Metal-Fluorocarbon Based Energetic Materials

This exciting new book details all aspects of a major class of pyrolants and elucidates the progress that has been made in the field, covering both the chemistry and applications of these compounds.

Written by a pre-eminent authority on the subject from the NATO Munitions Safety Information Analysis Center (MSIAC), it begins with a historical overview of the development of these materials, followed by a thorough discussion of their ignition, combustion and radiative properties. The next section explores the multiple facets of their military and civilian applications, as well as industrial synthetic techniques. The critical importance of the associated hazards, namely sensitivity, stability and aging, are discussed in detail, and the book is rounded off by an examination of the future of this vital and expanding field.

The result is a complete guide to the chemistry, manufacture, applications and required safety precautions of pyrolants for both the military and chemical industries.

From the preface:
?... This book fills a void in the collection of pyrotechnic literature...
it will make an excellent reference book that all researchers of pyrolants and energetics must have...?
Dr. Bernard E. Douda, Dr. Sara Pliskin, NAVSEA Crane, IN, USA

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 fluoropolymers 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

8.2 Porosity 95

8.3 Burn Rate Description 96

8.4 Combustion of Metal–Fluorocarbon Pyrolants with Fuels Other than Magnesium 97

8.5 Underwater Combustion 114

References 115

9 Spectroscopy 119

9.1 Introduction 119

9.2 UV–VIS Spectra 120

9.3 MWIR Spectra 135

9.4 Temperature Determination 141

References 148

10 Infrared Emitters 151

10.1 Decoy Flares 151

10.2 Nonexpendable Flares 153

10.3 Metal–Fluorocarbon Flare Combustion Flames as Sources of Radiation 158

10.4 Infrared Compositions 165

10.5 Operational Effects 184

10.6 Outlook 191

References 193

11 Obscurants 197

11.1 Introduction 197

11.2 Metal–Fluorocarbon Reactions in Aerosol Generation 199

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

14.2 Mine-Disposal Torch 238

14.3 Stored Chemical Energy 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

18.4 Pressing 286

18.5 Cutting 289

18.6 Priming 289

18.7 Miscellaneous 289

18.8 Accidents and Process Safety 290

References 296

19 Sensitivity 299

19.1 Introduction 299

19.2 Impact Sensitivity 300

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

19.7 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

References 332

21 Outlook 334

References 335

Index 337

Dr. Ernst-Christian Koch is Technical Specialist Officer at the NATO Munitions Safety Information Center (MSIAC), Brussels, Belgium. He studied chemistry at the Technical University of Kaiserslautern, Germany and was awarded his doctoral degree by the same university in 1995. Before joining NATO in 2008, Dr. Koch spent 12 years working as a scientist for the German defense industry, developing energetic mate-rials and countermeasures. He is author of more than 20 peer reviewed papers and two book chapters. He holds more than 100 patents on energetic materials and countermeasures. Dr. Koch is a Lecturer on Energetic Materials at Technical University of Kaiserslautern/Germany and Pardubice Univer-sity/Czech Republic and he currently serves as Vice President of the International Pyrotechnics Society and as an Editorial Board Member of Propellants Explosives Pyrotechnics.