Nitrogen-Rich Energetic Materials

Description

Nitrogen-Rich Energetic Materials Provides in-depth and comprehensive knowledge on both the chemistry and practical applications of nitrogen-rich energetic materials Energetic materials, a class of material with high amounts of stored chemical energy, include explosives, pyrotechnics, and propellants. Initially used for military applications, nitrogen-rich energetic materials have become important in the civil engineering and aerospace sectors, they are increasingly used in commercial mining and construction as well as in rocket propulsion. Making these nitrogen-rich energetic materials safer, more powerful, and more cost-effective requires a thorough understanding of their chemistry, physics, synthesis, properties, and applications. Nitrogen-Rich Energetic Materials presents a detailed summary of the development of nitrogen-rich energetic materials over the past decade and provides up-to-date knowledge on their applications in various areas of advanced engineering. Edited by a panel of international experts in the field, this book examines the chemistry of pentazoles, fused ring and laser ignitable nitrogen-rich compounds, polynitrogen and tetrazole-based energetic compounds, and more. The text also introduces applications of nitrogen-rich energetic materials in energetic polymers and metal-organic frameworks, as pyrotechnics materials for light and smoke, and in oxadiazoles from precursor molecules. This authoritative volume: Presents in-depth chapters written by leading experts in each sub-field covered Offers a systematic introduction to new and emerging applications of nitrogen-rich energetic materials such as in computational chemistry Discusses recent advances in nitrate ester chemistry with focus on propellant applications Discusses green and eco-friendly approaches to nitrogen-rich compounds Nitrogen-Rich Energetic Materials is an important resource for researchers, academics, and industry professionals across fields, including explosives specialists, pyrotechnicians, materials scientists, polymer chemists, laser specialists, physical chemists, environmental chemists, chemical engineers, and safety officers. Cover Half Title Nitrogen-Rich Energetic Materials Copyright Contents Preface About the Editors 1. Chemistry of Pentazole 1.1 Introduction 1.2. Substituted Pentazoles 1.3 Strategies for the Preparation of cyclo‐N5− 1.3.1 Using High‐Energy Electrons to Cleave the CN Bond in ArN5 1.3.2 Cleaving the CN Bond of ArN5 Using Redox Chemistry 1.3.3 Possible [3+2] Reaction of N3− and N2 at High Pressure 1.4 Complexes of Metal and cyclo‐N5− 1.4.1 Metal Salts of cyclo‐N5− (0D) 1.4.2 Metal–Inorganic Frameworks (MIFs) of cyclo‐N5− 1.4.3 Coordination Polymers 1.4.4 Structural Characterization 1.4.4.1 MS and NMR Characterization 1.4.4.2 Topology Analysis 1.4.4.3 Raman and IR Analysis 1.4.4.4 Stability Analysis 1.4.4.5 Bonding Study 1.4.4.6 Detonation Properties 1.5 cyclo‐N5−‐Based Nonmetallic Ionic Salts 1.5.1 Synthesis 1.5.2 Single‐Crystal X‐Ray Structures 1.5.3 Properties 1.5.3.1 15N NMR 1.5.3.2 IR Spectrum 1.5.3.3 Thermal Stability 1.5.3.4 Sensitivity 1.5.3.5 Density 1.5.3.6 Heat of Formation and Detonation Performance 1.6 Conclusions References 2. Aromatic Fused‐Ring‐Based Energetic Compounds 2.1 Introduction 2.2 Fused‐Ring Aromatic Energetic Compounds 2.2.1 [5,5]‐Bicyclic‐Backbone‐Based Energetic Compounds 2.2.2 [5,6]‐Bicyclic Energetic Compounds 2.2.3 Other Multicyclic Energetic Compounds 2.3 Conclusions References 3. Advances in Computations of Nitrogen‐Rich Materials 3.1 Why Computation and What Role It Plays? 3.2 Why Nitrogen‐Rich HEDMs and How They Work? 3.3 Advances in Computation of First‐Generation Nitrogen‐Rich HEDMs 3.4 Advances in Computation of Second‐Generation Nitrogen‐Rich HEDMs 3.5 Advances in Computation of Third‐Generation Nitrogen‐Rich HEDMs: Polynitrogen Materials 3.5.1 Nitrogen‐Rich HEDMs Composed of N3+ 3.5.2 Nitrogen‐Rich HEDMs Composed of N5+ 3.5.3 Nitrogen‐Rich HEDMs Composed of cyclo‐N5− 3.5.3.1 Synthesis and Related Mechanism at Ambient and High Pressures 3.5.3.2 Pentazole Compounds with Non‐nitrogen Stabilizer 3.5.3.3 Argument on the Protonation of cyclo‐N5− in (N5)6(H3O)3(NH4)4Cl 3.5.3.4 Stabilization Mechanism of Dual‐Aromatic cyclo‐N5− 3.5.4 All‐Nitrogen Cluster N4 3.5.5 All‐Nitrogen Cluster N6 3.5.6 All‐Nitrogen Crystals Composed of N8 3.5.7 All‐Nitrogen Crystals Composed of N10 3.5.8 All‐Nitrogen HEDMs with Cubic Gauche Structure 3.6 Final Remarks Acknowledgement References 4. Laser Ignition of Energetic Transition Metal Complexes 4.1 Introduction 4.2 Synthesis of Energetic Coordination Compounds 4.3 Synthesis of Energetic Tetrazole Ligands 4.4 Synthesis Energetic Coordination Complexes 4.5 Examples of Molecular Structures 4.6 Energetic Properties of Ligands and Corresponding Energetic Coordination Compounds 4.7 UV–Vis Spectroscopy of Energetic Coordination Compounds 4.8 Studies of Ignition Mechanism 4.9 Conclusions References 5. Energetic 1,2,3,4‐Tetrazines 5.1 Introduction 5.2 Methods of Synthesis and Reactivity of 1,2,3,4‐Tetrazines 5.2.1 1,2,3,4‐Tetrazines with Carbon Substituents at Nitrogen Atoms 5.2.2 Annulated 1,2,3,4‐Tetrazines with Bridgehead Nitrogen Atoms 5.2.3 Fully Unsaturated 1,2,3,4‐Tetrazines 5.2.3.1 Annulated 1,2,3,4‐Tetrazines 5.2.3.2 1,2,3,4‐Tetrazine 1‐Oxides and Benzotetrazine 1‐Oxides 5.2.3.3 1,2,3,4‐Tetrazine 1,3‐Dioxides 5.3 NMR and X‐ray Studies 5.4 Thermal Stability 5.4.1 Theoretical Stability 5.4.2 Heat Resistance 5.4.2.1 Non‐annulated 1,2,3,4‐Tetrazine 1,3‐Dioxides (TDOs) 5.4.2.2 Benzo‐1,2,3,4‐Tetrazine 1,3‐Dioxides (BTDOs) 5.4.2.3 BTDOs Annulated with TDO Ring 5.4.2.4 BTDOs Annulated with Tetraazapentalene System 5.4.2.5 BTDOs Annulated with Furoxan Ring 5.4.2.6 Tetrazine‐1,3‐Dioxides (TDOs) Annulated with Five‐Membered Heterocycles 5.4.2.7 TDOs Annulated with Tetraazapentalene Systems 5.4.2.8 TDO Annulated with Six‐Membered Heterocycle 5.4.2.9 1,2,3,4‐Tetrazines with Two Bridgehead Nitrogen Atoms 5.5 Applications References 6. Recent Advances in Chemistry of Nitrogen‐Rich Energetic Polymers and Plasticizers 6.1 Introduction 6.2 Heterocyclic Energetic Polymers and Plasticizers 6.3 Nitrogen‐Rich Energetic Polymers Lacking Traditional Explosophoric Groups 6.4 Azido‐Rich Energetic Polymers and Plasticizers 6.5 Azido Fluoropolymers 6.6 Azido Plasticizers 6.7 Nitro Group Containing Polymers 6.8 Aromatic C‐NO2 Containing Polymers 6.9 Conclusions References 7. Tetrazole Energetic Salts Based on Various Explosophores: Recent Overview of Synthesis and Energetic Properties 7.1 Introduction 7.2 Tetrazole‐Based Energetic Salts 7.2.1 Synthesis of Nitro, Nitramino, or Azido Tetrazole Energetic Salts 7.2.2 Synthesis of Amino/Hydrazine‐Tetrazole Energetic Salts 7.2.3 Synthesis of Tetrazole N‐oxide Energetic Salts 7.2.4 Synthesis of Bistetrazole or Bridged Bistetrazole Energetic Salts 7.3 Conclusion and Future Trends 7.4 Cautions Acknowledgments References 8. Properties and Application of Nitrogen‐Rich Compound BTATz in Low‐Signature Propellants 8.1 Introduction 8.2 Synthesis of BTATz 8.2.1 Experimental 8.2.2 Synthesis of 3,6‐Bis(3,5‐Dimethylpyrazole)‐1,2‐Dihydro‐1,2,4,5‐Tetrazine (3) 8.2.3 Synthesis of 3,6‐Bis(3,5‐Dimethylpyrazole)‐1,2,4,5‐Tetrazine (4) 8.2.4 Synthesis of BTATz (5) 8.3 Structure of BTATz 8.3.1 Geometric Configuration 8.3.2 Bond Orders 8.3.3 Vibration and Infrared Spectrum 8.4 Properties of BTATz 8.4.1 Energy Properties of BTATz and Other Energetic Compounds 8.4.2 Physicochemical Properties Detected for BTATz 8.5 Energetic Properties of the Propellants 8.6 Plume Smoke Signature of the Propellants 8.7 Preparation of the Propellants 8.7.1 BTATz–CMDB Propellants in DINA System 8.7.2 BTATz–HNIW–CMDB Propellants in DIANP System 8.8 Decomposition Reaction Kinetics and Thermal Safety of the Propellants 8.8.1 BTATz–CMDB Propellants in DINA System 8.8.1.1 Conditions for Thermal Decomposition Reaction 8.8.1.2 Thermal Behavior 8.8.1.3 Nonisothermal Reaction Kinetics 8.8.1.4 Thermal Safety 8.8.2 BTATz–HNIW–CMDB Propellants in DIANP System 8.8.2.1 Conditions for Thermal Decomposition Reaction 8.8.2.2 Thermal Behavior 8.8.2.3 Nonisothermal Reaction Kinetics 8.8.2.4 Thermal Safety 8.9 Combustion Properties of the Propellants 8.9.1 BTATz–CMDB Propellants in DINA System 8.9.1.1 Burning Rate Properties 8.9.1.2 Structures of Combustion Flames and Quenched Surfaces 8.9.2 BTATz–HNIW–CMDB Propellants in DIANP System 8.9.2.1 Burning Rate Properties 8.9.2.2 Structures of Combustion Flames and Quenched Surfaces 8.10 Correlation Between PDSC Characteristic Values and Burning Rates 8.11 Conclusions References 9. Nitro‐substituted Oxadiazoles: Important Building Blocks in the Synthesis of Energetic Compounds 9.1 Introduction 9.2 Enthalpy of Formation of Oxadiazoles 9.3 1,2,4‐Oxadiazoles 9.4 1,3,4‐Oxadiazoles 9.5 Furazans (1,2,5‐Oxadiazole) and Furoxans (1,2,5‐Oxadiazole‐2‐Oxides) 9.6 Summary Abbreviations References 10. Insensitive High Explosives Containing Tetraazapentalene Moiety 10.1 Introduction 10.2 Synthesis of TACOT Derivatives 10.3 Crystal and Molecular Structure 10.4 Spectroscopy 10.4.1 NMR Spectroscopy 10.5 Thermochemistry 10.6 Detonation Performance 10.7 Thermal Behavior 10.8 Sensitivity 10.9 Conclusions Acknowledgments References 11. Nitrogen‐Rich Pyrotechnic Materials for Light and Smoke 11.1 Light‐Generating Pyrotechnics 11.2 Smokes 11.2.1 White Smoke 11.2.2 Colored Smoke Acknowledgments References Index