Foreword .................................................. XIII
Preface ..................................................... XV
Acknowledgment ............................................ XVII
1 Introduction to Pyrolants .................................... 1
References ................................................... 3
2 History ...................................................... 6
2.1 Organometallic Beginning ................................ 6
2.2 Explosive & Obscurant Properties ........................ 8
2.3 Rise of Fluorocarbons .................................. 10
2.4 Rockets Fired Against Aircraft ......................... 13
2.5 Metal/Fluorocarbon Pyrolants ........................... 15
References .................................................. 17
Further Reading ............................................. 19
3 Properties of Fluorocarbons ................................. 20
3.1 Polytetrafluoroethylene (PTFE) ......................... 20
3.2 Polychlorotrifluoroethylene (PCTFE) .................... 22
3.3 Polyvinylidene Fluoride (PVDF) ......................... 24
3.4 Polycarbon Monofluoride (PMF) .......................... 25
3.5 Vinylidene Fluoride-Hexafluoropropene Copolymer ........ 27
3.5.1 LFC-1 ........................................... 28
3.6 Vinylidene Fluoride-Chlorotrifluoroethylene
Copolymer .............................................. 28
3.7 Copolymer of TFE and VDF ............................... 30
3.8 Terpolymers of TFE, HFP and VDF ........................ 31
3.9 Summary of chemical and physical properties of common
fiuoropolymers ......................................... 33
References .................................................. 33
4 Thermochemical and Physical Properties of Metals and their
Fluorides ................................................... 36
References .................................................. 41
5 Reactivity and Thermochemistry of Selected Metal/
Fluorocarbon Systems ........................................ 42
5.1 Lithium ................................................ 42
5.2 Magnesium .............................................. 45
5.3 Titanium ............................................... 47
5.4 Zirconium .............................................. 52
5.5 Hafnium ................................................ 53
5.6 Niob ................................................... 53
5.7 Tantalum ............................................... 54
5.8 Zinc ................................................... 55
5.9 Cadmium ................................................ 56
5.10 Boron .................................................. 57
5.11 Aluminium .............................................. 59
5.12 Silicon ................................................ 63
5.13 Calcium Silicide ....................................... 64
5.14 Tin .................................................... 65
References .................................................. 66
6 Ignition and Combustion Mechanism of MTV .................... 68
6.1 Ignition and Pre-Ignition of Metal/Fluorocarbon
Pyrolants .............................................. 68
6.2 Magnesium-Grignard Hypothesis .......................... 68
References .................................................. 77
7 Ignition of MTV ............................................. 80
References .................................................. 85
8 Combustion .................................................. 87
8.1 Magnesium/Teflon/Viton ................................. 87
8.1.1 Pressure Effects on the Burn Rate ............... 87
8.1.2 Particle Size Distribution and Surface Area
Effects on the Burn Rate ........................ 88
8.2 Porosity ............................................... 95
8.3 Burn Rate Description .................................. 96
8.4 Combustion of Metal-Fluorocarbon Pyrolants with Fuels
Other than Magnesium ................................... 97
8.4.1 Magnesium Hydride ............................... 97
8.4.2 Alkali and Alkaline Earth Metal ................. 98
8.4.2.1 Lithium ................................ 98
8.4.2.2 Magnesium-Aluminium Alloy .............. 99
8.4.3 Titan ........................................... 99
8.4.4 Zirconium ...................................... 102
8.4.5 Zinc ........................................... 103
8.4.6 Boron .......................................... 104
8.4.7 Magnesium Boride, MgB2 ......................... 105
8.4.8 Aluminium ...................................... 105
8.4.9 Silicon ........................................ 108
8.4.10 Silicides ...................................... 110
8.4.10.1 Dimagnesium Silicide, Mg2Si ........... 110
8.4.10.2 Calcium Disilicide .................... 111
8.4.10.3 Zirconium Disilicide .................. 113
8.4.11 Tungsten-Zirconium Alloy ....................... 113
8.5 Underwater Combustion ................................. 114
References ................................................. 115
9 Spectroscopy ............................................... 119
9.1 Introduction .......................................... 119
9.2 UV-VIS Spectra ........................................ 120
9.2.1 Polytetrafluoroethylene Combustion ............. 121
9.2.2 Magnesium/Fluorocarbon Pyrolants ............... 122
9.2.3 MgH2, MgB2, Mg3N2, Mg2Si/Mg3Al2/Fluorocarbon
Based pyrolants ................................ 128
9.2.4 Silicon/PTFE Based Pyrolants ................... 133
9.2.5 Boron/PTFE/Viton Based Pyrolants ............... 134
9.3 MWIR Spectra .......................................... 135
9.3.1 Polytetrafluoroethylene Combustion ............. 136
9.3.2 Magnesium/Fluorocarbon Combustion .............. 136
9.3.3 MgH2, MgB2, Mg3N2, Mg2Si/Fluorocarbon Based
Pyrolants ...................................... 139
9.3.4 Si/Fluorocarbon Based Pyrolants ................ 140
9.3.5 Boron/PTFE/Viton Based Pyrolants ............... 141
9.4 Temperature Determination ............................. 141
9.4.1 Condensed-Phase Temperature .................... 142
9.4.2 Gas-Phase Temperature .......................... 144
References ................................................. 148
10 Infrared Emitters .......................................... 151
10.1 Decoy Flares .......................................... 151
10.2 Nonexpendable Flares .................................. 153
10.2.1 Target Augmentation ............................ 153
10.2.2 Missile Tracking Flares ........................ 156
10.3 Metal-Fluorocarbon Flare Combustion Flames as Sources
of Radiation .......................................... 158
10.3.1 Flame Structure and Morphology ................. 160
10.3.2 Radiation of MTV ............................... 162
10.4 Infrared Compositions ................................. 165
10.4.1 Inherent Effects ............................... 166
10.4.1.1 Influence of Stoichiometry ............ 166
10.4.2 Spectral Flare Compositions .................... 180
10.4.3 Particle Size Issues ........................... 181
10.4.4 Geometrical Aspects ............................ 181
10.5 Operational Effects ................................... 184
10.5.1 Altitude Effects ............................... 184
10.5.2 Windspeed Effects .............................. 186
10.6 Outlook ............................................... 191
References ................................................. 193
11 Obscurants ................................................. 197
11.1 Introduction .......................................... 197
11.2 Metal-Fluorocarbon Reactions in Aerosol Generation .... 199
11.2.1 Metal-Fluorocarbon Reactions as an Exclusive
Aerosol Source ................................. 200
11.2.2 Metal-Fluorocarbon Reactions to Trigger
Aerosol Release ................................ 201
11.2.2.1 Metal-Fluorocarbon Reactions to
Trigger Soot Formation ................ 201
11.2.2.2 Metal-Fluorocarbon Reactions to
Trigger Phosphorus Vaporisation ....... 204
References ................................................. 208
12 Igniters ................................................... 210
References ................................................. 214
13 Incendiaries, Agent Defeat, Reactive Fragments and
Detonation Phenomena ....................................... 216
13.1 Incendiaries .......................................... 216
13.2 Curable Fluorocarbon Resin-Based Compositions ......... 217
13.3 Document Destruction .................................. 218
13.4 Agent Defeat .......................................... 221
13.5 Reactive Fragments .................................... 223
13.6 Shockwave Loading of Metal-Fluorocarbons and
Detonation-Like Phenomena ............................. 229
References ................................................. 232
Further Reading ............................................ 234
14 Miscellaneous Applications ................................. 235
14.1 Submerged Applications ................................ 235
14.1.1 Underwater Explosives .......................... 235
14.1.2 Underwater Flares .............................. 235
14.1.3 Underwater Cutting Torch ....................... 236
14.2 Mine-Disposal Torch ................................... 238
14.3 Stored Chemical Energy ................................ 240
14.3.1 Heating Device ................................. 240
14.3.2 Stored Chemical Energy Propulsion .............. 240
14.4 Tracers ............................................... 240
14.5 Propellants ........................................... 241
References ................................................. 244
15 Self-Propagating High-Temperature Synthesis ................ 247
15.1 Introduction .......................................... 247
15.2 Magnesium ............................................. 249
15.3 Silicon and Silicides ................................. 252
References ................................................. 256
16 Vapour-Deposited Materials ................................. 258
References ................................................. 262
17 Ageing ..................................................... 264
References ................................................. 270
18 Manufacture ................................................ 271
18.1 Introduction .......................................... 271
18.2 Treatment of Metal Powder ............................. 271
18.3 Mixing ................................................ 273
18.3.1 Shock Gel Process .............................. 273
18.3.1.1 Procedure A ........................... 273
18.3.1.2 Procedure В ........................... 275
18.3.2 Conventional Mixing ............................ 276
18.3.3 Experimental Super Shock Gel Process ........... 276
18.3.4 Experimental Dry Mixing Technique .............. 280
18.3.5 Experimental Cryo-N2 Process ................... 282
18.3.6 Extrusion ...................................... 282
18.3.6.1 Twin Screw Extrusion .................. 282
18.4 Pressing .............................................. 286
18.5 Cutting ............................................... 289
18.6 Priming ............................................... 289
18.7 Miscellaneous ......................................... 289
18.8 Accidents and Process Safety .......................... 290
18.8.1 Mixing ......................................... 290
18.8.2 Pressing ....................................... 293
18.8.3 Process Analysis ............................... 294
18.8.4 Personal Protection Equipment (PPE) ............ 294
References ................................................. 296
19 Sensitivity ................................................ 299
19.1 Introduction .......................................... 299
19.2 Impact Sensitivity .................................... 300
19.2.1 MTV ............................................ 300
19.2.2 Titanium/PTFE/Viton and Zirconium/PTFE/Viton ... 300
19.2.3 Metal-Fluorocarbon Solvents .................... 301
19.2.4 Viton as Binder in Mg/NaNO2 .................... 301
19.3 Friction and Shear Sensitivity ........................ 301
19.3.1 Metal/Fluorocarbon ............................. 303
19.4 Thermal Sensitivity ................................... 304
19.4.1 MTV ............................................ 304
19.5 ESD Sensitivity ....................................... 305
19.6 Insensitive Munitions Testing ......................... 310
19.6.1 Introduction ................................... 310
19.6.2 Cookoff ........................................ 314
19.6.3 Bullet Impact .................................. 316
19.6.4 Sympathetic Reaction ........................... 319
19.6.5 IM Signature Summary ........................... 320
19.7 Hazards Posed by Loose In-Process MTV Crumb and TNT
Equivalent ............................................ 321
References ................................................. 323
20 Toxic Combustion Products .................................. 326
20.1 MTV Flare Composition ................................. 326
20.2 Obscurant Formulations ................................ 330
20.3 Fluorine Compounds .................................... 331
20.3.1 Hydrogen Fluoride .............................. 331
20.3.2 Aluminium Fluoride ............................. 331
20.3.3 Magnesium Fluoride ............................. 332
References ................................................. 332
21 Outlook .................................................... 334
References ................................................. 335
Index ...................................................... 337
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