Green Energetic Materials -- Contents -- List of Contributors -- Preface -- 1. Introduction to Green Energetic Materials -- 1.1 Introduction -- 1.2 Green Chemistry and Energetic Materials -- 1.3 Green Propellants in Civil Space Travel -- 1.3.1 Green Oxidizers to Replace Ammonium Perchlorate -- 1.3.2 Green Liquid Propellants to Replace Hydrazine -- 1.3.3 Electric Propulsion -- 1.4 Conclusions -- References -- 2. Theoretical Design of Green Energetic Materials: Predicting Stability, Detection, Synthesis and Performance -- 2.1 Introduction -- 2.2 Computational Methods -- 2.3 Green Propellant Components -- 2.3.1 Trinitramide -- 2.3.1.1 Synthesis and Detection -- 2.3.1.2 Properties and Performance -- 2.3.2 Energetic Anions Rich in Oxygen and Nitrogen -- 2.3.2.1 Trinitrogen Dioxide Anion -- 2.3.2.2 1-Nitro-2-oxo-3-Amino-Triazene Anion -- 2.3.3 The Pentazolate Anion and its Oxy-Derivatives -- 2.3.3.1 Kinetic Stability -- 2.3.3.2 Spectroscopic Detection -- 2.3.3.3 Synthesis -- 2.3.3.4 Performance -- 2.3.4 Tetrahedral N4 -- 2.3.4.1 Potential Energy Surface -- 2.3.4.2 Spectroscopic Detection -- 2.3.4.3 Synthesis -- 2.3.4.4 Thermodynamic Stability and Performance -- 2.4 Conclusions -- References -- 3. Some Perspectives on Sensitivity to Initiation of Detonation -- 3.1 Energetic Materials and Green Chemistry -- 3.2 Sensitivity: Some Background -- 3.3 Sensitivity Relationships -- 3.4 Sensitivity: Some Relevant Factors -- 3.4.1 Amino Substituents -- 3.4.2 Layered (Graphite-Like) Crystal Lattice -- 3.4.3 Free Space in the Crystal Lattice -- 3.4.4 Weak Trigger Bonds -- 3.4.5 Molecular Electrostatic Potentials -- 3.5 Summary -- Acknowledgments -- References -- 4. Advances Toward the Development of "Green" Pyrotechnics -- 4.1 Introduction -- 4.2 The Foundation of "Green" Pyrotechnics -- 4.3 Development of Perchlorate-Free Pyrotechnics.

4.3.1 Perchlorate-Free Illuminating Pyrotechnics -- 4.3.2 Perchlorate-Free Simulators -- 4.4 Removal of Heavy Metals from Pyrotechnic Formulations -- 4.4.1 Barium-Free Green-Light Emitting Illuminants -- 4.4.2 Barium-Free Incendiary Compositions -- 4.4.3 Lead-Free Pyrotechnic Compositions -- 4.4.4 Chromium-Free Pyrotechnic Compositions -- 4.5 Removal of Chlorinated Organic Compounds from Pyrotechnic Formulations -- 4.5.1 Chlorine-Free Illuminating Compositions -- 4.6 Environmentally Friendly Smoke Compositions -- 4.6.1 Environmentally Friendly Colored Smoke Compositions -- 4.6.2 Environmentally Friendly White Smoke Compositions -- 4.7 Conclusions -- Acknowledgments -- Abbreviations -- References -- 5. Green Primary Explosives -- 5.1 Introduction -- 5.1.1 What is a Primary Explosive? -- 5.1.1.1 Common Initiating Devices: Detonators/Primers/Blasting Caps -- 5.1.2 The Case for Green Primary Explosives -- 5.1.3 Legacy Primary Explosives -- 5.1.3.1 Lead Azide (LA) -- 5.1.3.2 Lead Styphnate (LS) -- 5.2 Green Primary Explosive Candidates -- 5.2.1 Inorganic Compounds -- 5.2.1.1 Silver Azide (SA) -- 5.2.1.2 Other Inorganic Azides -- 5.2.1.3 Nickel Hydrazine Nitrate (NHN) -- 5.2.1.4 Metastable Intermolecular Composites (MICs) -- 5.2.1.5 Red Phosphorous -- 5.2.2 Organic-Based Compounds -- 5.2.2.1 Tetrazoles -- 5.2.2.2 Sodium 5-Nitrotetrazolate (NaNT) -- 5.2.2.3 Copper(II) 5-Nitrotetrazolate Coordination Compounds -- 5.2.2.4 Copper(I) 5-nitrotetrazolate (DBX-1) -- 5.2.2.5 Bis-(5-Nitrotetrazole)Tetraamine Cobalt(III) Perchlorate (BNCP) -- 5.2.2.6 Other Tetrazoles -- 5.2.2.7 2-Diazo-4,6-Dinitrophenol (DDNP) -- 5.2.2.8 Potassium 4,6-Dinitrobenzofuroxan (KDNBF) -- 5.2.2.9 Potassium 4,6-Dinitro-7-Hydroxybenzofuroxan (KDNP) -- 5.2.2.10 Cyanuric Triazide (CTA), aka Triazine Triazide (TTA).

5.2.2.11 Peroxide Explosives: Triacetone Triperoxide (TATP) and Hexamethylenetriperoxide Diamine (HMTD) -- 5.3 Conclusions -- Acknowledgments -- References -- 6. Energetic Tetrazole N-oxides -- 6.1 Introduction -- 6.2 Rationale for the Investigation of Tetrazole N-oxides -- 6.3 Synthetic Strategies for the Formation of Tetrazole N-oxides -- 6.3.1 HOF.CH3CN -- 6.3.2 Oxone® -- 6.3.3 CF3COOH/H2O2 -- 6.3.4 Cyclization of Azido-Oximes -- 6.4 Recent Examples of Energetic Tetrazole N-oxides -- 6.4.1 Tetrazole N-oxides -- 6.4.2 Bis(tetrazole-N-oxides) -- 6.4.3 5,5'-Azoxytetrazolates -- 6.4.4 Bis(tetrazole)dihydrotetrazine and Bis(tetrazole)tetrazine N-oxides -- 6.5 Conclusion -- Acknowledgments -- References -- 7. Green Propellants Based on Dinitramide Salts: Mastering Stability and Chemical Compatibility Issues -- 7.1 The Promises and Problems of Dinitramide Salts -- 7.2 Understanding Dinitramide Decomposition -- 7.2.1 The Dinitramide Anion -- 7.2.2 Dinitraminic Acid -- 7.2.3 Dinitramide Salts -- 7.2.3.1 Potassium Dinitramide (KDN) -- 7.2.3.2 Ammonium Dinitramide (ADN) -- 7.3 Vibrational Sum-Frequency Spectroscopy of ADN and KDN -- 7.4 Anomalous Solid-State Decomposition -- 7.5 Dinitramide Chemistry -- 7.5.1 Compatibility and Reactivity of ADN -- 7.5.2 Dinitramides in Synthesis -- 7.6 Dinitramide Stabilization -- 7.7 Conclusions -- References -- 8. Binder Materials for Green Propellants -- 8.1 Binder Properties -- 8.2 Inert Polymers for Binders -- 8.2.1 Polybutadiene -- 8.2.2 Polyethers -- 8.2.3 Polyesters and Polycarbonates -- 8.3 Energetic Polymers -- 8.3.1 Nitrocellulose -- 8.3.2 Poly(glycidyl azide) -- 8.3.3 Poly(3-nitratomethyl-3-methyloxetane) -- 8.3.4 Poly(glycidyl nitrate) -- 8.3.5 Poly[3,3-bis(azidomethyl)oxetane] -- 8.4 Energetic Plasticisers -- 8.5 Outlook for Design of New Green Binder Systems -- 8.5.1 Architecture of the Binder Polymer.

8.5.2 Chemical Composition and Crosslinking Chemistries -- References -- 9. The Development of Environmentally Sustainable Manufacturing Technologies for Energetic Materials -- 9.1 Introduction -- 9.2 Explosives -- 9.2.1 Sustainable Manufacturing of Explosives -- 9.2.2 Environmentally Friendly Materials for Initiation -- 9.2.3 Synthesis of Explosive Precursors -- 9.2.3.1 The Use of Oxone -- 9.3 Pyrotechnics -- 9.3.1 Commercial Pyrotechnics Manufacturing -- 9.3.2 Military Pyrotechnics -- 9.4 Propellants -- 9.4.1 The "Green Missile" Program -- 9.4.2 Other Rocket Propellant Efforts -- 9.4.3 Gun Propellants -- 9.5 Formulation -- 9.6 Conclusions -- Acknowledgments -- Abbreviations and Acronyms -- References -- 10. Electrochemical Methods for Synthesis of Energetic Materials and Remediation of Waste Water -- 10.1 Introduction -- 10.2 Practical Aspects -- 10.3 Electrosynthesis -- 10.3.1 Electrosynthesis of EM and EM Precursors -- 10.3.2 Electrosynthesis of Useful Reagents -- 10.4 Electrochemical Remediation -- 10.4.1 Direct Electrolysis -- 10.4.1.1 Cathodic Reduction -- 10.4.1.2 Combined Reduction and Oxidation -- 10.4.1.3 Anodic Oxidation -- 10.4.2 Indirect Electrolytic Methods -- 10.4.3 Electrokinetic Remediation of Soils -- 10.4.4 Electrodialysis -- 10.5 Current Developments and Future Directions -- References -- Index.