-wye.. Where jpoeeetry is the only con- sideration, as far iliasanttioii of the spatial rela tiooshtp of the prapeUaBt to other puts of the eagtn* or for assurance that tbe engine compete with propellant can be aMembied, the dummy may be built of wood and painted the proper color. Coal is as admirable mock-up lor black powder. <1. Maleate to repratac# physical properties. In order to demonstrate the phytical properties of a propellant by tbe use of an inert simulant, one needs unucihlng mors cloudy akin to the propel- lant than a wood mock-up. Mos', modern pre- рс0м1& жгг pAttbok, eid л pi**Tv^ dummy will icok, icd, sad haueie move fake ru live courier part. Must of the physical properties of propellants are traceable to the polymer content. In the case of fuel binder campoete propellants the same volume percent at ttie шве binder together with a suitable KJUr should result in a reasonable dupb- cation of tbe physical properties. The filler should, if possible, have the same specific gravity ana crystal structure aa the OJudaui used iu the iriv peepeJlant. For example, potassium chloride is г •ood replacement for ammoBium perchlorate 11 the specific gravity of the filler сашмх be precisely matched and demdy of tbe dummy u important, as in locating the center of gravity nf tbe e gjae, the volume percent cf tender can u-uaUy be com- prembed safely. Alternatively, two inert simu- lants for a propellant may be dtvtkpod, car, to dupbcsic density and another to diqd irate other phytical properties required. The problem it considerably more difficult when the polymer is itself a propedant as is nitroceilu- tore In this case an inert polymer should be found, with density and other phytic*! properties dupb- catiug the propellant polymer This has, in gcoeral. Dot been done. Cellulose acetate is a popular simu- lant for tutroceHufoK, but it is not very good Tbe dtflerence is appreciable m density, appearance, and feel, even with the best available plastscuen. In order to reproduce density it appears necessary to use crystalline tillers which worsen the match between duinaay and live propellant in other properties. An inert ausuhtnt for OlO cast doubte-base propellant {see SFLVM2) was formulated as follows. Outsat Cd "tins Powder Soireei CclhtioM M AMc 05? TriaceCa 0.10 0M2 Graphite 0.05 — RedteMl Э.УС — 2-№traiipbesylaatiae 0.034 100 LOO Соддагёюа ot the iaert with live 0)0: Inert Live Cniiu Poutier Detu-cy. f, (/cc l.t 5 13 Pwckiav dwity. » 'er »ro l Ol Casr Powder Dcatiry. p, 1.63 1.53 earik ш eseth, pei 465 WO EioafetiosL, peroral s 49 Volume со.&эеш ol expaasioe, per degree F ca x io-t Krw dX Simulants to reproduce maastactiartag pre^-ries. In the development of new manufac- turing equipment, for checking out esti-uders aod vtlsCr OfCi of piuCCSSiBg чаййГйтисгу aster main- tenance or prolonged inactivity, and to duplace Live propellant preparatory to shsamembiy cf proc- esaibg equipment, it й necessary to have • dumc?y formulation that behaves hix live propellant in process In general this requires matching mcchan- ica! properties not only dry and at ambient tem- perature but also over a temperature raryjr and 112
pcrhapr wtafaed with vofatife solvents Smce ii и the polymer whxh largely de'ennioes manufac- turing propertie* u well au product physical prop- C-iiXi, мёмёисмиий Ci fiiK f ii gvucPally adequate in fuel binder coopowtct It must be verified Ош the replacement filler will not aflect the reaction rate o< any chemical changes involved in the manufacture. There are do good maaufaccurng dmar.fes fix nitrocellulose-base propellants. Wax,' with or without sawdust, or similar carbonaceous material and ceiiukwc acetate compos;docs, respectively, have been used successfully for clear out and to put toads ж snachiuery, but they do sot duplicate the operating mechanical loads, nor do tw, dic- tate the dHDeosional changes .n the product during manufacture. <J. SoMBha. In order to overcome the dis- advantages of a completely men dummy ш studying manufacturing problems cf nitrocellulose system propellants, semilive simulants have bees developed, in which the nitrcctlititow: it retained as the polymer but all plasticizers used art fuel piasticuett 1 his results in compositions of few or negative calorific value. If igniwd these simulants will burn slowly and incompletely, allowing opct- aurtg personnel to escape safely but emphatically demonstrating any mechanical situations that could cause destructive damage With 11 vt propel- lant. In formulating a semilive propellant, the con- centration of nitrocellulose should be about tne saxtK as in the live counterpart ano the viscosity cf the fuel plasticizer rbould be as clo*e as pos- sible io the vivcosiry а йк combined plastioueii in the five propellant With these i-itaJ criteria the composition of the serai live propellant can be readib developed empirically. Tbs vomposiuon and physical ptvpe-rties of N-5 and its semilive analog are shown below. N 5 S<auijv, NarucelluJa»*, 11.4% N 50.К. 54.1» harog!j»c«na 34 .SK L>s-n txitj. phthalate — 3C.S7 Di (2-ethyt besyi ? f hiuAlue *£? 10ЭО Dtechyl phuuiue 10.50 2-burodtpbeajiair oe 2.0C 2 tl Lead m1U 2.40 2.10 CusdehUa OJO 021 Specific 1.56 1.31 Niirocclivic* cozaccatratioa, t 'cc 0.7» 0.71 Теш tie Kieafth. cronnfc, pa. 320 210 Tcoaih >иеед'.К length*at, pi. 4K 3JC t Всадоюе, pcrcuri 4? 73 The lower tensile strength and greater elongs- tioti ot the sc anil ve propellant are seen to follow the lower nitrocellulose cono.ntiauon as predicted. Extrusion pressure with the semilive was also con- sidcrabty fewer than will 'ive N-5. In spite ot the fact that the semilbe appears to be somewhat deficient in nitroccUuiose it has bce.i used success- fully to break in extrusion equipment of experi- mental des^n The measured calorific va’ue, 435 cal/g, is well аЬсле toe calculated value, demunstrari^ agari tt< lack of equilibrium in calorimetry ot cool propellants discussed in Chants 2. Tbe burning rare, about 0.01 in./see at 70'F, lOtiO psi, is low enough to prevent destruction of extrusion equip- ment in case ot fire 113
OLOisSAIiY The terae eelоь. as usacs in thu hoxieooK, ere Ordnance tante or are uaerf in a »₽» laliiw ыгй, Other V *s are as defined i'. AA 32b-6, feictioM.-j of ijniteu SUtee Ara> Тепн, *•* «II STO-444, Иаеаг.сlatere «ос definition» in the teoHr-.itior; ira« Herr -fee* ter» unabridged rftClioeary, or COMBO" ABC. tabbr;. Allegany Ba’itstics Laboratory- АША. fabbn Adtiuced Research Projects Agency bau-jokr rocket.. Shoulder fired rocket, specifi- cally tbe 2.36-incft. Waits. Continuous phase in which some ocher material is embedded. Sensing r*te, hosau. Tbe rate of burning erf a propellant measured normal to tbe burning wrfjux. caliber. The diameter of a projectile or the diam- eter of tbe bote of a gun or launching tube. Axia; distance equal to tbe caliber. сшюмг A complete ’’ssemhly, conjisting erf 2 tube and a breech mechanism, firing mech- anism or base cap, whKb is в component erf a gun, how-itKt, or mortar May include tnuzek appendages The term u generally limited io rahbers greater than 1 inch catapatL An engine which accelerates a load by nirans erf a piston driven by high pressure gas such as may be genet ated by tbe turning of a p< upe Han l. eitftnscteriflk relocily. A figure of merit of a rocket propellant, de lined as ^4^- К esmprjatte ргарейав». A propellant system com- ptmug a discrete wW phase dtspeisect in a continuous solid phase Ctrl orfaase. Volume occupied by a gas wbea coin preuod to its limit of cocoprcarioc critical thamtCrr. Diameter trf an explosive col- umn below which detonation will not propagate. de?sigiatKtt.” Buinig process in a soirfi system ccmsrisinp both oxidant and fuei tn which the reaction front ad-ances al less than sonic velocity and gase>?us products if produced move away from unrec.ted material. A defiagration may. but need not, be an explosion. «kgi-sai'lSy. Decrease of weight rale of burning as web is consumed. &ия*га«ь A material added to a propeluu; cotn- pouuuo w applied to the surfsue of a grain to decrease tbe dame temperature or rate idrfoaetioa.. An expiosiou chwactesized by props - gatioo of the reacuon front within tbe reacting medium at supersonic velocity and inotirn of the reaction products in the same direction as tbe reaction front diMtbk-basc prupdlsat. A propellant with two explosave ingr-dient», such as tutroueUuirae and cKroglycerin eroehe burning Burning at a rate higher thar normally associated with eximng pressure, due to velocit» erf coniburtinn rmyt -u-o rww ti»e burning surface expa&siou ratio- Tbe ratio of the кшк exit sec- tion area to the nuzzle Qu oat arra ехркмЬж. A very rapid chemical reaction or change <M state involving generally production of a large volume of gas and resulting in rup- ture of the coouiner if present and geuet alios of a shock wave in the surrounding medium. filit/.* Discrete material dispersed n substantial quantity in the continuous ot binda phaie of a composite propellant. tow, equihbriwu. Condition crl continuous chem- ical equilibrium during expansion ui the nozzle flow, taee-i;. Condition of no chemical reaction during expansion in the nozzle ’ Drffeis ugnifacaatl) from dahniuon C'ln ia MIL- УПк*44. 114
CHOPART । Cent in usd; for*.*. A figure of merit з gun orepeitx..:. tfcfined as -^~ t»M. An igniting or ехркмпе device in the form of * cord, consisting of a flexible fabfk tube and a core erf Io» or high explosive Used in bUning and tfemoiikon work, and in certain ammunition fates, A device with explosive components de- signed to initiate a train erf ere or detonation in an I’em of ammumucri by ?r, засол such at. hydrostatic pressure, eteetrkai energy, cheat tea) action, impact, mechanical lime. <x a cotnbina'KMi o< these Types .of fuzes are dis- oaguisbe-c by modify mg terms fonning pat t of toe item name. (In some cases the explosive components may be simulated or omitted.) fits generator. А аехке for producing gas. by burning of solid propellant to pressurize a tank. dr‘t an engine, or actuate a mechanism. £.ain. A s.ingie piece of solid ptopeiianl. regard- less of size or shape. used tr. a gun or rcxAei “green." Viet with solvent during the manufac- turing p'txess. giasl. Particle size distribution, especially that produced by gi’ndtng gen A piece of ordnance consisting essentially erf a tube or banes’ foi throw ing projectiles t • force, usua’iy the force of an cxploane but sometimes mat of ccwptessed r»> »n»inc et<- hea ci expiosioB. Heat evoked in burning (ex- ploding' a sample in a com' usuon bomb tn an inert atmosphere under standardized conditions of piesiure and temperature igtdier. A specially arranged charge of a ready burning composition, usually black powder, used to assist in the initiation of a propelling charge. hapulse. Product of thrust x time г., v ; ь, ta _ л „ _>__> - .1 <• - _—e. . . j . - r F; MiaZr».» srw . ri Mt-aMHiai армией tv >ujukv\sj LU pru>- pedant grains to pres ent burning co the coated surfaced). JANAF. labbr). Joint Army-Navy-Au Fortt Jafo. Jet-msist take off, a rocket motor cvl to supplement the eng.net of an aircraft or missile at takeoff M A ' • (abbri Moisture and volatile* кам. ratio. Ratio of the weight of the pi cpvUant to the weight erf tire loaded rocket km prop* Banta. Pr-wHin's which show neg-, five values rrf ч over short pressure ranges on a pkrf of log > verse- log P for r - bP* баоворгоревади.' A single physical phase com- prising both vudizing я. о Fuel elements mortal. A compiew projectile-ruing weapon, rifted or smoih tore, characterized by shorter barrel, lower velocity, shutter range, and higher angle erf hre than a howil&ts ora gun plastisol. A flowable suspension of a polymer tn aplasiKizet which die p-iytnci may later imbibe to produce gelation. phrUau propeUan;. Propellant showing a region ' markedly reduced slope on a plot of tog r v -. ^us tog P tor r ~ bi' port art a. The area of any opening through, winch gas moves SpecdKc 'y the area of a discharge end of a giain perforation pot life. Length ot time a temporarily fluid sys- tem can cc held or worked пепле setting up to a SO.rt; primer An. assembly v-hrth tg-iies a propelling charge, especially tn guo амтыиюп progressivity. Increase of weight rate of burning as web is consumed resorumce rod. A tod inserted into the pcrfoi a- lion erf a rocke: gram to depress the (endetRj toward unstable bunting Ewwtvi'i A arwiiaii bfretinutk. pfk> pulsion des ке that consists essentially of a thrust chamber end exhaust nozzle, and that carries it: own solid oxidizci-fuci cotnbination fiom which hot gases are generated by com- bustion and expanded through a nozzle shelf the. Tt« storage time during which an trim remains serviceable. smgie-b&se propellam. Propellant сотри- ,.ig only one explosive ingredieni. e.g., muoceli ilose ali»*n, Portions zf the gram remaining at bum- through email u-J. A gun of snsall caliber Wnhm the Ordnance Corps the term и presently applied to guns of caliber up to and including 1 tuch Such hand and shoulder xcapons as prsUiU, carbines, rifles, and siiotgjnj • Differs 1ц— die anil) from dcfuiHioc re» и МП- STD-444 11?
Glossary (Contimsd) «BiAtiess powder' Sob.d monoprr»peijant ссчп- pming ritroceiiulosc. with or without orMizirg and or fut; plasticizers SFlA. (abbri Solid Propellant lnf>rmatton Agency SflA, М2. propellant Mitniuzl St i.A.’Mi. issired by Scad Propellant Information Agency rpc-cihv Bnpu-U*. A figure of ment of a rocket propellant, defined as - Й •СНГ *n эдг.&здкГ) from de&uiaon f>ra ic M 1L STD-444. therunA*eajistn. The denvatxxt ai the ©ompo- sturet, temperature, and denied parameter? of the com bust i or, products froth lire сотпроыиоо of the propellant, the heats of formation of the in£7"d?ents and the tbennody naauc prupc.T-cs of the products trsplt-bsw pro, Ilaat. Propellant with three ел- plosive ingredients. икЬ *s rulrocelluioat, tutro- giycenr. and mtr©guanidine weti. ТЪкклем of propellant *a" consumed by burning 116
INDEX A Abe: Set Xobie-Abci e^tiat'Mi ABL •bort cakuiauo® lot specific impulse. 10 Accelerant», 20, 5b Acetone. 46 Aiiuraft iCAT’ci. 45 Alununv". 17 Aruncmu® nitrate. 44. 58, 69. 93 Aaimomwm pt r chlor ate. 14, 44. 89. 90 Агг-гкхиищ pscrJte, 94, 95 Aauiecling 80 Aspaaiu 89, 95 Auioigniuon lest. 53 a Baclunanr.-procws (RDXi, 43 Bail Pou At 74 Barium mtrate, 50 Barrci life St Erouua Bazooka, 56 Beaker, 88 binder, 16, 58, 89 fuel, 89-111 пюпо tof<ha?.t, 58 volume fractwo. 59, 8S. 94, 98. 101, 102. 112 Pitch, powder. 33-41, 89 Blasting powder, A. 33 Biasting powder, B, 33 Blending. 46. 65, 72, 88 Block breaku, 68 'tuuuvcijukMe,1, 62 Buttle temperaiure, 31 Burning area., or iurf»ce, 5, 13, 16, 17 fhiiaitcc, 17 of propellants, 12-17 rare, iuKsau, r, 3, J2, i j, 15, 36, 56, 90, 94, 95 rate, weight or ouu, F . 13, 19, 20 unstable, 17 Burrtitu charge, 40 € СаклШ value, Q, 6. 10, 45, 50, 53, 67 Culorimetet, Boat, 10 coal, 10 Calorimetry. 5 3 Салэсо propellant, 27 54, 74 Caicx»n black, 50 Carpel roUing, 80 Case bunding. 28, 45. 52, 88, 89. 94. 95. 99 Casting. 88, 89 C*« double-base ргомм, 74, 84 Casting powder, 74. 8.i Casting solvent. 85 Catalyst polym.nie'-KW, 95. 98 Catalyst. brirning rate. 15, 95 Catapult propellant. 20 Cellukue ax Ute, 46. 52. 95, 102. 112 СеЙРкн; nitrate. See Nitrocellulose Centralise ethyl. 48. 4S, 58 m-Hhvi. 49 Centrifugal wruige-. 62. 65 CNuacienstic текхлиу calculated. 4. 7, 50 measured, r*, 11 Cbmcoai. 33 Chromium, 93 Coating 19. 72. 75 CobalL 93 Cokl fltY*. 52, 89 Ccitoid. prot etive. 75 Composite fuel bender, 27, 59, 89-111 ttranop.-vpil'oui binder. 58-61 propel/ini, I j, 16 17, 27 CosnfxriiUon dust, 36 Сопфгтлт nrukhng 44, 94, 102 Cotupresaivi Hrength, 31,94-95, 102 Configuration, 17 Cco&fcrv atxxi espauun.’,, 6 Corni?2 ttvM, 33 Conodoo, 37, 93 Cvvuiumc, л, 3 Creep, 31 Cnixai duj&etei, 17 Cross-finking, 52, 95, 99, 101 Curing. 88, 89. 96, 99, 101 Cutting machine, 73
INDfcX (Continued) D Deflagration. 17 Deform* uoa, 31, 52 Degressivity, 18, 19 IXnit iUOfi, t>6 Detuiiy, f. 13, 27, 52. 90, 93, 99 bulk, 72 gravimetric, 2? de Saint Robert equa’uoo (burning rate). 13 Dtsaxant, 21 DewM-juo, 17, 27, 40 DeMrw, 66 Die, 66, "2. 80 Dtethylene giy.xd dmitrau, 49, 59 Dtftueija. 14, 27, 61, 92 Ditetxyaaate. 98 DtruUocoiueiic, 30 DtpbeoylanuDe, 48, 49, 74 Dcubte-bai* propellant, 45, 4b, 53, 6 \ 68 Du»ei red machine, 80 Dummy. Set Idui aimuiazu Du Poa: tEechamcal dipping prixeti. 62 L'u", 72 8 Etocgauoo (uuaikj, 28, 95, 99 fcmelijotL 7j Егккмйегшк group*, 102 Enthalpy, 6 jyi > /. w, У5 Equaaoc of itate, 3 Eroeoc, 45 Exoeive burning. 15, 23 Erotinty remnant. 15 Ether-alcobcl (mlventj, 46, 66 Ethyl кили, 74 Ethyl txatraliie See Ccnu alite, ethyl Ехрагшои ruUo, 11,23 Explosive, high, 40 Eapk*u*c, primary, 42 Extruder, 101 Extruuon, aoJveat, 61, 66 aolventkn, 66, 80, 94 f Filler, 16, U2 Firedamp. 40 Fuz гиие, 12 Flame tetDperitwe a? cotutit-t presrme, Tt, 5. 6. 7. 10, 93 temperature a; oorutant volume, 7,, 5. 6. 7, 9. 20, 45, 50, 53, 58 ZDlte, 12 Flwb, 37, 50, 54, 58 Raw >. 84, 88 How equilibrium, 7 truer и ccmpoaitMXi, 7 lamina., 15 tuxbukut, 15 Flying cutter, 80 Foam tone, 12 Faue Srr SpeczSc force relative, Rf, 10, 11 Free racbcal, 4. Fuel, 16 Fuse, Шегу, 40 Fuze. 40 • Gar generator propellant, 2ч, 50, 54, 56, 58, 80, 89.93 SxMiepjwer, Ghp, 4, 5 1 , _ „„ *М*Ы£ЛЖ, Glazing. 7 2 Grain, 17 cord, 20 cruuforni, 23 dual composiuoc, 19 mulupk-peifocateJ, 19 rod and aoeli, 16, 23 segmented, 102 iloaed-rube, 18, 23 alar-perforated, 18, 23 strip, 20, 80 GranuLauoo, 17 C-rn., 58. 91, 94. 96 Gun, 19 Guocotwo, 46, 6L- Gunpuwdei, 33 Gun рторе'йаш, 37, 53, 58, 67, 80 118
H Heat capacity C,. 6 Sois. 22 of explosion.. £>, 6, IQ of fcrtnahoo, i£. 6 ten, 52 H inc Me kier -Sher m ar. сышил, 7, 9, 10. 5? constants, HMX, 43, 94 Humidity «tlauiie, 2" 92 Hydrogen cbkwide. 89. 92 H)groscc₽<ity 27, 56, 44. 46, 48, 52, 93 ! Igmie*, 40 Igiz-tWity 45 Ig-Uon, 95 Impact uienfc .r 31 Impetus. Sei Specific ioetx Impulse, total, 22, $5 Ibcc’poratKM?.. 37 loert simulant, 112-113 Inhibitor, 17, 26, 52, 80, 85, 101 IntcrkM balhi’oct, 3 J JANAJ Fhyucai Properuei Fcnel, 28 Suuk Test Panel, 11 TbernwchemWal Panel, 7 Jerk, 20 Jordan engoe. 65 I Lacquer, 75 Lead. 14, 50 Lithium perohkniii, 93 M M асе г aих, 68 Mandrel, 96 Mannaa, 66 Mui frutbon. Set M.u> ratio mt cf discharge, 22 ratio, 89 Melting pc*nt, *2. 61 Me t propellant*. 14 Metal fouling. -5 Millian Wend (nitrocellulose’, 45 Mifon Nue, 93 Mineral jelly- 49 Miter Schraedei. 68. 77 ««ma blade. 67, 77, 95. <4>. ’02 vet пса), 96 Mriing. 67 Mock-up, 112 Modulus (\ uung sj, 28. 31. 45, 52, 95. 99 Moid, 88, 96 MWeculbi weight, 6, 48 MoOopropcUant. 1, 12. 16, 17. 42, 44, 58, 93 Mixur propellant, 54 M1 itrpe-grun charge. 29 Muraour equation (bunung raiej. 13 Muzak eoctg- 54 velocity 59 N Neck, 80 Neutrabty, 17, 19 Futruoc (nitrocellulose.), 62 NiL-oceliukae, 45, 58, 62, 112 basing 62 inihur) bead, 46 oitrator, 62 nitrogen content, 46, 65 poaching, 65 reclaimed, 74 aduiality, 46, 66 vi*coaity, 46, 48, 66 wood, 66 x-Nitrocupbetij ssinine, 48 Nitrogen content (nitroccUukw), 46, 65 Nitrogivcenn, 45, 46, 48, 49, 52, 68, 75 Nitrogitanidine, 37, 42, 58, 94 Noble- Abel equxuoc, 3 Nozzle half-an^k, 11 Opacity 50 Oxidizer, 16, 89, 102
р Perfect gas equation. 3 PETN, 44 Phau cbangcs. 44 Phthaiatei. 49 Piobett a Law, i 3 Ptsto! propel!-nt, 50 Plasitcity, 57, 66 PlMUCOer. 4b. 52. 75, 95, 96, 9у, 1C2, 113 fuel, 4э, 50, 68 oiudtni, 45, 4s. 49, 58. 68 Piaausol. Iff Plateau propellants, 54 Poaching, nitrocellulose, 65 Poiytsobuumc, 95 Polymer. 45, 69, 95. 112 cotK-xnwatioi,. 51. 52. 54, 67, 84, 113 Pubimcihyi ШС1СЖ.1 yiatei. 48 Pofyipcsm actyiatc.1. 48 Polyp;opjкЛс glycol, 98 Pol ^irir-itroeihyl ccry—tc;, 48 Fol> vinyl chloride}. *'5. 99 Polyvinyl ustrate). 48 Porosity, I ? Port to throat ratio, 23 Pot life, 8s, 101 Potassium threw, 3' r»,. SO on salts, 50, 58 Premixmg, 67 Prepolymer, 95 Frew blocking, 72, 102 dehy, 67 eiLitwoa, 80, 102 finishing. 72 macaroni. 72 screening See t tets, macaroni Ptcwure chamber, P, 11, 13 maximum, 19 index, n, 13, 45, 94 .Primer, 40 Progressivity, 18, 19, 20 Prussian blue, 93 Puhervxr, 36 Pycsxnueier, 2? Py.v.ellulose (nitroceiluk; c), 46 Pyrolysis, 12 a Quality assurance or ctsntro’, 11. 20, 28. 84 Quickness, relauve. KQ. 2'0, 43 R RDX. 43. 58 Reduced characteristic velocity, 4 specific impulse, 4 Reel. 36 Resonance reds. I7 Foberts process (mtroguanid;ne\ 43 Rocket propellant, 22, 37, 40. 54, 56, 58. 74, 8u, 89. 93 Roll mills, 77 Rolled sheet process, 77 Relit cutting, 37 sizing. 75 Rubber, 95 butadiene —acrylic acid copolymer (PUAA}, 99 butadiene—2-tnethyi-5-vtny ipyndme copolynnu, 101 GR-I, 102 .,,,14;^. nt t гмггг ( v< polyurethane. 91 Rule die. 80 S Saltpeter, 33 Screening. 72, 75 Second order transition temperature, 31 Semilive, 11 3 Shear. 31 Shelf life See Stability Shock. 17 Single-base propellar.L, 45, 53, 68, 72 Slivers, 19 Slurry casting. 75, 88. 95, 102 m’sing. 68, 77 Small arms propellant, 27, 54, 67, 72 Smoke, 40, 50, 29. 90. 92, 93 Smokeless pc* Jer, 45
INutK (Concluded) Soffium mtrau’. 3? Solubility I r;ilr scehulowi. 46. fr& Solvent removal. 72 residual. 27. 50, 5 3. 6b volatile, 2?, 52, 54 Spect.'K force. Г. 4. Г ,0 20. P. 46, 50. 53, 58 heat ratio, y. 6, 7, ! ( impulse, 4, 1 ’, 22. 4$. 56. 90. 93, 99 calculated, /£. 4 5. 7, 5v measared. 11 volume. 5 soJume, 3' SPIA lato Manual. 2"' Spotting propellant, 5*i, 67, 72 Stability. 36, 42, 52. 61 Stabilizer, 45, 48 Stalk. eicctr^nty. 72 Static test, 23 Suh. 7a Stress telajcairon, 28 Sulfur, 33 Summerfield equation (burning ratej, 13 Supersonics, 84 Suneillarsce teA, 52 Sweetie barrel, 72 1 Tailings, 27, 72 Tapani test. 52 Temperature соейскпь of burning. 14, 15 Temperature, initial, 14 Tensile strength, 28, 51, 99 Thermal conductivity. 2£ decwr.psmkon. 4b. 52 expansion ojefficient, 28. 52 msinanoa, gu User theory, 92 TbernuKisemistry of prspellanu. 3, 5, 33. 42 Thermoplastic. 95, 10? Thiocyanate process (nitroguanidme), 42 Thrust. ) I coefikieni. 11, 23 coefficient arid expansion tauo tables, 11 Tnaccun. 50 Triethyiene g._.col dim irate, <9 Trip’e-basc propellant, 58, 74 Two-tempctatuie theory, 91 V V apor pressure. 49. 50, 52 Velocity, burned, 56 Vibration modes, 17 Viscosity. 94. 113 of nitrocellulose, 46, 48, 66 Volumeter, 2/ Volumetric efficiency, 27 W Water gas eqiilibnum, 6 Web. 18 54. 67, 72 Kneel null, 3 7 Kite, 50, 101 Woolwich process (RDXj, 43 X X-rays, 84 Xylan, 66 «: * oc'f илbx>: раднтж. o*r,.e 121