Green Energetic Materials

This comprehensive book presents a detailed account of research and recent developments in the field of green energetic materials, including pyrotechnics, explosives and propellants. This area is attracting increasing interest in the community as it undergoes a transition from using traditional processes, to more environmentally-friendly procedures. The book covers the entire line of research from the initial theoretical modelling and design of new materials, to the development of sustainable manufacturing processes. It also addresses materials that have already reached the production line, as well as considering future developments in this evolving field.

Professor Tore Brinck, KTH – Royal Institute of Technology, School of Chemical Science and Engineering, Sweden
Tore Brinck received his Ph.D. in Chemistry in 1993 from the University of New Orleans. He was appointed full Professor of Physical Chemistry at the Royal Institute of Technology (KTH) in 2006. His research has focused on theoretical and experimental characterization of novel high energy materials. He is the author of more than 80 scientific articles.

Preface xi

1 Introduction to Green Energetic Materials 1
Tore Brinck

1.1 Introduction 1

1.2 Green Chemistry and Energetic Materials 2

1.3 Green Propellants in Civil Space Travel 5

1.3.1 Green Oxidizers to Replace Ammonium Perchlorate 6

1.3.2 Green Liquid Propellants to Replace Hydrazine 8

1.3.3 Electric Propulsion 10

1.4 Conclusions 10

References 11

2 Theoretical Design of Green Energetic Materials: Predicting Stability, Detection, and Synthesis and Performance 15
Tore Brinck and Martin Rahm

2.1 Introduction 15

2.2 Computational Methods 17

2.3 Green Propellant Components 20

2.3.1 Trinitramide 20

2.3.2 Energetic Anions Rich in Oxygen and Nitrogen 24

2.3.3 The Pentazolate Anion and its Oxy-Derivatives 27

2.3.4 Tetrahedral N4 33

2.4 Conclusions 38

References 39

3 Some Perspectives on Sensitivity to Initiation of Detonation 45
Peter Politzer and Jane S. Murray

3.1 Energetic Materials and Green Chemistry 45

3.2 Sensitivity: Some Background 46

3.3 Sensitivity Relationships 47

3.4 Sensitivity: Some Relevant Factors 48

3.4.1 Amino Substituents 48

3.4.2 Layered (Graphite-Like) Crystal Lattice 49

3.4.3 Free Space in the Crystal Lattice 50

3.4.4 Weak Trigger Bonds 50

3.4.5 Molecular Electrostatic Potentials 51

3.5 Summary 56

Acknowledgments 56

References 57

4 Advances Toward the Development of “Green” Pyrotechnics 63
Jesse J. Sabatini

4.1 Introduction 63

4.2 The Foundation of “Green” Pyrotechnics 65

4.3 Development of Perchlorate-Free Pyrotechnics 67

4.3.1 Perchlorate-Free Illuminating Pyrotechnics 67

4.3.2 Perchlorate-Free Simulators 72

4.4 Removal of Heavy Metals from Pyrotechnic Formulations 75

4.4.1 Barium-Free Green-Light Emitting Illuminants 76

4.4.2 Barium-Free Incendiary Compositions 78

4.4.3 Lead-Free Pyrotechnic Compositions 80

4.4.4 Chromium-Free Pyrotechnic Compositions 82

4.5 Removal of Chlorinated Organic Compounds from Pyrotechnic Formulations 83

4.5.1 Chlorine-Free Illuminating Compositions 83

4.6 Environmentally Friendly Smoke Compositions 84

4.6.1 Environmentally Friendly Colored Smoke Compositions 84

4.6.2 Environmentally Friendly White Smoke Compositions 88

4.7 Conclusions 93

Acknowledgments 94

Abbreviations 95

References 97

5 Green Primary Explosives 103
Karl D. Oyler

5.1 Introduction 103

5.1.1 What is a Primary Explosive? 104

5.1.2 The Case for Green Primary Explosives 107

5.1.3 Legacy Primary Explosives 108

5.2 Green Primary Explosive Candidates 110

5.2.1 Inorganic Compounds 111

5.2.2 Organic-Based Compounds 116

5.3 Conclusions 125

Acknowledgments 126

References 126

6 Energetic Tetrazole N-oxides 133
Thomas M. Klap€otke and J€org Stierstorfer

6.1 Introduction 133

6.2 Rationale for the Investigation of Tetrazole N-oxides 133

6.3 Synthetic Strategies for the Formation of Tetrazole N-oxides 136

6.3.1 HOF CH3CN 136

6.3.2 Oxone1 137

6.3.3 CF3COOH/H2O2 138

6.3.4 Cyclization of Azido-Oximes 139

6.4 Recent Examples of Energetic Tetrazole N-oxides 139

6.4.1 Tetrazole N-oxides 140

6.4.2 Bis(tetrazole-N-oxides) 150

6.4.3 5,50-Azoxytetrazolates 164

6.4.4 Bis(tetrazole)dihydrotetrazine and bis(tetrazole)tetrazine N-oxides 170

6.5 Conclusion 173

Acknowledgments 174

References 174

7 Green Propellants Based on Dinitramide Salts: Mastering Stability and Chemical Compatibility Issues 179
Martin Rahm and Tore Brinck

7.1 The Promises and Problems of Dinitramide Salts 179

7.2 Understanding Dinitramide Decomposition 181

7.2.1 The Dinitramide Anion 182

7.2.2 Dinitraminic Acid 184

7.2.3 Dinitramide Salts 185

7.3 Vibrational Sum-Frequency Spectroscopy of ADN and KDN 189

7.4 Anomalous Solid-State Decomposition 192

7.5 Dinitramide Chemistry 194

7.5.1 Compatibility and Reactivity of ADN 194

7.5.2 Dinitramides in Synthesis 196

7.6 Dinitramide Stabilization 198

7.7 Conclusions 200

References 201

8 Binder Materials for Green Propellants 205
Carina Elds€ater and Eva Malmstr€om

8.1 Binder Properties 209

8.2 Inert Polymers for Binders 210

8.2.1 Polybutadiene 210

8.2.2 Polyethers 212

8.2.3 Polyesters and Polycarbonates 213

8.3 Energetic Polymers 215

8.3.1 Nitrocellulose 215

8.3.2 Poly(glycidyl azide) 216

8.3.3 Poly(3-nitratomethyl-3-methyloxetane) 220

8.3.4 Poly(glycidyl nitrate) 221

8.3.5 Poly[3,3-bis(azidomethyl)oxetane] 222

8.4 Energetic Plasticisers 223

8.5 Outlook for Design of New Green Binder Systems 223

8.5.1 Architecture of the Binder Polymer 224

8.5.2 Chemical Composition and Crosslinking Chemistries 225

References 226

9 The Development of Environmentally Sustainable Manufacturing Technologies for Energetic Materials 235
David E. Chavez

9.1 Introduction 235

9.2 Explosives 236

9.2.1 Sustainable Manufacturing of Explosives 236

9.2.2 Environmentally Friendly Materials for Initiation 240

9.2.3 Synthesis of Explosive Precursors 244

9.3 Pyrotechnics 246

9.3.1 Commercial Pyrotechnics Manufacturing 246

9.3.2 Military Pyrotechnics 248

9.4 Propellants 249

9.4.1 The “Green Missile” Program 249

9.4.2 Other Rocket Propellant Efforts 250

9.4.3 Gun Propellants 251

9.5 Formulation 253

9.6 Conclusions 254

Acknowledgments 254

Abbreviations and Acronyms 255

References 256

10 Electrochemical Methods for Synthesis of Energetic Materials and Remediation of Waste Water 259
Lynne Wallace

10.1 Introduction 259

10.2 Practical Aspects 260

10.3 Electrosynthesis 262

10.3.1 Electrosynthesis of EM and EM Precursors 262

10.3.2 Electrosynthesis of Useful Reagents 265

10.4 Electrochemical Remediation 266

10.4.1 Direct Electrolysis 267

10.4.2 Indirect Electrolytic Methods 269

10.4.3 Electrokinetic Remediation of Soils 272

10.4.4 Electrodialysis 273

10.5 Current Developments and Future Directions 273

References 275

Index 281

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